Solvothermal Construction of ZIF-8/MnS Z-Scheme Heterojunctions for Enhanced Photocatalytic Degradation of Organic Dyes

Solvothermal Construction of ZIF-8/MnS Z-Scheme Heterojunctions for Enhanced Photocatalytic Degradation of Organic Dyes | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Solvothermal Construction of ZIF-8/MnS Z-Scheme Heterojunctions for Enhanced Photocatalytic Degradation of Organic Dyes min Zhou, Yancheng Wu, Wenbo Zhang, Xiaofang Li, Xiaoqiang Feng This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-9420342/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract The construction of heterojunctions is a proven method to improve photocatalytic efficiency. Herein, a series of ZIF-8/MnS composites were synthesized and thoroughly characterized. The photocatalytic degradation performance was evaluated under UV irradiation using Congo red (CR) as a model pollutant. The optimized ZIF-8/MnS composite with a Zn:Mn ratio of 10:3 displayed exceptional photocatalytic efficacy, degrading 99.4% of CR within 30 minutes under UV irradiation, surpassing the individual performances of pristine ZIF-8 and MnS. This superior activity is ascribed to the heterojunction interface established between ZIF-8 and MnS, which facilitates efficient charge carrier separation and migration. Through radical trapping experiments, it was determined that ·O₂⁻ and h⁺ are the predominant active species, underscoring the potential of ZIF-8/MnS heterojunctions for effective photocatalytic treatment of wastewater. The work provides important insights for designing efficient MOF-based photocatalysts. ZIF-8/MnS Photocatalytic degradation Congo red Mechanism Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 1 Introduction Large volume of wastewater are discharged into water bodies as a result of industrial development, polluting water resources and the environment while posing serious threats to human health. Organic dyes are common water pollutants classified into anionic, cationic, and non-ionic categories based on their chemical properties [ 1 ]. Organic dyes wastewater is characterized by high concentration, complex composition, high chroma, low biodegradability, and large discharge volumes. Moreover, these effluents often contain toxic compounds that severely threaten aquatic organisms and the ecological environment [ 2 , 3 ]. Conventional treatment methods primarily include biodegradation [ 4 ], chemical oxidation [ 5 ], photocatalytic oxidation [ 6 ], physical adsorption [ 7 , 8 ], ion exchange, coagulation, and electrochemical methods [ 9 – 12 ]. Unfortunately, most of these methods fall short of achieving full mineralization of persistent dyes, frequently resulting in secondary contamination [ 13 – 16 ]. As a promising green purification technology, photocatalysis offers significant potential because of its minimal energy usage, gentle reaction parameters, and capability to entirely mineralize organic contaminants into CO₂ and water [ 17 ]. Metal-organic frameworks (MOFs) are crystalline porous materials constructed from metal nodes and organic linkers that self-assemble into periodic architectures [ 18 , 19 ]. Their exceptional porosity, tunable structures, and abundant active sites make them promising candidates for photocatalytic applications. Among MOFs, zeolitic imidazolate framework-8(ZIF-8) has attracted significant interest owing to its sodalite topology, comprising Zn²⁺ ions tetrahedrally coordinated by 2-methylimidazolate ligands [ 20 , 21 ]. This unique structure confers exceptional thermal and chemical stability, a large surface area, and enduring microporosity [ 22 – 24 ], rendering it highly effective for pollutant adsorption and photocatalytic degradation. However, the photocatalytic activity of ZIF-8 is hindered by its high recombination rate of photogenerated carriers and limited visible light absorption capacity. Manganese sulfide (MnS) has attracted considerable interest in photocatalysis due to its high redox activity and visible-light response. Nevertheless, practical applications of MnS are hindered by its susceptibility to photocorrosion, low carrier mobility, and rapid charge recombination [ 25 , 26 ]. Recent studies demonstrate that coupling MnS with semiconductors possessing suitable band structures can mitigate these drawbacks and enhance light utilization efficiency [ 27 ]. Based on the band structures of ZIF-8 and MnS, ZIF-8/MnS composites are expected to construct a heterojunction that fully leverages the advantages of both components, promotes photogenerated carrier separation, and thereby enhances the photocatalytic degradation efficiency of organic pollutants. In the present work, ZIF-8/MnS composites were prepared via an in-situ growth method, and the photocatalytic enhancement mechanism was elucidated through systematic characterization and performance evaluation. Experimental results demonstrate that the optimized ZIF-8/MnS (Zn:Mn = 10:3) sample exhibits excellent degradation performance under UV light, with the performance enhancement attributed to an extended photoresponse range, efficient charge separation, and abundant surface active sites. The work provides important insights for designing efficient MOF-based photocatalysts. 2 Experimental 2.1 Materials 2-methylimidazole (C 4 H 6 N 2 ), zinc acetate ( Zn(Ac) 2 ·2H 2 O), manganese chloride (MnCl 2 ·4H 2 O), thiourea (CH 4 N 2 S), Congo red (CR), methanol, 1,4-benzoquinone (BQ), isopropanol (IPA), and ethylenediaminetetraacetic acid disodium salt (EDTA), and ethanol were all analytical grade and obtained from Xilong Scientific. All the chemicals were analytical grade and used without purification. 2.2 Synthesis of ZIF-8 ZIF-8 was synthesized based on a reported procedure with slight modifications [ 28 ]. 0.02 moles of Zn (Ac)₂·2H₂O were dissolved in 30 mL of methanol via sonication to create solution A. Simultaneously, 0.08 moles of 2-methylimidazole were dissolved in 30 mL of distilled water through sonication to produce solution B. Solution B was then gradually introduced into solution A while stirring continuously at room temperature. Following 1 hour of stirring, the mixture was moved to a polytetrafluoroethylene-lined autoclave and heated at 120°C for 24 h. After cooling to room temperature, the resulting product was gathered through vacuum filtration, washed iteratively with methanol and distilled water, and ultimately vacuum-dried at 60°C for 12 h to yield the ZIF-8 sample. 2.3 Synthesis of MnS MnCl₂·4H₂O (0.05 mol) was dissolved in 30 mL of water through sonication. Thiourea (0.05 mol) was separately dissolved in 30 mL of distilled water using sonication. Subsequently, the thiourea solution was carefully introduced into the manganese chloride solution at room temperature with stirring. After 1 h, the mixture was transferred to a polytetrafluoroethylene-lined autoclave and heated at 180°C for 24 h. Upon cooling, the product was collected by centrifugation, washed repeatedly with ethanol and distilled water, and vacuum-dried at 60°C for 12 h to afford the MnS sample. 2.4 Synthesis of ZIF-8/MnS photocatalysts Composites of ZIF-8/MnS were synthesized using an in-situ growth approach. In Fig. 1 a, the preparation involved dissolving 20.0 mmol of Zn(Ac)₂·2H₂O and 2.00 mmol of MnCl₂·4H₂O in 30 mL of methanol to create a metal salt solution. Simultaneously, a ligand solution was prepared by dissolving 2-methylimidazole (80.0 mmol) and thiourea (2.00 mmol) in 30 mL distilled water. The ligand solution was then slowly added to the metal salt solution at room temperature with continuous stirring. After 1 h, the mixture was transferred to a polytetrafluoroethylene-lined autoclave and was heated at 120°C for 24 h. Following cooling to room temperature, the product underwent collection by centrifugation, multiple washings with methanol and distilled water, and vacuum drying at 60°C for 12 h, resulting in the production of ZIF-8/MnS-1 (Zn²⁺:Mn²⁺=10:1). Composites with different MnS loadings (ZIF-8/MnS-2, ZIF-8/MnS-3, and ZIF-8/MnS-4) were prepared similarly by adjusting the manganese chloride and thiourea amounts while keeping other conditions constant. 2.5 Characterization XRD patterns were collected on a Shimadzu XRD-6100 diffractometer (Cu Kα radiation, λ = 0.15418 nm, 40 kV, 40 mA) over 2θ = 5–80°. FTIR spectra were recorded on a PerkinElmer Spectrum 100 spectrometer (4000–400 cm⁻¹). Surface morphology was observed via FE-SEM (JEOL JSM-7100, Japan) with EDS (Oxford Instruments). UV–vis DRS were obtained on a Shimadzu UV-3600 spectrophotometer (200–900 nm). XPS (Thermo Scientific Escalab 250Xi) determined elemental composition and valence states. BET surface areas were measured using N₂ adsorption–desorption at 77 K (Micromeritics Tristar ASAP 3000). PL spectra were recorded at room temperature on a Shimadzu RF-5301 PC spectrophotometer (Japan) with λ ex = 350 nm. Photoelectrochemical tests (LSV, CV, TPR, EIS, and M–S) were performed on a CEL-QPCE3000 workstation (Beijing Zhongjiao Jinyuan Technology) in 0.1 M Na₂SO₄ using a three-electrode configuration with a sample-coated FTO glass working electrode (1 cm × 1 cm), a carbon rod counter electrode, and an Ag/AgCl reference electrode. A 300 W Xe lamp provided chopped illumination for transient photocurrent measurements. 2.6 Photocatalytic activity measurements CR was selected as the model pollutant for photocatalytic degradation experiments under UV irradiation. In a standard procedure, 15 mg of the photocatalyst was dispersed in 30 mL of a CR solution (20 mg/L) and stirred magnetically in the dark for 30 minutes to reach adsorption-desorption equilibrium. Subsequently, the suspension was irradiated with a 300 W UV lamp at 20°C. At predetermined time intervals, 3 mL of the sample was collected and centrifuged. The absorbance of the supernatant was then measured at 496 nm using a UV–vis spectrophotometer. Degradation efficiency (De,%) was calculated according to the following formula: De % = (A 0 - A t )/ A 0 × 100% = (C 0 - C t )/ C 0 × 100% where A₀ and Aₜ are the initial and time-dependent absorbance values of CR, respectively, and C₀ and Cₜ indicate the corresponding initial and time-dependent concentrations. 3 Results and discussion 3.1 Structural characterization XRD patterns (Fig. 1 b) confirm that pure MnS consists of mixed γ-MnS (hexagonal, PDF#89-4089) and α-MnS (cubic, PDF#06-0518) phases. Peaks at 25.78°, 27.69°, 45.46°, and 50.00° correspond to γ-MnS (100), (002), (110), and (103) planes, while peaks at 34.30°, 49.30°, and 61.39° can be indexed to α-MnS (200), (220), and (222) planes. In ZIF-8/MnS composites, MnS diffraction peaks partially overlap with those of ZIF-8. However, increasing Mn content progressively attenuates ZIF-8 peak intensities, while MnS peaks exhibit slight shifts attributed to enhanced surface loading and interfacial strain. Higher Mn loading expands the heterojunction, increasing lattice distortion and interfacial defects, thereby reducing ZIF-8 crystallinity [ 30 ]. No unattributed diffraction peaks were observed, indicating ZIF-8 and MnS did not react chemically to form new phases [ 31 ]. XRD confirms all composites were successfully prepared as phase-pure materials with the desired crystal structure. FTIR spectra (Fig. 1 c) show weak MnS signals. Broad peaks at 3200–3500 cm⁻¹ correspond to O-H stretching of adsorbed water [ 32 ]. ZIF-8 displays characteristic bands at 3134 and 2929 cm⁻¹ (C-H stretching) [ 33 ], 1445 cm⁻¹ (C = N stretching), 1350–950 cm⁻¹ (in-plane imidazole vibrations), 760 cm⁻¹ (out-of-plane imidazole bending), and 420 cm⁻¹ (Zn-N stretching) [ 34 ]. The ZIF-8/MnS composites retain these core features, though altered peak intensities and shapes indicate MnS modifies the ZIF-8 vibrational environment without destroying its framework. SEM analysis reveals MnS (Fig. 2 a-b) as irregular, rough aggregates of low crystallinity. ZIF-8 (Fig. 2 c-d) exhibits uniformly sized, well-dispersed polyhedral nanocrystals typical of its zeolitic imidazolate framework. In the ZIF-8/MnS composite (Fig. 2 e-f), small spherical MnS particles are deposited on ZIF-8 surfaces and within interstitial spaces. While the ZIF-8 framework is preserved, increased surface roughness confirms successful heterogeneous composite formation. EDS mapping (Fig. 2 g) confirms the presence of C, N, S, Mn, and Zn, verifying successful ZIF-8/MnS composite synthesis. XPS analysis (Fig. 3 a) is conducted to examine the surface chemical composition of ZIF-8/MnS composites, verifying the existence of Zn, N, O, C, Mn, and S. In the Zn 2p region (Fig. 3 b), the spectrum exhibits spin-orbit doublet peaks at 1021.55 eV (2p₃/₂) and 1044.61 eV (2p₁/₂), consistent with Zn²⁺ in the framework structure of ZIF-8. The N 1s spectrum (Fig. 3 c) can be deconvoluted into two components at 399.20 eV (Zn-N) and 398.56 eV (C-N), corresponding to nitrogen coordination within the imidazolate linker. The O 1s spectrum (Fig. 3 d) shows three distinct peaks at 530.35 eV (Zn-O), 531.35 eV (C-O), and 532.17 eV (O-H), which align well with literature-reported values for ZIF-8 [ 35 – 37 ]. The C 1s spectrum (Fig. 3 e) reveals three characteristic peaks at 284.38 eV (sp² C), 284.99 eV (C = N), and 285.72 eV (C = O) [ 38 , 39 ]. Notably, the Mn 2p spectrum (Fig. 3 f) displays Mn²⁺ spin-orbit doublets at 641.06 eV (2p₃/₂) and 653.80 eV (2p₁/₂), accompanied by characteristic satellite peaks at 643.09 eV and 656.10 eV that confirm the formation of MnS [ 40 , 41 ]. The S 2p spectrum (Fig. 3 g) reveals two peaks at 161.31 eV (2p₃/₂) and 162.57 eV (2p₁/₂), corresponding to S²⁻ species in MnS [ 42 ]. N 2 adsorption-desorption measurements were conducted to assess the textural characteristics of ZIF-8, MnS, and the ZIF-8/MnS-3 composite (Fig. 4 and Table 1). ZIF-8 displays a Type I isotherm, indicating a microporous nature, along with a substantial Brunauer-Emmett-Teller (BET) surface area of 1449.68 m²/g and a significant pore volume of 0.6661 cm³/g, which offer ample catalytic reaction sites. In contrast, MnS displays a Type IV isotherm, indicative of a mesoporous structure; however, its surface area (2.67 m²/g) and pore volume (0.0034 cm³/g) are drastically lower, severely limiting active site availability and consequently impairing photocatalytic performance. The ZIF-8/MnS composite shows a hybrid Type I + IV isotherm, confirming a hierarchical micro-mesoporous architecture. It retains a substantial surface area (553.05 m²/g) and pore volume (0.2577 cm³/g) with an expanded average pore size (17.36 nm). This hierarchical structure enhances light harvesting efficiency by increasing the accessible surface area and exposing more photoactive sites. Additionally, it facilitates the separation of photogenerated charge carriers and promotes rapid mass transfer. Consequently, the synergistic combination of enriched active sites and improved diffusion kinetics significantly boosts the photocatalytic reaction rate and overall removal efficiency. Table 1 BET parameters of ZIF-8, MnS and ZIF-8/MnS-3 Sample S BET (m 2 /g) Pore volume(cm 3 /g) Average pore size (nm) ZIF-8 1449.6770 0.666053 10.4403 MnS 2.6699 0.003424 16.9619 ZIF-8/MnS 553.0454 0.257692 17.3626 3.2. Photocatalytic performance CR is a classic diazo anionic dye with a molecular structure centered on a linear planar aromatic skeleton, containing two azo chromophores (-N = N-) and a sulfonic acid group (-SO₃Na). This structural feature endows it with high stability and recalcitrance to degradation [ 43 ]. As depicted in Fig. 5 a, the self-degradation rate of CR is insignificant. Pure ZIF-8, leveraging its high specific surface area and porous structure that efficiently accumulate CR molecules via π-π stacking and electrostatic interactions [ 44 – 46 ], attains a CR degradation rate of 72.3%. Upon compositing with MnS, the ZIF-8/MnS composite photocatalyst exhibits further enhanced adsorption and photocatalytic performance, with ZIF-8/MnS-3 showing optimal activity by almost completely removing CR from aqueous solution within 30 min. This is attributed to the heterojunction structure formed between ZIF-8 and MnS, which not only fully exploits the synergistic enhancement effect of both components, promoting effective coupling of substrate enrichment and catalytic sites, but also accelerates photogenerated charge carrier separation through matched energy level structures, thereby significantly improving the yield of reactive oxygen species [ 47 ]. Photocatalytic degradation of organic pollutants typically follows first-order kinetics, as articulated by the Langmuir-Hinshelwood model (ln(C₀/Cₜ) = k t), where C₀ and Cₜ denote the initial concentration and concentration at time t, respectively, and k signifies the apparent rate constant (min⁻¹) derived from the gradient of ln(C₀/Cₜ) versus t [ 48 ]. A greater k value typically signifies enhanced photocatalytic efficacy [ 49 ]. As shown in Fig. 5 b, the k value for CR degradation by ZIF-8/MnS-3 is approximately 3.61 and 11.46 times those of pure ZIF-8 and MnS, respectively. Furthermore, the photocatalytic performance exhibits a volcano-shaped trend with increasing Mn content, which indicates that excessive Mn has an adverse effect on the generation and separation of photogenerated electron-hole pairs. Catalyst dosage critically affects both efficiency and cost in practical applications. As shown in Fig. 5 c, the ZIF-8/MnS system exhibits optimal CR degradation at 0.5 mg/mL. Degradation efficiency initially increased with dosage (0.25–2 mg/mL) due to more active sites [ 50 , 51 ], but declined at higher concentrations from reduced light utilization [ 52 ]. This optimal dosage effectively balances catalytic performance with material cost. Figure 5 d shows degradation efficiency decreases with increasing initial CR concentration [ 53 ], dropping from 99.4% to 67.0% within 50 minutes as concentration rises from 10 to 50 mg/L. This decline results from active site saturation and reduced photon penetration at high dye loadings [ 54 , 55 ]. During the 30-minute dark adsorption stage, C/C₀ remained near 0.93 across all concentrations, indicating negligible adsorption. The catalyst-free control showed no significant C/C₀ change, confirming CR degradation is entirely photocatalyst-mediated. In natural water systems, coexisting anions significantly influence photocatalytic oxidation. We investigated the effects of five common anions (Cl⁻, SO₄²⁻, CO₃²⁻, HCO₃⁻, NO₂⁻) on the ZIF-8/MnS system (Fig. 5 e). Chloride enhances oxidation by reacting with sulfate radicals and •OH to generate chlorine radicals [ 56 , 57 ], while sulfate improves degradation efficiency through its intrinsic oxidizing capability toward pollutants [ 58 ]. Nitrite exhibits a modest accelerating effect. Conversely, carbonate and bicarbonate markedly suppress photodegradation by acting as potent •OH scavengers [ 59 , 60 ] and competing with anionic CR for positively charged adsorption sites [ 61 ]. Table 2 compares the catalytic activity of ZIF-8/MnS for dye degradation with recently reported ZIF-8-based composites. For practical applications, photocatalyst stability is crucial. The reusability of ZIF-8/MnS-3 was evaluated through four consecutive cycles under identical conditions. As shown in Fig. 5 f, the CR rate of degradation has fallen to 70.6% in the fourth cycle—a 28.8% reduction from the first cycle—this is a result of the loss of catalyst during the recovery process, as well as surface passivation by degradation intermediates that have accumulated. Despite this moderate decline, the composite demonstrates appreciable stability and sustained photocatalytic activity, as corroborated by post-cycling XRD and SEM (Fig. S1 ) analyses that revealed no significant structural or morphological alterations. Catalysts Pollutants Experimental conditions Degradation (%) Light source Time (min) Reference MnS/ZnO TC 97.8 300W Xe lamp (λ > 400 nm) 100 30 ZIF-8@NH 2 -MIL-125 TCH 92.9 visible LED light UVC lamps (TUV Philips, 15 W) 100 35 AgNPs/Ag 2 S/ZIF-8 MG 98.6 visible LED light 50 62 CdZnS@ ZIF − 8 MB 99.5 visible light 90 63 ZIF-8/NiFe 2 O 4 MB 94 500 W halogen lamp 120 64 ZIF-8 derived ZnO MB 76 UV lamp/18 W 60 65 MoO 3 @ZIF-8 MB 95 PL-XQ 350 W xenon 300 66 Ag/AgCl@ZIF-8 MB 100 Hg lamp/175 W 90 67 CdSNPs@ZIF-8 MB 83.2 UV-visible 120 68 ZIF-8/Zn-Al LDH MB 58 UV light/70 W 180 69 ZIF-8@TiO 2 (0.3% Gd) neutral red dye 96.55 UV 60 70 Ag/AgCl@ZIF-8 RhB 99.12 500W Xe lamp(λ > 400 nm) 60 71 CuONPs/ZIF-8 Rh6G 96.5 Sunlight 105 72 ZIF-8/g-C 3 N 4 RhB 99.8 Xe lamp/300 W 60 73 ZIF-8/Ag 2 S RhB 100 100 W Xe and 100 W LED 75 74 CuO-ZnO/ZiF-8 AO7 98.1 Solar light 100 75 ZIF-8/MnS CR 99.4 UV light 30 this work 3.3 Photocatalytic mechanism Photoluminescence (PL) spectroscopy at 320 nm excitation is used to evaluate photogenerated carrier separation efficiency. In general, PL intensity is inversely related to the rate of carrier separation and directly proportional to the recombination rate [ 76 – 78 ]. Figure 6 a shows emission peaks near 420 nm for all photocatalysts. ZIF-8/MnS composites exhibit lower peak intensity than ZIF-8, indicating suppressed carrier recombination and enhanced separation. ZIF-8/MnS-4 shows the lowest intensity, suggesting optimal interfacial interaction between ZIF-8 and MnS that most effectively inhibits recombination, thereby maximizing active species generation and photocatalytic performance. The investigation into charge separation and transfer in ZIF-8/MnS photocatalysts is conducted through the utilisation of two analytical techniques: transient photocurrent response (TPR) and electrochemical impedance spectroscopy (EIS). It can be posited that an enhanced photocurrent is indicative of an optimised carrier separation efficiency [ 79 ]. Figure 6 b shows ZIF-8/MnS composites exhibit enhanced photocurrent compared to pristine ZIF-8, demonstrating MnS incorporation accelerates charge separation and extends carrier lifetime. EIS Nyquist plots (Fig. 6 c) reveal arc radius corresponds to charge transfer resistance (Rct) [ 80 , 81 ]. ZIF-8 displays the largest radius, while ZIF-8/MnS composites showed composition-dependent decreases, indicating improved charge mobility. Linear sweep voltammetry (LSV) (Fig. 6 d) confirms reduced electron transfer resistance and suppressed recombination [ 82 ]. The cyclic voltammetry (CV) curve (Fig. 6 e) shows the ZIF-8/MnS composite's current density is between those of pure MnS and ZIF-8, indicating the heterostructure inherits combined electrochemical properties. The electrochemical double-layer capacitance (C dl ), measured by cyclic voltammetry (Fig. 6 f), reflects the electrochemically active surface area. Furthermore, ZIF-8/MnS-3 exhibits a C dl of 4.5737 mF/cm², which is 182 times that of ZIF-8 (0.0251 mF/cm²), indicating substantially more accessible active sites and enhanced photocatalytic performance. An exhaustive analysis of the optical response characteristics of ZF-8, MnS and ZF-8/MnS is conducted by means of diffuse reflectance spectroscopy (DRS) spectroscopy. As shown in Fig. 7 a, ZIF-8 exhibits UV absorption only below 259 nm, with a negligible visible-light response. MnS absorbs strongly in both UV and visible regions. The ZIF-8/MnS composites show red-shifted absorption edges and enhanced light-harvesting capacity compared to pristine ZIF-8. It is generally that it has been demonstrated that the photocatalytic performance of a material is contingent upon the width of its absorption range in relation to the narrowness of its band gap [ 83 ], indicating that the introduction of MnS in ZIF-8 could enhance the photocatalytic activity. Band gap energies (E g ) were determined from Tauc plots (Fig. 7 b): ZIF-8 (5.12 eV), MnS (3.66 eV), and the ZIF-8/MnS1-4 composites are 5.01 eV, 4.94 eV, 3.37 eV, and 3.31 eV, respectively. The progressive band gap narrowing with increasing MnS content demonstrates tunable electronic structure. This heterojunction architecture simultaneously broadens the spectral response range and reduces the band gap, synergistically enhancing photocatalytic efficiency. Semiconductor type and flat-band potentials (E fb ) were determined by Mott-Schottky (M-S) analysis. As shown in Figs. 7 c-d ZIF-8 exhibits n-type behaviour, as indicated by a positive slope, while MnS demonstrates p-type characteristics, as evidenced by a negative slope [ 84 ]. The E fb values for ZIF-8 and MnS were − 1.75 and 1.05 V (vs. Ag/AgCl), respectively. The band structure was calculated using the following equation. E NHE = E Ag/AgCl + 0.2 V (1) E VB = E g + E CB (2) As per formula 1, the flat-band potentials of ZIF-8 and MnS were computed as -1.55 and 1.25 V (vs. NHE) correspondingly, employing Eq. (1). For n-type semiconductors, E fb is typically ~ 0.1 eV above the conduction band edge (E CB ) [ 85 ], for p-type, E fb is ~ 0.1 eV below the valence band edge (E VB ) [ 86 ]. Thus, the E CB of ZIF-8 is -1.65 V (vs. NHE), and the E VB of MnS is 1.35 V (vs. NHE). Given band gap energies (E g ) of 5.12 eV for ZIF-8 and 3.66 eV for MnS, Eq. (2) yields an E VB of 3.47 V vs. NHE for ZIF-8 and an E CB of -2.31 V vs. NHE for MnS. Density functional theory (DFT) calculations reveal HOMO-LUMO gaps of 4.67 eV for the ZIF-8 characteristic cluster model and 3.13 eV for the MnS unit cell model (Table 3 ), which agrees well with experimental UV-Vis DRS data. This validates our computational approach and its ability to capture the electronic structure of these materials. Orbital distribution analysis (Fig. 8 a) shows that the HOMO of ZIF-8 is localized on the imidazole ligands, while the LUMO resides at the Zn-N cluster center, indicating directional ligand-to-metal charge transfer upon photoexcitation. For MnS, both HOMO and LUMO arise primarily from Mn 3d and S 3p orbitals, exhibiting strong spatial localization that may hinder photogenerated carrier separation and mobility. Electrostatic potential mapping (Fig. 8 b) identifies negative potential extrema (in red) around the imidazole nitrogen atoms in ZIF-8, which can electrostatically adsorb cationic pollutants and facilitate interfacial electron transfer. In the ZIF-8/MnS heterojunction, this complementary potential distribution drives directional migration of photogenerated electrons from ZIF-8 to MnS while promoting hole transfer in the opposite direction. This charge transfer pathway aligns perfectly with the proposed Z-scheme mechanism. DFT results thus provide direct theoretical evidence for the matched band structure and favorable interfacial charge distribution in the Z-type ZIF-8/MnS heterojunction. Table 3 Frontier orbital energy levels and band gaps of ZIF-8 cluster and MnS unit cell Sample HOMO (eV) LUMO (eV) Band gap (eV) ZIF-8 -6.44 -1.77 4.67 MnS -4.99 -1.86 3.13 The active species governing CR photodegradation were identified through scavenging experiments using 2 mmol of BQ, IPA, and EDTA as traps for •O₂⁻, •OH, and h⁺, respectively [ 87 , 88 ]. As shown in Fig. 8 c, It is evident that EDTA and BQ exhibit a substantial inhibitory effect on the degradation efficiency, while IPA showed only weak suppression, establishing the h⁺ and •O₂⁻ as the primary reactive species. Based on band alignment and scavenger experiments, a direct Z-scheme mechanism is proposed (Fig. 9). Under simulated sunlight irradiation, electrons in both ZIF-8 and MnS are excited from their valence bands (VB) to conduction bands (CB). Driven by the interfacial band potential gradient, electrons in the ZIF-8 CB spontaneously transfer to the MnS VB and recombine with holes there, achieving directional charge separation. This Z-scheme preserves highly reductive electrons in the MnS CB and strongly oxidative holes in the ZIF-8 VB. Subsequently, MnS CB electrons reduce O₂ to •O₂⁻ (E θ (O₂/•O₂⁻) = -0.33 V vs. NHE), while ZIF-8 VB holes oxidize H₂O (or OH⁻) to •OH (E θ (H₂O/•OH) = +2.27 V vs. NHE). These reactive species, together with MnS VB holes that directly oxidize CR, initiate a cascade degradation process that generates short-chain intermediates en route to complete mineralization into CO₂ and H₂O. By suppressing charge recombination and maintaining robust redox potentials, this Z-scheme architecture significantly enhances degradation efficiency. The proposed photocatalytic degradation pathway proceeds as follows: ZIF-8 + h n ® ZIF-8 (h + ) + ZIF-8 (e - ) MnS + h n ® MnS (h + ) + MnS (e - ) ZIF-8 (e - ) + MnS (h + ) ® ZIF-8/MnS(e - + h + ) MnS (e - ) + O 2 ® •O₂⁻ ZIF-8 (h + ) + H 2 O/OH - ® •OH •O₂⁻ +H 2 O ® 2 •OH +2OH - Active species (O₂⁻, h + , •OH) + CR ® Intermediate products, CO₂ + H₂O 4 Conclusions In summary, we successfully fabricated a ZIF-8/MnS Z-scheme heterojunction for the degradation of organic pollutants through photocatalysis. Our findings demonstrate that this Z-scheme configuration significantly enhances photocatalytic efficiency by widening light absorption, improving the separation of photogenerated carriers, and decreasing charge transfer resistance. Specifically, the optimal composite ZIF-8/MnS achieved nearly 100% CR removal within 30 minutes and demonstrated stable photocatalytic performance over four consecutive cycles, showcasing excellent photoelectrochemical stability. Radical trapping experiments confirmed that •O₂⁻ and •OH are the primary reactive species. The work provides a rational design strategy for developing efficient, stable MOF-based sulfide heterojunction photocatalysts for organic pollutant treatment. Declarations Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Author Contribution Min Zhou: Methodology, Investigation, Data curation, writing-original draft. Yancheng Wu: Methodology, formal analysis, Data curation; Wenbo Zhang: Formal analysis, Data curation; Xiao-fang Li: General concept, funding acquisition, project administration; Xiaofiang Feng: Methodology, conceptualization, methodology, funding acquisition, project administration. Acknowledgement None Data availability Data will be made available on request. References P.W. Li, T. Zhao, Z.H. Zhao, H.X. Tang, W.S. Feng, Z.J. Zhang, Biochar derived from Chinese herb medicine residues for Rhodamine B dye adsorption. ACS Omega. 8 , 4813–4825 (2023). https://doi.org/10.1021/acsomega.2c06968 Z.Z. Yin, M. Li, Z.W. Chen, X.X. Chen, K.Y. Liu, D.P. Zhou, M.S. Xue, J.F. Ou, Y. Xie, S. Lei, C. Xie, Y.D. Luo, A superhydrophobic pulp/cellulose nanofiber (CNF) membrane via coating ZnO suspensions for multifunctional applications. Ind. Crop Prod. 187 , 115526 (2022). https://doi.org/10.1016/J.INDCROP.2022.115526 X.F. Li, R.X. Li, X.Q. Feng, Efficient adsorption and photocatalytic degradation of organic pollutant by Ag₃PO₄/ZnO/chitosan-biochar composites. Russ J. Inorg. Chem. 68 , 1386–1398 (2023). https://doi.org/10.1134/S0036023623601307 E. Fosso-Kankeu, H. Mittal, S.B. Mishra, A.K. Mishra, Gum ghatti and acrylic acid based biodegradable hydrogels for the effective adsorption of cationic dyes. J. Ind. Eng. Chem. 22 , 171–178 (2015). https://doi.org/10.1016/j.jiec.2014.07.007 D. Liu, K.H. Li, L. Zhou, J.Y. Lei, L.Z. Wang, J.L. Zhang, Y.D. Liu, N, O co-doping enhanced the ability of carbon/Fe composites for peroxymonosulfate activation to degrade sulfadiazine: the advantages of nitrate saturated MOFs as precursors. Sep. Purif. Technol. 314 , 123556 (2023). https://doi.org/10.1016/j.seppur.2023.123556 S.P. Keerthana, R. Yuvakkumar, G. Ravi, S.I. Hong, G. Abdullah, Fabrication of Ce doped TiO₂ for efficient organic pollutants removal from wastewater. Chemosphere. 29 , 133540 (2022). https://doi.org/10.1016/j.chemosphere.2022.133540 I.I. Albanio, P.C.L. Muraro, W.L. da Silva, Rhodamine B dye adsorption onto biochar from olive biomass waste. Water Air Soil. Pollut. 232 , 214 (2021). https://doi.org/10.1007/s11270-021-05117-8 Q.D. Zha, Y.K. Yao, Z.Z. Yin, Y.T. Deng, Z.H. Li, Y. Xie, Y.H. Chen, C.G. Yang, Y.D. Luo, M.S. Xue, Facile construction of multifunctional 3D smart MOF-based polyurethane sponges with photocatalytic ability for efficient separation of oil-in-water emulsions and co-existing organic pollutant. Chem. Eng. J. 490 , 51747 (2024). https://doi.org/10.1016/j.cej.2024.51747 R. Kishor, D. Purchase, G.D. Saratale, R.G. Saratale, L.F.R. Ferreira, M. Bilal, R. Chandra, Ecotoxicological and health concerns of persistent coloring pollutants of textile industry wastewater and treatment approaches for environmental safety. J. Environ. Chem. Eng. 9 , 105012 (2021). https://doi.org/10.1016/j.jece.2021.105012 M.F. Chowdhury, S. Khandaker, F. Sarker, A. Islam, M.T. Rahman, Current treatment technologies and mechanisms for removal of indigo carmine dyes from wastewater: a review. J. Mol. Liq. 318 , 114061 (2020). https://doi.org/10.1016/j.molliq.2020.114061 H. Chen, X. Yu, X. Wang, Y. He, C. Zhang, G. Xue, Z. Liu, H. Lao, H. Song, W. Chen, Y. Qian, A. Zhang, X. Li, Dyeing and finishing wastewater treatment in China: state of the art and perspective. J. Clean. Prod. 326 , 129353 (2021). https://doi.org/10.1016/j.jclepro.2021.129353 H. Wu, S. Wang, Impacts of operating parameters on oxidation-reduction potential and pretreatment efficacy in the pretreatment of printing and dyeing wastewater by Fenton process. J. Hazard. Mater. 243 , 86–94 (2012). https://doi.org/10.1016/j.jhazmat.2012.08.025 J.C. Cardoso, G.G. Bessegato, M.V. Boldrin, Zanoni, Efficiency comparison of ozonation, photolysis, photocatalysis and photoelectrocatalysis methods in real textile wastewater decolorization. Water Res. 98 , 39–46 (2016). https://doi.org/10.1016/j.watres.2016.04.025 H. Lin, W. Peng, M. Zhang, J. Chen, H. Hong, Y. Zhang, A review on anaerobic membrane bioreactors: applications, membrane fouling and future perspectives. Desalination. 314 , 169–188 (2013). https://doi.org/10.1016/j.desal.2012.11.027 J. Liu, Q.H. Dai, R.X. Xiao, T.T. Zhou, J.L. Han, B. Fu, Immobilization of ZnIn₂S₄ on sodium alginate foam for efficient hexavalent chromium removal. Int. J. Biol. Macromol. 236 , 123848 (2023). https://doi.org/10.1016/j.ijbiomac.2023.123848 B. Liu, Z. Li, S. Xu, X. Ren, D. Han, D. Lu, Facile in situ hydrothermal synthesis of BiVO₄/MWCNT nanocomposites as high performance visible-light driven photocatalysts. J. Phys. Chem. Solids. 75 , 977–983 (2014). https://doi.org/10.1016/j.jpcs.2014.07.015 X. Li, N. Yang, T. Xu, Y. Yang, Y.F. Lv, Enhancing visible-light photocatalytic activity of AgCl photocatalyst by CeO₂ modification for degrading multiple organic pollutants. Nanomaterials. 15 , 537 (2025). https://doi.org/10.3390/nano15070537 X.F. Zhang, C. Han, W.L. Xu, Imaging analysis of scanning electrochemical microscopy in energy catalysis. Chem. Biomol. Imaging. 1 , 205–219 (2023). https://doi.org/10.1021/cbmi.2c00008 Y.J. Chen, J. Hao, Z.H. Yin, Q.H. Wang, Y.T. Zhou, L.P. Jia, H.M. Li, W.L. Liao, K.P. Liu, An accuracy improved ratiometric SERS sensor for rhodamine 6G in chili powder using a metal-organic framework support. RSC Adv. 13 , 10135–10143 (2023). https://doi.org/10.1039/d3ra00790a U. Marta Pérez-Miana, Javier, J. Reséndiz-Ordóñez, Coronas, Solventless synthesis of ZIF-L and ZIF-8 with hydraulic press and high temperature. Microporous Mesoporous Mater. 328 , 111487 (2021). https://doi.org/10.1016/j.micromeso.2021.111487 T.T. Li, Y.J. Fan, X.X. Cen, Y. Wang, B.C. Shiu, H.T. Ren, H.K. Peng, Q. Jiang, C.W. Lou, J.H. Lin, Polypropylene/polyvinyl alcohol/metal-organic framework-based melt-blown electrospun composite membranes for highly efficient filtration of PM 2.5 , Nanomaterials, 10 (2020) 2025. https://doi.org/10.3390/nano10102025 G.F. Huang, Y.J. Zhang, R.R. Zhang, M.Y. Zhang, L.W. Zhang, Y.F. Xin, Y.Y. Liu, J.F. Chen, Removal of methyl orange and methylene blue by bimetallic zinc/cobalt metal-organic skeleton/carbon nanotubes (Zn/Co-ZIF@CNTs). RSC Adv. 15 , 4681–4692 (2025). https://doi.org/10.1039/D4RA07021F L.H. Feng, X.F. Zhang, Z.K. Jin, J.S. Chen, X. Duan, S.Y. Ma, T.F. Xia, An anionic porous indium-organic framework with nitrogen-rich linker for efficient and selective removal of trace cationic dyes. Molecules. 28 , 4980 (2023). https://doi.org/10.3390/molecules28134980 P.Q. Li, J.J. Qian, L. Du, Q.H. Zhao, Zinc-tetracarboxylate framework material with nano-cages and one-dimensional channels for excellent selective and effective adsorption of methyl blue dye. RSC Adv. 10 , 3539–3543 (2020). https://doi.org/10.1039/c9ra08983g Y. Meng, W.H. Zhou, D.X. Kou, Z.J. Zhou, Y.N. Meng, S.X. Wu, Cu₂ZnSnS₄ decorated CdS nanorods for enhanced visible-light-driven photocatalytic hydrogen production. Int. J. Hydrog Energy. 43 , 20408–20416 (2018). https://doi.org/10.1016/j.ijhydene.2018.09.161 I. Muhammad, A.B. Yousaf, F. Muhammad, P. Kasak, Enhanced Z-scheme visible light photocatalytic hydrogen production over α-Bi₂O₃/CZS heterostructure. Int. J. Hydrog Energy. 43 , 4256–4264 (2018). https://doi.org/10.1016/j.ijhydene.2018.01.056 Z.Y. Fan, Z.L. Wang, Y.Q. Wang, J. Li, Y. Xie, Y. Ling, Y. Chen, In₂S₃-modified ZnIn₂S₄ enhanced photogenerated carrier separation efficiency and photocatalytic hydrogen evolution under visible light. Fuel. 373 , 132401 (2024). https://doi.org/10.1016/J.FUEL.2024.132401 H. Li, Y.L. Cheng, J.X. Li, T.H. Li, J. Zhu, W.B. Deng, J.J. Zhu, D.L. He, Preparation and adsorption performance study of graphene quantum dots@ZIF-8 composites for highly efficient removal of volatile organic compounds. Nanomaterials. 12 , 4008 (2022). https://doi.org/10.3390/nano12224008 L.L. Dai, M.J. Yao, Z.X. Fu, X. Li, X.M. Zheng, S.Y. Meng, Z. Yuan, K.Y. Cai, H. Yang, Y.L. Zhao, Multifunctional metal-organic framework-based nanoreactor for starvation/oxidation improved indoleamine 2,3-dioxygenase-blockade tumor immunotherapy. Nat. Commun. 13 , 2688 (2022). https://doi.org/10.1038/S41467-022-30436-Y G.L. Zuo, Y.X. Fu, H. Zhou, J. Du, X. Ding, H.Y. Ye, S-scheme MnS/ZnO heterojunction composites for photocatalytic degradation of tetracycline. J. Mater. Sci. : Mater. Electron. 36 , 745 (2025). https://doi.org/10.1007/S10854-025-14823-X A. Das, D.Y. Liu, R.R. Wary, A.S. Vasenko, O.V. Prezhdo, R.G. Nair, Mn-modified ZnO nanoflakes for optimal photoelectrochemical performance under visible light: experimental design and theoretical rationalization. J. Phys. Chem. Lett. 14 , 9604–9611 (2023). https://doi.org/10.1021/acs.jpclett.3c02730 C. Chang, L.Y. Zhu, S.F. Wang, X.L. Chu, L.F. Yue, A novel mesoporous graphite carbon nitride/BiOI heterojunction for enhancing photocatalytic performance under visible light irradiation. ACS Appl. Mater. Interfaces. 6 , 5083–5093 (2014). https://doi.org/10.1021/am4057488 K. Li, M.M. Chen, L. Chen, S.Y. Zhao, W.B. Pan, P. Li, Y.C. Han, Adsorption of tetracycline from aqueous solution by ZIF-8: isotherms, kinetics and thermodynamics. Environ. Res. 241 , 117588 (2023). https://doi.org/10.1016/j.envres.2023.117588 J.H. Ran, H.B. Chen, S.G. Bi, Q.F. Guo, Z.M. Deng, G.M. Cai, D.S. Cheng, X.N. Tang, X. Wang, One-step in-situ growth of zeolitic imidazole frameworks-8 on cotton fabrics for photocatalysis and antimicrobial activity. Cellulose. 27 , 10867–10879 (2020). https://doi.org/10.1007/s10570-020-03483-1 X. Bo, C.R. Yang, M. Chang, D.H. Liu, Structural design of core-shell ZIF-8@NH₂-MIL-125 photocatalyst for synergistic adsorption-photocatalytic degradation of tetracycline hydrochloride. J. Alloys Compd. 973 , 172850 (2024). https://doi.org/10.1016/j.jallcom.2023.172850 R.G. Yang, Y.M. Fu, H.N. Wang, D.P. Zhang, Z. Zhou, Y.Z. Cheng, X. Meng, Y.O. He, Z.M. Su, ZIF-8/covalent organic framework for enhanced CO₂ photocatalytic reduction in gas-solid system. Chem. Eng. J. 450 , 138040 (2022). https://doi.org/10.1016/j.cej.2022.138040 Q. Cui, H. Li, F.J. Wang, Z.M. Li, H. Li, Y. Song, H.T. Wu, X.Z. Wang, S.S. Chen, In situ fabrication of ZIF-8 Shell on Polyamidoxime nanofibers for enhanced uranium extraction from seawater through a synergistic effect. Desalination. 621 , 119741–119741 (2025). https://doi.org/10.1016/J.DESAL.2025.119741 Y.C. Pang, X.H. Zang, H.D. Li, J.Y. Liu, Q.Y. Chang, S.H. Zhang, C. Wang, Z. Wang, Solid-phase microextraction of organophosphorous pesticides from food samples with a nitrogen-doped porous carbon derived from g-C₃N₄ templated MOF as the fiber coating. J. Hazard. Mater. 384 , 121430 (2020). https://doi.org/10.1016/j.jhazmat.2019.121430 X.R. Hu, J.H. Hou, L. Pang, Z.G. Feng, J.H. Liu, H.Y. Feng, Y. Kong, C. Liu, MIL-125@ZIF-8 based solid phase microextraction coating for sensitive determination of organophosphate esters in aqueous environments. Microchim Acta. 192 , 269 (2025). https://doi.org/10.1007/s00604-025-07127-8 Y.R. Zhu, R. Zhao, Y.T. Xu, W.H. Chen, Z.L. Hu, L.J. Xi, Y.J. Xie, H.S. Hou, T.C. Liu, K. Amine, X.B. Ji, G.Q. Zou, Anion vacancies coupling with heterostructures enable advanced aerogel cathode for ultrafast aqueous zinc-ion storage. Adv. Mater. 37 , e2419582 (2025). https://doi.org/10.1002/adma.202419582 C.C. Guo, R.Y. Zhou, X.R. Liu, R.Y. Tang, W.X. Xi, Y.R. Zhu, Activating the MnS 0.5 Se 0.5 microspheres as high-performance cathode materials for aqueous zinc-ion batteries: insight into in situ electrooxidation behavior and energy storage mechanisms. Small. 15 , e2306237–e2306237 (2023). https://doi.org/10.1002/smll.202306237 Z. Qiao, T. Yan, W. Li, B. Huang, In situ anion exchange synthesis of In₂S₃/In(OH)₃ heterostructures for efficient photocatalytic degradation of MO under solar ligh. New. J. Chem. 41 , 3134–3142 (2017). https://doi.org/10.1039/c6nj04119a G.S. Lekshmi, T. Ramasamy, O. Bazaka, I. Levchenko, K. Bazaka, R. Govindan, M. Mandhakini, Antioxidant, anti-bacterial, and Congo red dye degradation activity of AgₓO-decorated mustard oil-derived rGO nanocomposites. Molecules. 27 , 5950 (2022). https://doi.org/10.3390/molecules27185950 Z.L. Mo, D.Z. Tai, H. Zhang, A. Shahab, A comprehensive review on the adsorption of heavy metals by zeolite imidazole framework (ZIF-8) based nanocomposite in water. Chem. Eng. J. 443 , 136320 (2022). https://doi.org/10.1016/j.cej.2022.136320 H. Yang, S. Hu, H. Zhao, X.F. Luo, Y. Liu, C.F. Deng, Y.L. Yu, T.D. Hu, S.Y. Shan, Y.F. Zhi, H.Y. Su, L.H. Jiang, High-performance Fe-doped ZIF-8 adsorbent for capturing tetracycline from aqueous solution. J. Hazard. Mater. 416 , 126046 (2021). https://doi.org/10.1016/j.jhazmat.2021.126046 J. Wang, K.P. Shi, W.J. Liu, L. Yin, Y. Xu, D.S. Kong, L.X. Ni, Y.R. Yao, S.Y. Li, Y. Zhang, S.G. Yang, H. He, Novel ZIF-8@CHs catalysts for photocatalytic degradation of tetracycline hydrochloride. Chem. Eng. J. 461 , 142130 (2023). https://doi.org/10.1016/j.cej.2023.142130 Z.Y. Wang, J.F. Li, Y.Q. Qiao, X.M. Liu, Y.F. Zheng, Z.Y. Li, J. Shen, Y. Zhang, S.L. Zhu, H. Jiang, Y.Q. Liang, Z.D. Cui, P.K. Chu, S.L. Wu, Rapid ferroelectric-photoexcited bacteria-killing of Bi₄Ti₃O₁₂/Ti₃C₂Tₓ nanofiber membranes. Adv. Fiber Mater. 5 , 11–13 (2022). https://doi.org/10.1007/s42765-022-00234-8 N. Kumaresan, M.A.A.S. Sinthiya, K. Ramamurthi, R.R.B. Babu, K. Sethuraman, Visible light driven photocatalytic activity of ZnO/CuO nanocomposites coupled with rGO heterostructures synthesized by solid-state method for RhB dye degradation. Arab. J. Chem. 13 , 3910–3928 (2020). https://doi.org/10.1016/j.arabjc.2019.03.002 W. Shao, Y.R. Chen, F. Xie, H. Zhang, H.T. Wang, N. Chang, Facile construction of a ZIF-67/AgCl/Ag heterojunction via chemical etching and surface ion exchange strategy for enhanced visible light driven photocatalysis. RSC Adv. 10 , 38174–38183 (2020). https://doi.org/10.1039/D0RA06842J W. Luo, W.Y. Huang, X.Q. Feng, Y. Huang, X.W. Song, H.F. Lin, S.F. Wang, G. Mailhot, The utilization of Fe-doped g-C₃N₄ in a heterogeneous photo-Fenton-like catalytic system: the effect of different parameters and a system mechanism investigation. RSC Adv. 10 , 21876–21886 (2020). https://doi.org/10.1039/D0RA00993H P. Dhiman, G. Sharma, A.N. Alodhayb, A. Kumar, G. Rana, T. Sithole, Z.A. AlOthman, Constructing a visible-active CoFe₂O₄@Bi₂O₃/NiO nanoheterojunction as magnetically recoverable photocatalyst with boosted ofloxacin degradation efficiency. Molecules. 27 , 8234 (2022). https://doi.org/10.3390/molecules27238234 F. Chen, Q. Yang, J. Sun, F. Yao, S. Wang, Y. Wang, X. Wang, X. Li, C. Niu, D. Wang, G. Zeng, Enhanced photocatalytic degradation of tetracycline by AgI/BiVO₄ heterojunction under visible-light irradiation: mineralization efficiency and mechanism. ACS Appl. Mater. Interfaces. 8 , 32887–32900 (2016). https://doi.org/10.1021/acsami.6b12278 S.H. Miao, H.C. Gao, H.Y. Xia, X.X. Mao, L.J. Zhang, M.Q. Shi, Y.G. Zhang, Accelerated Fenton degradation of azo dye wastewater via a novel Z-scheme CoFeN-g-C₃N₄ heterojunction photocatalyst with excellent charge transfer under visible light irradiation. Dalton Trans. 51 , 17243–17253 (2022). https://doi.org/10.1039/D2DT02790A R.A. Nasr, A.F. El-Sayed, G.M. El Komy, G.T. El-Bassyouni, S.M. Mousa, Modification of photocatalytic activity and antibacterial properties of Mn₂O₃ by Zn ions doping. Sci. Rep. 15 , 14325 (2025). https://doi.org/10.1038/s41598-025-95769-2 T.A. Alrebdi, R.A. Rezk, S.M. Alghamdi, H.A. Ahmed, F.H. Alkallas, R.A. Pashameah, A.M. Mostafa, E.A. Mwafy, Photocatalytic performance improvement by doping Ag on ZnO/MWCNTs nanocomposite prepared with pulsed laser ablation method based photocatalysts degrading Rhodamine B organic pollutant dye. Membranes. 12 , 877 (2022). https://doi.org/10.3390/membranes12090877 E. Atinault, V. De Waele, U. Schmidhammer, M. Fattahi, M. Mostafavi, Scavenging of e s – and ·OH radicals in concentrated HCl and NaCl aqueous solutions. Chem. Phys. Lett. 460 , 461–465 (2008). https://doi.org/10.1016/j.cplett.2008.08.047 Y.X. Wang, Z.M. Ao, H.Q. Sun, X.G. Duan, S.B. Wang, Activation of peroxymonosulfate by carbonaceous oxygen groups: experimental and density functional theory calculations. Appl. Catal. B: Environ. 198 , 295–302 (2016). https://doi.org/10.1016/j.apcatb.2016.08.025 T.S. Alkhuraiji, Effect of Co⁶⁰ irradiation on the degradation and mineralization of sulfonated aromatic compounds in aqueous solutions. Chemosphere. 228 , 769–777 (2019). https://doi.org/10.1016/j.chemosphere.2019.05.144 Y.Q. Yan, X.Y. Zhang, J.H. Wei, M. Chen, J.T. Bi, Y. Bao, Understanding the iron-cobalt synergies in ZSM-5: enhanced peroxymonosulfate activation and organic pollutant degradation. ACS Omega. 7 , 17811–17821 (2022). https://doi.org/10.1021/acsomega.2c01031 Z.M. Dong, R.D. Zhou, L.Y. Xiong, H. Li, Q. Liu, L.Z. Zheng, Z.R. Guo, Z.X. Deng, Preparation of a Ti 0.7 W 0.3 O₂/TiO₂ nanocomposite interfacial photocatalyst and its photocatalytic degradation of phenol pollutants in wastewater. Nanoscale Adv. 2 , 425–437 (2020). https://doi.org/10.1039/c9na00478e D. Polak, S. Kamocki, M. Szwast, Evaluation of the potential of metal–organic compounds ZIF-8 and F300 in a membrane filtration–adsorption process for the removal of antibiotics from water. Antibiotics. 14 , 619 (2025). https://doi.org/10.3390/antibiotics14060619 M.K. Far, R. Mohebat, M. Ghaedi, M. Tabatabaee, Efficient photocatalytic degradation of malachite green dye from wastewater using facilely synthesized ternary ZIF-8/Ag/Ag₂S nanocomposite: optimization by RSM (CCD), Process Saf. Environ. Prot. 190 , 46–62 (2024). https://doi.org/10.1016/j.psep.2024.08.036 H. Liu, J.M. Cao, W.L. Zhang, T. Jiang, G.H. Pan, Y. Wu, The development and synthesis of a CdZnS@metal–organic framework ZIF-8 for the highly efficient photocatalytic degradation of organic dyes. Molecules. 28 , 7904 (2023). https://doi.org/10.3390/molecules28237904 Z.C. Liu, Y. Zhong, Z.C. Hu, W.Q. Zhang, X.T. Zhang, X. Ji, X.M. Wang, Modification of ZIF-8 nanocomposite by a Gd atom doped TiO₂ for high efficiency photocatalytic degradation of neutral red dye: an experimental and theoretical study. J. Mol. Liq. 380 , 121729 (2023). https://doi.org/10.1016/j.molliq.2023.121729 Y.Q. Jing, Q. Lei, C. Xia, Y. Guan, Y.D. Yang, J.X. He, Y. Yang, Y.H. Zhang, M. Yan, Synthesis of Ag and AgCl co-doped ZIF-8 hybrid photocatalysts with enhanced photocatalytic activity through a synergistic effect. RSC Adv. 10 , 698–704 (2020). https://doi.org/10.1039/c9ra10100d A. Chakraborty, D.A. Islam, H. Acharya, Facile synthesis of CuO nanoparticles deposited zeolitic imidazolate frameworks (ZIF-8) for efficient photocatalytic dye degradation. J. Solid State Chem. 269 , 566–574 (2019). https://doi.org/10.1016/j.jssc.2018.10.036 A. Faraji, N. Mehrdadi, N.M. Mahmoodi, M. Baghdadi, A. Pardakhti, Enhanced photocatalytic activity by synergic action of ZIF-8 and NiFe₂O₄ under visible light irradiation. J. Mol. Struct. (2020). https://doi.org/10.1016/j.molstruc.2020.129028 J.H. He, J. Ye, Y. Zhang, L.B. Kong, X.J. Zhou, Y.H. Ma, Y.F. Yang, Synergistic RGO/Black TiO₂/2D-ZIF-8 Ternary Heterogeneous Composite with Highly Efficient Photocatalytic Activity, ChemistrySelect, 5 (2020) 3746–3755. https://doi.org/10.1002/slct.201904939 B. Abdollahi, A. Najafidoust, E. Abbasi Asl, M. Sillanpaa, Fabrication of ZIF-8 metal organic framework (MOFs)-based CuO-ZnO photocatalyst with enhanced solar-light-driven property for degradation of organic dyes. Arab. J. Chem. 14 , 103444 (2021). https://doi.org/10.1016/j.arabjc.2021.103444 J. Abdi, Synthesis of Ag-doped ZIF-8 photocatalyst with excellent performance for dye degradation and antibacterial activity, Colloids Surf. A: Physicochem Eng. Asp. 604 , 125330 (2020). https://doi.org/10.1016/j.colsurfa.2020.125330 X. Liu, J. Zhang, Y.M. Dong, H.X. Li, Y.M. Xia, H.J. Wang, A facile approach for the synthesis of Z-scheme photocatalyst ZIF-8/g-C₃N₄ with highly enhanced photocatalytic activity under simulated sunlight. New. J. Chem. 42 , 12180–12187 (2018). https://doi.org/10.1039/c8nj01782d N. Chang, Y.R. Chen, F. Xie, Y.P. Liu, H.T. Wang, Facile construction of Z-scheme AgCl/Ag-doped-ZIF-8 heterojunction with narrow band gaps for efficient visible-light photocatalysis. Colloids Surf. A: Physicochem Eng. Asp. 616 , 126351 (2021). https://doi.org/10.1016/j.colsurfa.2021.126351 A. Malik, M. Nath, S. Mohiyuddin, G. Packirisamy, Multifunctional CdSNPs@ZIF-8: potential antibacterial agent against GFP-expressing Escherichia coli and Staphylococcus aureus and efficient photocatalyst for degradation of methylene blue. ACS Omega. 3 , 8288–8308 (2018). https://doi.org/10.1021/acsomega.8b00664 M.Q. Hu, H. Lou, X.L. Yan, X.Y. Hu, R. Feng, M. Zhou, In-situ fabrication of ZIF-8 decorated layered double oxides for adsorption and photocatalytic degradation of methylene blue. Microporous Mesoporous Mater. 271 , 68–72 (2018). https://doi.org/10.1016/j.micromeso.2018.05.048 Y.H. Si, X.R. Li, G. Yang, X.L. Mie, L.B. Ge, Fabrication of a novel core–shell CQDs@ZIF-8 composite with enhanced photocatalytic activity. J. Mater. Sci. 55 , 13049–13061 (2020). https://doi.org/10.1007/s10853-020-04909-8 A.J. Vakayil, T.K. Bindu Sharmila, C.S. Sasi Sreesha, Julie Chandra, P.H. Raman Vidya, Fathima Fasna, Water solubility, photoluminescence and photocatalytic activity of ZnS quantum dot sulfonated polystyrene composite. J. Lumin. 263 , 120147 (2023). https://doi.org/10.1016/j.jlumin.2023.120147 C.C. Wang, C.J. You, K. Rong, C.Q. Shen, F. Yang, S.J. Li, An S-scheme MIL-101(Fe)-on-BiOCl heterostructure with oxygen vacancies for boosting photocatalytic removal of Cr(VI). Acta Phys. -Chim Sin. 40 , 2307045 (2024). https://doi.org/10.3866/PKU.WHXB202307045 S.J. Li, C.C. Wang, K.X. Dong, P. Zhang, X.B. Chen, X. Li, MIL-101(Fe)/BiOBr S-scheme photocatalyst for promoting photocatalytic abatement of Cr(VI) and enrofloxacin antibiotic: performance and mechanism. Chin. J. Catal. 51 , 101–112 (2023). https://doi.org/10.1016/S1872-2067(22)64151-8 P. Lian, A.M. Qin, Z.S. Liu, H. Ma, L. Liao, K.Y. Zhang, N. Li, Facile synthesis to porous TiO₂ nanostructures at low temperature for efficient visible-light degradation of tetracycline. Nanomaterials. 14 , 943 (2024). https://doi.org/10.3390/nano14110943 Z.Y. Zhang, X.Y. Xiao, M.L. Lu, Novel Z-scheme 2D/2D Bi₄O₅Br₂/BiOCl heterojunction with enhanced photocatalytic activity for RhB degradation. J. Chem. Technol. Biotechnol. 97 , 1280–1292 (2022). https://doi.org/10.1002/jctb.7023 Z. Guo, H.X. Hou, J.Y. Zhang, P.L. Cai, J. Lin, Prominent roles of Ni(OH)₂ deposited on ZnIn₂S₄ microspheres in efficient charge separation and photocatalytic H₂ evolution. RSC Adv. 11 , 12442–12448 (2021). https://doi.org/10.1039/d1ra01648b J.F. Zheng, C.Z. Fan, X.M. Li, Enhanced photodegradation of tetracycline hydrochloride by hexameric AgBr/Zn-Al MMO S-scheme heterojunction photocatalysts: low metal leaching, degradation mechanism and intermediates. Chem. Eng. J. 446 , 137371 (2022). https://doi.org/10.1016/j.cej.2022.137371 Z.W. Liu, J.J. Wang, S.H. Dong, L.Y. Wang, L. Li, Z.Z. Cao, Y.F. Zhang, L. Cheng, J.C. Yang, Ultrasonic controllable synthesis of sulfur-functionalized metal–organic frameworks (S-MOFs) and their application in piezo-photocatalytic rapid reduction of hexavalent chromium (Cr), Ultrason. Sonochem, 107 (2024) 106912. https://doi.org/10.1016/j.ultsonch.2024.106912 Y.M. Wang, T.T. Zhang, T.T. Wei, F.Y. Li, L. Xu, Bimetallic phosphide NiₓCo₁₋ₓP decorated flower-like ZnIn₂S₄ for enhanced photocatalytic hydrogen evolution. New. J. Chem. 45 , 11261–11268 (2021). https://doi.org/10.1039/d1nj02019f Z.T. Song, L.M. Wang, Construction of Ag/Ag₂S nanoparticles modified CoSₓ/ZnIn₂S₄ heterojunction for boosting photocatalytic organics degradation. J. Alloys Compd. 937 , 168419 (2023). https://doi.org/10.1016/j.jallcom.2022.168419 B.Q. Gao, Y. Pan, Q.Q. Chang, Z.H. Xi, H. Yang, Hierarchically Z-scheme photocatalyst of {0 1 0}BiVO₄/Ag/CdS with enhanced performance in synergistic adsorption-photodegradation of fluoroquinolones in water. Chem. Eng. J. 435 , 134834 (2022). https://doi.org/10.1016/j.cej.2022.134834 Y.P. Huo, T.L. Yu, Y.Y. Xue, G.S. Zhang, S.X. Song, Y.H. Shao, X.J. Han, Three CoS/CoO microspheres and their mixed matrix membranes for the highly efficient photocatalytic degradation of methyl blue. RSC Adv. 14 , 25811–25819 (2024). https://doi.org/10.1039/D4RA03261F A. Mancuso, N. Blangetti, O. Sacco, F.S. Freyria, B. Bonelli, S. Esposito, D. Sannino, V. Vaiano, Photocatalytic degradation of crystal violet dye under visible light by Fe-doped TiO₂ prepared by reverse-micelle sol–gel method. Nanomaterials. 13 , 270 (2023). https://doi.org/10.3390/nano13020270 Additional Declarations No competing interests reported. Supplementary Files Fig.S1.docx Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-9420342","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":625570915,"identity":"5e3a0d2e-9cb9-432f-8260-4964c34ed54d","order_by":0,"name":"min Zhou","email":"","orcid":"","institution":"Tianshui Normal University","correspondingAuthor":false,"prefix":"","firstName":"min","middleName":"","lastName":"Zhou","suffix":""},{"id":625570916,"identity":"2819de8c-d492-4436-bf16-1060ec2a23f7","order_by":1,"name":"Yancheng Wu","email":"","orcid":"","institution":"Tianshui Normal University","correspondingAuthor":false,"prefix":"","firstName":"Yancheng","middleName":"","lastName":"Wu","suffix":""},{"id":625570920,"identity":"7cfcc866-ce78-4089-b57e-977c6b134e8b","order_by":2,"name":"Wenbo Zhang","email":"","orcid":"","institution":"Tianshui Normal University","correspondingAuthor":false,"prefix":"","firstName":"Wenbo","middleName":"","lastName":"Zhang","suffix":""},{"id":625570922,"identity":"0ff3379d-04ad-42a0-a407-23b586fb92aa","order_by":3,"name":"Xiaofang Li","email":"","orcid":"","institution":"Tianshui Normal University","correspondingAuthor":false,"prefix":"","firstName":"Xiaofang","middleName":"","lastName":"Li","suffix":""},{"id":625570924,"identity":"5d7e0fb1-1ff7-4d14-b12f-75b7c1f09940","order_by":4,"name":"Xiaoqiang Feng","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAzklEQVRIiWNgGAWjYBACefb+h4//VNTw8LM3EKnFsOcMswHPmWNykj0HiLXmRg6bAG8bs7HBjQQidTDOyD3GIMHGlthw8/HGGww1NtEEtbDzvEt7YMAjk9g4O63YguFYWm4DQVvaE8wNEiTYEpulc8wkGBsOE9bCcCDBTOKAAXNim+QZYrWcyDGTbEhgNuaR4CFSi2HPsWRjhgPH5CR4gH5JIMYv8uzNBx8z/qvhsT9+eOONDzU2RDgMCRhIJJCiHKKFVB2jYBSMglEwMgAA1ps/pIwahFQAAAAASUVORK5CYII=","orcid":"","institution":"Tianshui Normal University","correspondingAuthor":true,"prefix":"","firstName":"Xiaoqiang","middleName":"","lastName":"Feng","suffix":""}],"badges":[],"createdAt":"2026-04-15 01:23:55","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-9420342/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-9420342/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":107868986,"identity":"e85c230d-fb96-4691-85f2-ba2234f9fe41","added_by":"auto","created_at":"2026-04-27 07:35:32","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":416824,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Schematic illustration of the preparation of ZIF-8/MnS photocatalyst, (b) XRD patterns, and (c) FTIR spectra of the ZIF-8, MnS and ZIF-8/MnS\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-9420342/v1/dcaee39db8c2a1477938b038.png"},{"id":107719959,"identity":"ac61af70-e22f-45d2-aa8c-197ae3503143","added_by":"auto","created_at":"2026-04-24 10:47:09","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":382094,"visible":true,"origin":"","legend":"\u003cp\u003eFESEM images of (a, b) MnS, (c, d) ZIF-8 and (e,f) ZIF-8/MnS-3, (g) EDS mapping of ZIF-8/MnS-3 composite.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-9420342/v1/ae5d19fd4b744f459db317bb.png"},{"id":107869599,"identity":"74d29546-3d97-4434-98ac-e9ce25cced54","added_by":"auto","created_at":"2026-04-27 07:37:32","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":156565,"visible":true,"origin":"","legend":"\u003cp\u003e(a)XPS survey spectrum and high-resolution spectra of (b) Zn 2p, (c) N 1s, (d) O 1s, (e) C 1s, (f) Mn 2p and (g) S 2p of ZIF-8/MnS-3.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-9420342/v1/3d55c64d963ac051d44da9e7.png"},{"id":107719962,"identity":"db0194b0-c8a2-4ebe-b69c-afe1ae5e5a1b","added_by":"auto","created_at":"2026-04-24 10:47:09","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":156775,"visible":true,"origin":"","legend":"\u003cp\u003e(a) N\u003csub\u003e2\u003c/sub\u003e adsorption–desorption isotherms and (b) corresponding pore size distribution plots of ZIF-8, MnS and ZIF-8/MnS-3 samples.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-9420342/v1/d5fdbe3c35fcc7c5ede16c59.png"},{"id":107868969,"identity":"2bb01db8-a014-48d8-ac2c-e1a6c5cb2c03","added_by":"auto","created_at":"2026-04-27 07:35:22","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":266547,"visible":true,"origin":"","legend":"\u003cp\u003e(a)Photocatalytic degradation of ZIF-8/MnS for CR (20 mg/L), (b)photocatalytic degradation kinetic curves for CR,(c)photocatalytic degradation of ZIF-8/MnS-3 with different dosage for CR (20 mg/L), (d) photocatalytic degradation for CR with different concentrations by ZIF-8/MnS-3, (e)Photocatalytic degradation of CR with different anions by ZIF-8/MnS-3 and (f)Reusability of ZIF-8/MnS for CR degradation.\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-9420342/v1/3ec349208ab407e668c84a59.png"},{"id":107869867,"identity":"206125b0-d545-409d-820f-a7864bdbad9d","added_by":"auto","created_at":"2026-04-27 07:38:20","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":262345,"visible":true,"origin":"","legend":"\u003cp\u003e(a) PL spectra, (b) transient photocurrent response, (c) EIS Nyquist plots, (d) linear sweep voltammograms, (e)Cyclic voltammetry and (f) double-layer capacitance (Cdl) of ZIF-8, MnS, and ZIF-8/MnS samples\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-9420342/v1/d1b47a2fb0c18a7418484d05.png"},{"id":107719964,"identity":"a63d2fd4-936e-42b2-9795-85882f5abc97","added_by":"auto","created_at":"2026-04-24 10:47:09","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":220033,"visible":true,"origin":"","legend":"\u003cp\u003eUV–vis DRS spectra (a) and corresponding bandgap values of samples(b), Mott-Schottky of ZIF-8l (c) and MnS(d).\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-9420342/v1/bbee1005404d5e935f6822d0.png"},{"id":107868864,"identity":"52a5a724-bb17-4a65-bb0b-a1c1290bd47b","added_by":"auto","created_at":"2026-04-27 07:34:35","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":271565,"visible":true,"origin":"","legend":"\u003cp\u003e(a) ESP mapping, (b) molecular orbital electron densities, and (c) active species trapping tests of ZIF-8/MnS-3\u003c/p\u003e","description":"","filename":"8.png","url":"https://assets-eu.researchsquare.com/files/rs-9420342/v1/687dce26dc284fbac8970b74.png"},{"id":107719965,"identity":"32b7b7f2-3bf1-4e88-8a79-156d617100fd","added_by":"auto","created_at":"2026-04-24 10:47:09","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":170358,"visible":true,"origin":"","legend":"\u003cp\u003ePossible photodegradation mechanism of the ZIF-8/MnS for CR\u003c/p\u003e","description":"","filename":"9.png","url":"https://assets-eu.researchsquare.com/files/rs-9420342/v1/8691051db35cac127de60806.png"},{"id":108490960,"identity":"0ac5e42f-271b-4571-b1a7-c0bebb5a8a32","added_by":"auto","created_at":"2026-05-05 09:50:27","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2621272,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-9420342/v1/f8d1b86e-37bd-4223-a6e8-03ebf9180ba6.pdf"},{"id":107719957,"identity":"f994b95d-7de7-487e-9807-4ce927a7b4b7","added_by":"auto","created_at":"2026-04-24 10:47:09","extension":"docx","order_by":0,"title":"","display":"","copyAsset":false,"role":"supplement","size":251081,"visible":true,"origin":"","legend":"","description":"","filename":"Fig.S1.docx","url":"https://assets-eu.researchsquare.com/files/rs-9420342/v1/4f4a329cc388a3c9dd7d54c3.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Solvothermal Construction of ZIF-8/MnS Z-Scheme Heterojunctions for Enhanced Photocatalytic Degradation of Organic Dyes","fulltext":[{"header":"1 Introduction","content":"\u003cp\u003eLarge volume of wastewater are discharged into water bodies as a result of industrial development, polluting water resources and the environment while posing serious threats to human health. Organic dyes are common water pollutants classified into anionic, cationic, and non-ionic categories based on their chemical properties [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e]. Organic dyes wastewater is characterized by high concentration, complex composition, high chroma, low biodegradability, and large discharge volumes. Moreover, these effluents often contain toxic compounds that severely threaten aquatic organisms and the ecological environment [\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e, \u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e]. Conventional treatment methods primarily include biodegradation [\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e], chemical oxidation [\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e], photocatalytic oxidation [\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e], physical adsorption [\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e, \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e], ion exchange, coagulation, and electrochemical methods [\u003cspan additionalcitationids=\"CR10 CR11\" citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e]. Unfortunately, most of these methods fall short of achieving full mineralization of persistent dyes, frequently resulting in secondary contamination [\u003cspan additionalcitationids=\"CR14 CR15\" citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e]. As a promising green purification technology, photocatalysis offers significant potential because of its minimal energy usage, gentle reaction parameters, and capability to entirely mineralize organic contaminants into CO₂ and water [\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eMetal-organic frameworks (MOFs) are crystalline porous materials constructed from metal nodes and organic linkers that self-assemble into periodic architectures [\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e, \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e]. Their exceptional porosity, tunable structures, and abundant active sites make them promising candidates for photocatalytic applications. Among MOFs, zeolitic imidazolate framework-8(ZIF-8) has attracted significant interest owing to its sodalite topology, comprising Zn\u0026sup2;⁺ ions tetrahedrally coordinated by 2-methylimidazolate ligands [\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e, \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]. This unique structure confers exceptional thermal and chemical stability, a large surface area, and enduring microporosity [\u003cspan additionalcitationids=\"CR23\" citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e], rendering it highly effective for pollutant adsorption and photocatalytic degradation. However, the photocatalytic activity of ZIF-8 is hindered by its high recombination rate of photogenerated carriers and limited visible light absorption capacity. Manganese sulfide (MnS) has attracted considerable interest in photocatalysis due to its high redox activity and visible-light response. Nevertheless, practical applications of MnS are hindered by its susceptibility to photocorrosion, low carrier mobility, and rapid charge recombination [\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e, \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e]. Recent studies demonstrate that coupling MnS with semiconductors possessing suitable band structures can mitigate these drawbacks and enhance light utilization efficiency [\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eBased on the band structures of ZIF-8 and MnS, ZIF-8/MnS composites are expected to construct a heterojunction that fully leverages the advantages of both components, promotes photogenerated carrier separation, and thereby enhances the photocatalytic degradation efficiency of organic pollutants. In the present work, ZIF-8/MnS composites were prepared via an in-situ growth method, and the photocatalytic enhancement mechanism was elucidated through systematic characterization and performance evaluation. Experimental results demonstrate that the optimized ZIF-8/MnS (Zn:Mn\u0026thinsp;=\u0026thinsp;10:3) sample exhibits excellent degradation performance under UV light, with the performance enhancement attributed to an extended photoresponse range, efficient charge separation, and abundant surface active sites. The work provides important insights for designing efficient MOF-based photocatalysts.\u003c/p\u003e"},{"header":"2 Experimental","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1 Materials\u003c/h2\u003e \u003cp\u003e2-methylimidazole (C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003eN\u003csub\u003e2\u003c/sub\u003e), zinc acetate ( Zn(Ac)\u003csub\u003e2\u003c/sub\u003e\u0026middot;2H\u003csub\u003e2\u003c/sub\u003eO), manganese chloride (MnCl\u003csub\u003e2\u003c/sub\u003e\u0026middot;4H\u003csub\u003e2\u003c/sub\u003eO), thiourea (CH\u003csub\u003e4\u003c/sub\u003eN\u003csub\u003e2\u003c/sub\u003eS), Congo red (CR), methanol, 1,4-benzoquinone (BQ), isopropanol (IPA), and ethylenediaminetetraacetic acid disodium salt (EDTA), and ethanol were all analytical grade and obtained from Xilong Scientific. All the chemicals were analytical grade and used without purification.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2 Synthesis of ZIF-8\u003c/h2\u003e \u003cp\u003eZIF-8 was synthesized based on a reported procedure with slight modifications [\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e]. 0.02 moles of Zn (Ac)₂\u0026middot;2H₂O were dissolved in 30 mL of methanol via sonication to create solution A. Simultaneously, 0.08 moles of 2-methylimidazole were dissolved in 30 mL of distilled water through sonication to produce solution B. Solution B was then gradually introduced into solution A while stirring continuously at room temperature. Following 1 hour of stirring, the mixture was moved to a polytetrafluoroethylene-lined autoclave and heated at 120\u0026deg;C for 24 h. After cooling to room temperature, the resulting product was gathered through vacuum filtration, washed iteratively with methanol and distilled water, and ultimately vacuum-dried at 60\u0026deg;C for 12 h to yield the ZIF-8 sample.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3 Synthesis of MnS\u003c/h2\u003e \u003cp\u003eMnCl₂\u0026middot;4H₂O (0.05 mol) was dissolved in 30 mL of water through sonication. Thiourea (0.05 mol) was separately dissolved in 30 mL of distilled water using sonication. Subsequently, the thiourea solution was carefully introduced into the manganese chloride solution at room temperature with stirring. After 1 h, the mixture was transferred to a polytetrafluoroethylene-lined autoclave and heated at 180\u0026deg;C for 24 h. Upon cooling, the product was collected by centrifugation, washed repeatedly with ethanol and distilled water, and vacuum-dried at 60\u0026deg;C for 12 h to afford the MnS sample.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e2.4 Synthesis of ZIF-8/MnS photocatalysts\u003c/h2\u003e \u003cp\u003eComposites of ZIF-8/MnS were synthesized using an in-situ growth approach. In Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea, the preparation involved dissolving 20.0 mmol of Zn(Ac)₂\u0026middot;2H₂O and 2.00 mmol of MnCl₂\u0026middot;4H₂O in 30 mL of methanol to create a metal salt solution. Simultaneously, a ligand solution was prepared by dissolving 2-methylimidazole (80.0 mmol) and thiourea (2.00 mmol) in 30 mL distilled water. The ligand solution was then slowly added to the metal salt solution at room temperature with continuous stirring. After 1 h, the mixture was transferred to a polytetrafluoroethylene-lined autoclave and was heated at 120\u0026deg;C for 24 h. Following cooling to room temperature, the product underwent collection by centrifugation, multiple washings with methanol and distilled water, and vacuum drying at 60\u0026deg;C for 12 h, resulting in the production of ZIF-8/MnS-1 (Zn\u0026sup2;⁺:Mn\u0026sup2;⁺=10:1). Composites with different MnS loadings (ZIF-8/MnS-2, ZIF-8/MnS-3, and ZIF-8/MnS-4) were prepared similarly by adjusting the manganese chloride and thiourea amounts while keeping other conditions constant.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003e2.5 Characterization\u003c/h2\u003e \u003cp\u003eXRD patterns were collected on a Shimadzu XRD-6100 diffractometer (Cu Kα radiation, λ\u0026thinsp;=\u0026thinsp;0.15418 nm, 40 kV, 40 mA) over 2θ\u0026thinsp;=\u0026thinsp;5\u0026ndash;80\u0026deg;. FTIR spectra were recorded on a PerkinElmer Spectrum 100 spectrometer (4000\u0026ndash;400 cm⁻\u0026sup1;). Surface morphology was observed via FE-SEM (JEOL JSM-7100, Japan) with EDS (Oxford Instruments). UV\u0026ndash;vis DRS were obtained on a Shimadzu UV-3600 spectrophotometer (200\u0026ndash;900 nm). XPS (Thermo Scientific Escalab 250Xi) determined elemental composition and valence states. BET surface areas were measured using N₂ adsorption\u0026ndash;desorption at 77 K (Micromeritics Tristar ASAP 3000). PL spectra were recorded at room temperature on a Shimadzu RF-5301 PC spectrophotometer (Japan) with λ\u003csub\u003eex\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;350 nm. Photoelectrochemical tests (LSV, CV, TPR, EIS, and M\u0026ndash;S) were performed on a CEL-QPCE3000 workstation (Beijing Zhongjiao Jinyuan Technology) in 0.1 M Na₂SO₄ using a three-electrode configuration with a sample-coated FTO glass working electrode (1 cm \u0026times; 1 cm), a carbon rod counter electrode, and an Ag/AgCl reference electrode. A 300 W Xe lamp provided chopped illumination for transient photocurrent measurements.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003e2.6 Photocatalytic activity measurements\u003c/h2\u003e \u003cp\u003eCR was selected as the model pollutant for photocatalytic degradation experiments under UV irradiation. In a standard procedure, 15 mg of the photocatalyst was dispersed in 30 mL of a CR solution (20 mg/L) and stirred magnetically in the dark for 30 minutes to reach adsorption-desorption equilibrium. Subsequently, the suspension was irradiated with a 300 W UV lamp at 20\u0026deg;C. At predetermined time intervals, 3 mL of the sample was collected and centrifuged. The absorbance of the supernatant was then measured at 496 nm using a UV\u0026ndash;vis spectrophotometer. Degradation efficiency (De,%) was calculated according to the following formula:\u003c/p\u003e \u003cp\u003eDe % = (A\u003csub\u003e0\u003c/sub\u003e - A\u003csub\u003et\u003c/sub\u003e)/ A\u003csub\u003e0\u003c/sub\u003e \u0026times; 100% = (C\u003csub\u003e0\u003c/sub\u003e - C\u003csub\u003et\u003c/sub\u003e)/ C\u003csub\u003e0\u003c/sub\u003e\u0026times; 100%\u003c/p\u003e \u003cp\u003ewhere A₀ and Aₜ are the initial and time-dependent absorbance values of CR, respectively, and C₀ and Cₜ indicate the corresponding initial and time-dependent concentrations.\u003c/p\u003e \u003c/div\u003e"},{"header":"3 Results and discussion","content":"\u003cdiv id=\"Sec10\" class=\"Section2\"\u003e \u003ch2\u003e3.1 Structural characterization\u003c/h2\u003e \u003cp\u003eXRD patterns (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb) confirm that pure MnS consists of mixed γ-MnS (hexagonal, PDF#89-4089) and α-MnS (cubic, PDF#06-0518) phases. Peaks at 25.78\u0026deg;, 27.69\u0026deg;, 45.46\u0026deg;, and 50.00\u0026deg; correspond to γ-MnS (100), (002), (110), and (103) planes, while peaks at 34.30\u0026deg;, 49.30\u0026deg;, and 61.39\u0026deg; can be indexed to α-MnS (200), (220), and (222) planes. In ZIF-8/MnS composites, MnS diffraction peaks partially overlap with those of ZIF-8. However, increasing Mn content progressively attenuates ZIF-8 peak intensities, while MnS peaks exhibit slight shifts attributed to enhanced surface loading and interfacial strain. Higher Mn loading expands the heterojunction, increasing lattice distortion and interfacial defects, thereby reducing ZIF-8 crystallinity [\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e]. No unattributed diffraction peaks were observed, indicating ZIF-8 and MnS did not react chemically to form new phases [\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e]. XRD confirms all composites were successfully prepared as phase-pure materials with the desired crystal structure.\u003c/p\u003e \u003cp\u003eFTIR spectra (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ec) show weak MnS signals. Broad peaks at 3200\u0026ndash;3500 cm⁻\u0026sup1; correspond to O-H stretching of adsorbed water [\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e]. ZIF-8 displays characteristic bands at 3134 and 2929 cm⁻\u0026sup1; (C-H stretching) [\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e], 1445 cm⁻\u0026sup1; (C\u0026thinsp;=\u0026thinsp;N stretching), 1350\u0026ndash;950 cm⁻\u0026sup1; (in-plane imidazole vibrations), 760 cm⁻\u0026sup1; (out-of-plane imidazole bending), and 420 cm⁻\u0026sup1; (Zn-N stretching) [\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e]. The ZIF-8/MnS composites retain these core features, though altered peak intensities and shapes indicate MnS modifies the ZIF-8 vibrational environment without destroying its framework.\u003c/p\u003e \u003cp\u003eSEM analysis reveals MnS (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea-b) as irregular, rough aggregates of low crystallinity. ZIF-8 (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec-d) exhibits uniformly sized, well-dispersed polyhedral nanocrystals typical of its zeolitic imidazolate framework. In the ZIF-8/MnS composite (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ee-f), small spherical MnS particles are deposited on ZIF-8 surfaces and within interstitial spaces. While the ZIF-8 framework is preserved, increased surface roughness confirms successful heterogeneous composite formation. EDS mapping (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eg) confirms the presence of C, N, S, Mn, and Zn, verifying successful ZIF-8/MnS composite synthesis.\u003c/p\u003e \u003cp\u003eXPS analysis (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea) is conducted to examine the surface chemical composition of ZIF-8/MnS composites, verifying the existence of Zn, N, O, C, Mn, and S. In the Zn 2p region (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eb), the spectrum exhibits spin-orbit doublet peaks at 1021.55 eV (2p₃/₂) and 1044.61 eV (2p₁/₂), consistent with Zn\u0026sup2;⁺ in the framework structure of ZIF-8. The N 1s spectrum (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ec) can be deconvoluted into two components at 399.20 eV (Zn-N) and 398.56 eV (C-N), corresponding to nitrogen coordination within the imidazolate linker. The O 1s spectrum (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ed) shows three distinct peaks at 530.35 eV (Zn-O), 531.35 eV (C-O), and 532.17 eV (O-H), which align well with literature-reported values for ZIF-8 [\u003cspan additionalcitationids=\"CR36\" citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e]. The C 1s spectrum (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ee) reveals three characteristic peaks at 284.38 eV (sp\u0026sup2; C), 284.99 eV (C\u0026thinsp;=\u0026thinsp;N), and 285.72 eV (C\u0026thinsp;=\u0026thinsp;O) [\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e, \u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e]. Notably, the Mn 2p spectrum (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ef) displays Mn\u0026sup2;⁺ spin-orbit doublets at 641.06 eV (2p₃/₂) and 653.80 eV (2p₁/₂), accompanied by characteristic satellite peaks at 643.09 eV and 656.10 eV that confirm the formation of MnS [\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e, \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e]. The S 2p spectrum (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eg) reveals two peaks at 161.31 eV (2p₃/₂) and 162.57 eV (2p₁/₂), corresponding to S\u0026sup2;⁻ species in MnS [\u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e].\u003c/p\u003e\u003cp\u003eN\u003csub\u003e2\u003c/sub\u003e adsorption-desorption measurements were conducted to assess the textural characteristics of ZIF-8, MnS, and the ZIF-8/MnS-3 composite (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e and Table\u0026nbsp;1). ZIF-8 displays a Type I isotherm, indicating a microporous nature, along with a substantial Brunauer-Emmett-Teller (BET) surface area of 1449.68 m\u0026sup2;/g and a significant pore volume of 0.6661 cm\u0026sup3;/g, which offer ample catalytic reaction sites. In contrast, MnS displays a Type IV isotherm, indicative of a mesoporous structure; however, its surface area (2.67 m\u0026sup2;/g) and pore volume (0.0034 cm\u0026sup3;/g) are drastically lower, severely limiting active site availability and consequently impairing photocatalytic performance. The ZIF-8/MnS composite shows a hybrid Type I\u0026thinsp;+\u0026thinsp;IV isotherm, confirming a hierarchical micro-mesoporous architecture. It retains a substantial surface area (553.05 m\u0026sup2;/g) and pore volume (0.2577 cm\u0026sup3;/g) with an expanded average pore size (17.36 nm). This hierarchical structure enhances light harvesting efficiency by increasing the accessible surface area and exposing more photoactive sites. Additionally, it facilitates the separation of photogenerated charge carriers and promotes rapid mass transfer. Consequently, the synergistic combination of enriched active sites and improved diffusion kinetics significantly boosts the photocatalytic reaction rate and overall removal efficiency.\u003c/p\u003e\u003cp\u003eTable\u0026nbsp;1 BET parameters of ZIF-8, MnS and ZIF-8/MnS-3\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"No\" id=\"Tabe\" border=\"1\"\u003e \u003ccolgroup cols=\"4\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSample\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eS\u003csub\u003eBET\u003c/sub\u003e(m\u003csup\u003e2\u003c/sup\u003e/g)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003ePore volume(cm\u003csup\u003e3\u003c/sup\u003e/g)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eAverage pore size (nm)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZIF-8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e1449.6770\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.666053\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e10.4403\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eMnS\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e2.6699\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.003424\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e16.9619\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZIF-8/MnS\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e553.0454\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.257692\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e17.3626\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec11\" class=\"Section2\"\u003e \u003ch2\u003e3.2. Photocatalytic performance\u003c/h2\u003e \u003cp\u003eCR is a classic diazo anionic dye with a molecular structure centered on a linear planar aromatic skeleton, containing two azo chromophores (-N\u0026thinsp;=\u0026thinsp;N-) and a sulfonic acid group (-SO₃Na). This structural feature endows it with high stability and recalcitrance to degradation [\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e]. As depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ea, the self-degradation rate of CR is insignificant. Pure ZIF-8, leveraging its high specific surface area and porous structure that efficiently accumulate CR molecules via π-π stacking and electrostatic interactions [\u003cspan additionalcitationids=\"CR45\" citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e], attains a CR degradation rate of 72.3%. Upon compositing with MnS, the ZIF-8/MnS composite photocatalyst exhibits further enhanced adsorption and photocatalytic performance, with ZIF-8/MnS-3 showing optimal activity by almost completely removing CR from aqueous solution within 30 min. This is attributed to the heterojunction structure formed between ZIF-8 and MnS, which not only fully exploits the synergistic enhancement effect of both components, promoting effective coupling of substrate enrichment and catalytic sites, but also accelerates photogenerated charge carrier separation through matched energy level structures, thereby significantly improving the yield of reactive oxygen species [\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e].\u003c/p\u003e \u003cp\u003ePhotocatalytic degradation of organic pollutants typically follows first-order kinetics, as articulated by the Langmuir-Hinshelwood model (ln(C₀/Cₜ)\u0026thinsp;=\u0026thinsp;\u003cem\u003ek\u003c/em\u003et), where C₀ and Cₜ denote the initial concentration and concentration at time t, respectively, and k signifies the apparent rate constant (min⁻\u0026sup1;) derived from the gradient of ln(C₀/Cₜ) versus t [\u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e]. A greater k value typically signifies enhanced photocatalytic efficacy [\u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e49\u003c/span\u003e]. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eb, the \u003cem\u003ek\u003c/em\u003e value for CR degradation by ZIF-8/MnS-3 is approximately 3.61 and 11.46 times those of pure ZIF-8 and MnS, respectively. Furthermore, the photocatalytic performance exhibits a volcano-shaped trend with increasing Mn content, which indicates that excessive Mn has an adverse effect on the generation and separation of photogenerated electron-hole pairs. Catalyst dosage critically affects both efficiency and cost in practical applications. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ec, the ZIF-8/MnS system exhibits optimal CR degradation at 0.5 mg/mL. Degradation efficiency initially increased with dosage (0.25\u0026ndash;2 mg/mL) due to more active sites [\u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e50\u003c/span\u003e, \u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e51\u003c/span\u003e], but declined at higher concentrations from reduced light utilization [\u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e52\u003c/span\u003e]. This optimal dosage effectively balances catalytic performance with material cost. Figure\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ed shows degradation efficiency decreases with increasing initial CR concentration [\u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e53\u003c/span\u003e], dropping from 99.4% to 67.0% within 50 minutes as concentration rises from 10 to 50 mg/L. This decline results from active site saturation and reduced photon penetration at high dye loadings [\u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e54\u003c/span\u003e, \u003cspan citationid=\"CR55\" class=\"CitationRef\"\u003e55\u003c/span\u003e]. During the 30-minute dark adsorption stage, C/C₀ remained near 0.93 across all concentrations, indicating negligible adsorption. The catalyst-free control showed no significant C/C₀ change, confirming CR degradation is entirely photocatalyst-mediated.\u003c/p\u003e \u003cp\u003eIn natural water systems, coexisting anions significantly influence photocatalytic oxidation. We investigated the effects of five common anions (Cl⁻, SO₄\u0026sup2;⁻, CO₃\u0026sup2;⁻, HCO₃⁻, NO₂⁻) on the ZIF-8/MnS system (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ee). Chloride enhances oxidation by reacting with sulfate radicals and \u0026bull;OH to generate chlorine radicals [\u003cspan citationid=\"CR56\" class=\"CitationRef\"\u003e56\u003c/span\u003e, \u003cspan citationid=\"CR57\" class=\"CitationRef\"\u003e57\u003c/span\u003e], while sulfate improves degradation efficiency through its intrinsic oxidizing capability toward pollutants [\u003cspan citationid=\"CR58\" class=\"CitationRef\"\u003e58\u003c/span\u003e]. Nitrite exhibits a modest accelerating effect. Conversely, carbonate and bicarbonate markedly suppress photodegradation by acting as potent \u0026bull;OH scavengers [\u003cspan citationid=\"CR59\" class=\"CitationRef\"\u003e59\u003c/span\u003e, \u003cspan citationid=\"CR60\" class=\"CitationRef\"\u003e60\u003c/span\u003e] and competing with anionic CR for positively charged adsorption sites [\u003cspan citationid=\"CR61\" class=\"CitationRef\"\u003e61\u003c/span\u003e]. Table\u0026nbsp;2 compares the catalytic activity of ZIF-8/MnS for dye degradation with recently reported ZIF-8-based composites.\u003c/p\u003e \u003cp\u003eFor practical applications, photocatalyst stability is crucial. The reusability of ZIF-8/MnS-3 was evaluated through four consecutive cycles under identical conditions. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ef, the CR rate of degradation has fallen to 70.6% in the fourth cycle\u0026mdash;a 28.8% reduction from the first cycle\u0026mdash;this is a result of the loss of catalyst during the recovery process, as well as surface passivation by degradation intermediates that have accumulated. Despite this moderate decline, the composite demonstrates appreciable stability and sustained photocatalytic activity, as corroborated by post-cycling XRD and SEM (Fig. \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e) analyses that revealed no significant structural or morphological alterations.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"No\" id=\"Tabf\" border=\"1\"\u003e \u003ccolgroup cols=\"6\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003eCatalysts\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003ePollutants\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"4\" nameend=\"c6\" namest=\"c3\"\u003e \u003cp\u003eExperimental conditions\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eDegradation\u003c/p\u003e \u003cp\u003e(%)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eLight source\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eTime\u003c/p\u003e \u003cp\u003e(min)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eReference\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eMnS/ZnO\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eTC\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e97.8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e300W Xe lamp (λ\u0026thinsp;\u0026gt;\u0026thinsp;400 nm)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e30\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZIF-8@NH\u003csub\u003e2\u003c/sub\u003e-MIL-125\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eTCH\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e92.9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003evisible LED light\u003c/p\u003e \u003cp\u003eUVC lamps (TUV Philips, 15 W)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e35\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAgNPs/Ag\u003csub\u003e2\u003c/sub\u003eS/ZIF-8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eMG\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e98.6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003evisible LED light\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e50\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e62\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCdZnS@ ZIF\u0026thinsp;\u0026minus;\u0026thinsp;8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eMB\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e99.5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003evisible light\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e63\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZIF-8/NiFe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eMB\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e94\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e500 W halogen lamp\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e120\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e64\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZIF-8 derived ZnO\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eMB\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e76\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eUV lamp/18 W\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e65\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eMoO\u003csub\u003e3\u003c/sub\u003e@ZIF-8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eMB\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e95\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003ePL-XQ 350 W xenon\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e300\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e66\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAg/AgCl@ZIF-8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eMB\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eHg lamp/175 W\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e67\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCdSNPs@ZIF-8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eMB\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e83.2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eUV-visible\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e120\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e68\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZIF-8/Zn-Al LDH\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eMB\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e58\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eUV light/70 W\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e180\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e69\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZIF-8@TiO\u003csub\u003e2\u003c/sub\u003e(0.3% Gd)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eneutral red dye\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e96.55\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eUV\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e70\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAg/AgCl@ZIF-8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eRhB\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e99.12\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e500W Xe lamp(λ\u0026thinsp;\u0026gt;\u0026thinsp;400 nm)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e71\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCuONPs/ZIF-8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eRh6G\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e96.5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eSunlight\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e105\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e72\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZIF-8/g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eRhB\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e99.8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eXe lamp/300 W\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e73\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZIF-8/Ag\u003csub\u003e2\u003c/sub\u003eS\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eRhB\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e100 W Xe and 100 W LED\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e75\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e74\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCuO-ZnO/ZiF-8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eAO7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e98.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eSolar light\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e75\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZIF-8/MnS\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eCR\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e99.4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eUV light\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e30\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003ethis work\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec12\" class=\"Section2\"\u003e \u003ch2\u003e3.3 Photocatalytic mechanism\u003c/h2\u003e \u003cp\u003ePhotoluminescence (PL) spectroscopy at 320 nm excitation is used to evaluate photogenerated carrier separation efficiency. In general, PL intensity is inversely related to the rate of carrier separation and directly proportional to the recombination rate [\u003cspan additionalcitationids=\"CR77\" citationid=\"CR76\" class=\"CitationRef\"\u003e76\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR78\" class=\"CitationRef\"\u003e78\u003c/span\u003e]. Figure\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ea shows emission peaks near 420 nm for all photocatalysts. ZIF-8/MnS composites exhibit lower peak intensity than ZIF-8, indicating suppressed carrier recombination and enhanced separation. ZIF-8/MnS-4 shows the lowest intensity, suggesting optimal interfacial interaction between ZIF-8 and MnS that most effectively inhibits recombination, thereby maximizing active species generation and photocatalytic performance.\u003c/p\u003e \u003cp\u003eThe investigation into charge separation and transfer in ZIF-8/MnS photocatalysts is conducted through the utilisation of two analytical techniques: transient photocurrent response (TPR) and electrochemical impedance spectroscopy (EIS). It can be posited that an enhanced photocurrent is indicative of an optimised carrier separation efficiency [\u003cspan citationid=\"CR79\" class=\"CitationRef\"\u003e79\u003c/span\u003e]. Figure\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eb shows ZIF-8/MnS composites exhibit enhanced photocurrent compared to pristine ZIF-8, demonstrating MnS incorporation accelerates charge separation and extends carrier lifetime. EIS Nyquist plots (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ec) reveal arc radius corresponds to charge transfer resistance (Rct) [\u003cspan citationid=\"CR80\" class=\"CitationRef\"\u003e80\u003c/span\u003e, \u003cspan citationid=\"CR81\" class=\"CitationRef\"\u003e81\u003c/span\u003e]. ZIF-8 displays the largest radius, while ZIF-8/MnS composites showed composition-dependent decreases, indicating improved charge mobility. Linear sweep voltammetry (LSV) (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ed) confirms reduced electron transfer resistance and suppressed recombination [\u003cspan citationid=\"CR82\" class=\"CitationRef\"\u003e82\u003c/span\u003e]. The cyclic voltammetry (CV) curve (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ee) shows the ZIF-8/MnS composite's current density is between those of pure MnS and ZIF-8, indicating the heterostructure inherits combined electrochemical properties. The electrochemical double-layer capacitance (C\u003csub\u003edl\u003c/sub\u003e), measured by cyclic voltammetry (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ef), reflects the electrochemically active surface area. Furthermore, ZIF-8/MnS-3 exhibits a C\u003csub\u003edl\u003c/sub\u003e of 4.5737 mF/cm\u0026sup2;, which is 182 times that of ZIF-8 (0.0251 mF/cm\u0026sup2;), indicating substantially more accessible active sites and enhanced photocatalytic performance.\u003c/p\u003e \u003cp\u003eAn exhaustive analysis of the optical response characteristics of ZF-8, MnS and ZF-8/MnS is conducted by means of diffuse reflectance spectroscopy (DRS) spectroscopy. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ea, ZIF-8 exhibits UV absorption only below 259 nm, with a negligible visible-light response. MnS absorbs strongly in both UV and visible regions. The ZIF-8/MnS composites show red-shifted absorption edges and enhanced light-harvesting capacity compared to pristine ZIF-8. It is generally that it has been demonstrated that the photocatalytic performance of a material is contingent upon the width of its absorption range in relation to the narrowness of its band gap [\u003cspan citationid=\"CR83\" class=\"CitationRef\"\u003e83\u003c/span\u003e], indicating that the introduction of MnS in ZIF-8 could enhance the photocatalytic activity. Band gap energies (E\u003csub\u003eg\u003c/sub\u003e) were determined from Tauc plots (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003eb): ZIF-8 (5.12 eV), MnS (3.66 eV), and the ZIF-8/MnS1-4 composites are 5.01 eV, 4.94 eV, 3.37 eV, and 3.31 eV, respectively. The progressive band gap narrowing with increasing MnS content demonstrates tunable electronic structure. This heterojunction architecture simultaneously broadens the spectral response range and reduces the band gap, synergistically enhancing photocatalytic efficiency.\u003c/p\u003e \u003cp\u003eSemiconductor type and flat-band potentials (E\u003csub\u003efb\u003c/sub\u003e) were determined by Mott-Schottky (M-S) analysis. As shown in Figs.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ec-d ZIF-8 exhibits n-type behaviour, as indicated by a positive slope, while MnS demonstrates p-type characteristics, as evidenced by a negative slope [\u003cspan citationid=\"CR84\" class=\"CitationRef\"\u003e84\u003c/span\u003e]. The E\u003csub\u003efb\u003c/sub\u003e values for ZIF-8 and MnS were \u0026minus;\u0026thinsp;1.75 and 1.05 V (vs. Ag/AgCl), respectively. The band structure was calculated using the following equation.\u003c/p\u003e \u003cp\u003eE\u003csub\u003eNHE\u003c/sub\u003e = E\u003csub\u003eAg/AgCl\u003c/sub\u003e + 0.2 V (1)\u003c/p\u003e \u003cp\u003eE\u003csub\u003eVB\u003c/sub\u003e = E\u003csub\u003eg\u003c/sub\u003e + E\u003csub\u003eCB\u003c/sub\u003e (2)\u003c/p\u003e \u003cp\u003eAs per formula 1, the flat-band potentials of ZIF-8 and MnS were computed as -1.55 and 1.25 V (vs. NHE) correspondingly, employing Eq.\u0026nbsp;(1). For n-type semiconductors, E\u003csub\u003efb\u003c/sub\u003e is typically\u0026thinsp;~\u0026thinsp;0.1 eV above the conduction band edge (E\u003csub\u003eCB\u003c/sub\u003e) [\u003cspan citationid=\"CR85\" class=\"CitationRef\"\u003e85\u003c/span\u003e], for p-type, E\u003csub\u003efb\u003c/sub\u003e is ~\u0026thinsp;0.1 eV below the valence band edge (E\u003csub\u003eVB\u003c/sub\u003e) [\u003cspan citationid=\"CR86\" class=\"CitationRef\"\u003e86\u003c/span\u003e]. Thus, the E\u003csub\u003eCB\u003c/sub\u003e of ZIF-8 is -1.65 V (vs. NHE), and the E\u003csub\u003eVB\u003c/sub\u003e of MnS is 1.35 V (vs. NHE). Given band gap energies (E\u003csub\u003eg\u003c/sub\u003e) of 5.12 eV for ZIF-8 and 3.66 eV for MnS, Eq.\u0026nbsp;(2) yields an E\u003csub\u003eVB\u003c/sub\u003e of 3.47 V vs. NHE for ZIF-8 and an E\u003csub\u003eCB\u003c/sub\u003e of -2.31 V vs. NHE for MnS.\u003c/p\u003e \u003cp\u003eDensity functional theory (DFT) calculations reveal HOMO-LUMO gaps of 4.67 eV for the ZIF-8 characteristic cluster model and 3.13 eV for the MnS unit cell model (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e3\u003c/span\u003e), which agrees well with experimental UV-Vis DRS data. This validates our computational approach and its ability to capture the electronic structure of these materials. Orbital distribution analysis (Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003ea) shows that the HOMO of ZIF-8 is localized on the imidazole ligands, while the LUMO resides at the Zn-N cluster center, indicating directional ligand-to-metal charge transfer upon photoexcitation. For MnS, both HOMO and LUMO arise primarily from Mn 3d and S 3p orbitals, exhibiting strong spatial localization that may hinder photogenerated carrier separation and mobility. Electrostatic potential mapping (Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003eb) identifies negative potential extrema (in red) around the imidazole nitrogen atoms in ZIF-8, which can electrostatically adsorb cationic pollutants and facilitate interfacial electron transfer. In the ZIF-8/MnS heterojunction, this complementary potential distribution drives directional migration of photogenerated electrons from ZIF-8 to MnS while promoting hole transfer in the opposite direction. This charge transfer pathway aligns perfectly with the proposed Z-scheme mechanism. DFT results thus provide direct theoretical evidence for the matched band structure and favorable interfacial charge distribution in the Z-type ZIF-8/MnS heterojunction.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 3\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eFrontier orbital energy levels and band gaps of ZIF-8 cluster and MnS unit cell\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"4\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSample\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eHOMO (eV)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eLUMO (eV)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eBand gap (eV)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZIF-8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e-6.44\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e-1.77\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e4.67\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eMnS\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e-4.99\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e-1.86\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e3.13\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eThe active species governing CR photodegradation were identified through scavenging experiments using 2 mmol of BQ, IPA, and EDTA as traps for \u0026bull;O₂⁻, \u0026bull;OH, and h⁺, respectively [\u003cspan citationid=\"CR87\" class=\"CitationRef\"\u003e87\u003c/span\u003e, \u003cspan citationid=\"CR88\" class=\"CitationRef\"\u003e88\u003c/span\u003e]. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003ec, It is evident that EDTA and BQ exhibit a substantial inhibitory effect on the degradation efficiency, while IPA showed only weak suppression, establishing the h⁺ and \u0026bull;O₂⁻ as the primary reactive species.\u003c/p\u003e \u003cp\u003eBased on band alignment and scavenger experiments, a direct Z-scheme mechanism is proposed (Fig. 9). Under simulated sunlight irradiation, electrons in both ZIF-8 and MnS are excited from their valence bands (VB) to conduction bands (CB). Driven by the interfacial band potential gradient, electrons in the ZIF-8 CB spontaneously transfer to the MnS VB and recombine with holes there, achieving directional charge separation. This Z-scheme preserves highly reductive electrons in the MnS CB and strongly oxidative holes in the ZIF-8 VB. Subsequently, MnS CB electrons reduce O₂ to \u0026bull;O₂⁻ (E\u003csup\u003e\u0026theta;\u003c/sup\u003e(O₂/\u0026bull;O₂⁻) = -0.33 V vs. NHE), while ZIF-8 VB holes oxidize H₂O (or OH⁻) to \u0026bull;OH (E\u003csup\u003e\u0026theta;\u003c/sup\u003e(H₂O/\u0026bull;OH) = +2.27 V vs. NHE). These reactive species, together with MnS VB holes that directly oxidize CR, initiate a cascade degradation process that generates short-chain intermediates en route to complete mineralization into CO₂ and H₂O. By suppressing charge recombination and maintaining robust redox potentials, this Z-scheme architecture significantly enhances degradation efficiency.\u0026nbsp;The proposed photocatalytic degradation pathway proceeds as follows:\u003c/p\u003e\n\u003cp\u003eZIF-8 + \u003cem\u003eh\u003c/em\u003e\u003cem\u003en\u003c/em\u003e \u0026reg;\u0026nbsp;ZIF-8 (h\u003csup\u003e+\u003c/sup\u003e) + ZIF-8 (e\u003csup\u003e-\u003c/sup\u003e)\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eMnS + \u003cem\u003eh\u003c/em\u003e\u003cem\u003en\u003c/em\u003e \u0026reg;\u0026nbsp;MnS (h\u003csup\u003e+\u003c/sup\u003e)\u0026nbsp;+ MnS (e\u003csup\u003e-\u003c/sup\u003e)\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eZIF-8 (e\u003csup\u003e-\u003c/sup\u003e) + MnS (h\u003csup\u003e+\u003c/sup\u003e)\u0026nbsp;\u0026reg;\u0026nbsp;ZIF-8/MnS(e\u003csup\u003e-\u0026nbsp;\u003c/sup\u003e+ h\u003csup\u003e+\u003c/sup\u003e)\u003c/p\u003e\n\u003cp\u003eMnS (e\u003csup\u003e-\u003c/sup\u003e) + O\u003csub\u003e2\u003c/sub\u003e \u0026reg;\u0026nbsp;\u0026bull;O₂⁻\u003c/p\u003e\n\u003cp\u003eZIF-8 (h\u003csup\u003e+\u003c/sup\u003e) + H\u003csub\u003e2\u003c/sub\u003eO/OH\u003csup\u003e-\u003c/sup\u003e\u0026reg;\u0026nbsp;\u0026bull;OH\u003c/p\u003e\n\u003cp\u003e\u0026bull;O₂⁻ +H\u003csub\u003e2\u003c/sub\u003eO\u0026nbsp;\u0026reg;\u0026nbsp;2 \u0026bull;OH +2OH\u003csup\u003e-\u003c/sup\u003e\u003c/p\u003e\n\u003cp\u003eActive species (O₂⁻, h\u003csup\u003e+\u003c/sup\u003e, \u0026bull;OH) + CR \u0026reg; Intermediate products, CO₂ + H₂O\u003c/p\u003e\u003c/div\u003e"},{"header":"4 Conclusions","content":"\u003cp\u003eIn summary, we successfully fabricated a ZIF-8/MnS Z-scheme heterojunction for the degradation of organic pollutants through photocatalysis. Our findings demonstrate that this Z-scheme configuration significantly enhances photocatalytic efficiency by widening light absorption, improving the separation of photogenerated carriers, and decreasing charge transfer resistance. Specifically, the optimal composite ZIF-8/MnS achieved nearly 100% CR removal within 30 minutes and demonstrated stable photocatalytic performance over four consecutive cycles, showcasing excellent photoelectrochemical stability. Radical trapping experiments confirmed that \u0026bull;O₂⁻ and \u0026bull;OH are the primary reactive species. The work provides a rational design strategy for developing efficient, stable MOF-based sulfide heterojunction photocatalysts for organic pollutant treatment.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eDeclaration of competing interest\u003c/h2\u003e \u003cp\u003eThe authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.\u003c/p\u003e \u003c/p\u003e\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eMin Zhou: Methodology, Investigation, Data curation, writing-original draft. Yancheng Wu: Methodology, formal analysis, Data curation; Wenbo Zhang: Formal analysis, Data curation; Xiao-fang Li: General concept, funding acquisition, project administration; Xiaofiang Feng: Methodology, conceptualization, methodology, funding acquisition, project administration.\u003c/p\u003e\u003ch2\u003eAcknowledgement\u003c/h2\u003e\u003cp\u003eNone\u003c/p\u003e\u003ch2\u003eData availability\u003c/h2\u003e \u003cp\u003eData will be made available on request.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eP.W. Li, T. Zhao, Z.H. Zhao, H.X. Tang, W.S. Feng, Z.J. Zhang, Biochar derived from Chinese herb medicine residues for Rhodamine B dye adsorption. ACS Omega. \u003cb\u003e8\u003c/b\u003e, 4813\u0026ndash;4825 (2023). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1021/acsomega.2c06968\u003c/span\u003e\u003cspan address=\"10.1021/acsomega.2c06968\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZ.Z. Yin, M. Li, Z.W. Chen, X.X. Chen, K.Y. Liu, D.P. Zhou, M.S. Xue, J.F. Ou, Y. Xie, S. Lei, C. Xie, Y.D. Luo, A superhydrophobic pulp/cellulose nanofiber (CNF) membrane via coating ZnO suspensions for multifunctional applications. Ind. Crop Prod. \u003cb\u003e187\u003c/b\u003e, 115526 (2022). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/J.INDCROP.2022.115526\u003c/span\u003e\u003cspan address=\"10.1016/J.INDCROP.2022.115526\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eX.F. Li, R.X. Li, X.Q. Feng, Efficient adsorption and photocatalytic degradation of organic pollutant by Ag₃PO₄/ZnO/chitosan-biochar composites. Russ J. Inorg. Chem. \u003cb\u003e68\u003c/b\u003e, 1386\u0026ndash;1398 (2023). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1134/S0036023623601307\u003c/span\u003e\u003cspan address=\"10.1134/S0036023623601307\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eE. Fosso-Kankeu, H. Mittal, S.B. Mishra, A.K. Mishra, Gum ghatti and acrylic acid based biodegradable hydrogels for the effective adsorption of cationic dyes. J. Ind. Eng. Chem. \u003cb\u003e22\u003c/b\u003e, 171\u0026ndash;178 (2015). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.jiec.2014.07.007\u003c/span\u003e\u003cspan address=\"10.1016/j.jiec.2014.07.007\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eD. Liu, K.H. Li, L. Zhou, J.Y. Lei, L.Z. Wang, J.L. Zhang, Y.D. Liu, N, O co-doping enhanced the ability of carbon/Fe composites for peroxymonosulfate activation to degrade sulfadiazine: the advantages of nitrate saturated MOFs as precursors. Sep. Purif. Technol. \u003cb\u003e314\u003c/b\u003e, 123556 (2023). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.seppur.2023.123556\u003c/span\u003e\u003cspan address=\"10.1016/j.seppur.2023.123556\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eS.P. Keerthana, R. Yuvakkumar, G. Ravi, S.I. Hong, G. Abdullah, Fabrication of Ce doped TiO₂ for efficient organic pollutants removal from wastewater. Chemosphere. \u003cb\u003e29\u003c/b\u003e, 133540 (2022). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.chemosphere.2022.133540\u003c/span\u003e\u003cspan address=\"10.1016/j.chemosphere.2022.133540\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eI.I. Albanio, P.C.L. Muraro, W.L. da Silva, Rhodamine B dye adsorption onto biochar from olive biomass waste. Water Air Soil. Pollut. \u003cb\u003e232\u003c/b\u003e, 214 (2021). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/s11270-021-05117-8\u003c/span\u003e\u003cspan address=\"10.1007/s11270-021-05117-8\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eQ.D. Zha, Y.K. Yao, Z.Z. Yin, Y.T. Deng, Z.H. Li, Y. Xie, Y.H. Chen, C.G. Yang, Y.D. Luo, M.S. Xue, Facile construction of multifunctional 3D smart MOF-based polyurethane sponges with photocatalytic ability for efficient separation of oil-in-water emulsions and co-existing organic pollutant. Chem. Eng. J. \u003cb\u003e490\u003c/b\u003e, 51747 (2024). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.cej.2024.51747\u003c/span\u003e\u003cspan address=\"10.1016/j.cej.2024.51747\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eR. Kishor, D. Purchase, G.D. Saratale, R.G. Saratale, L.F.R. Ferreira, M. Bilal, R. Chandra, Ecotoxicological and health concerns of persistent coloring pollutants of textile industry wastewater and treatment approaches for environmental safety. J. Environ. Chem. Eng. \u003cb\u003e9\u003c/b\u003e, 105012 (2021). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.jece.2021.105012\u003c/span\u003e\u003cspan address=\"10.1016/j.jece.2021.105012\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eM.F. Chowdhury, S. Khandaker, F. Sarker, A. Islam, M.T. Rahman, Current treatment technologies and mechanisms for removal of indigo carmine dyes from wastewater: a review. J. Mol. Liq. \u003cb\u003e318\u003c/b\u003e, 114061 (2020). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.molliq.2020.114061\u003c/span\u003e\u003cspan address=\"10.1016/j.molliq.2020.114061\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eH. Chen, X. Yu, X. Wang, Y. He, C. Zhang, G. Xue, Z. Liu, H. Lao, H. Song, W. Chen, Y. Qian, A. Zhang, X. Li, Dyeing and finishing wastewater treatment in China: state of the art and perspective. J. Clean. Prod. \u003cb\u003e326\u003c/b\u003e, 129353 (2021). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.jclepro.2021.129353\u003c/span\u003e\u003cspan address=\"10.1016/j.jclepro.2021.129353\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eH. Wu, S. Wang, Impacts of operating parameters on oxidation-reduction potential and pretreatment efficacy in the pretreatment of printing and dyeing wastewater by Fenton process. J. Hazard. Mater. \u003cb\u003e243\u003c/b\u003e, 86\u0026ndash;94 (2012). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.jhazmat.2012.08.025\u003c/span\u003e\u003cspan address=\"10.1016/j.jhazmat.2012.08.025\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJ.C. Cardoso, G.G. Bessegato, M.V. Boldrin, Zanoni, Efficiency comparison of ozonation, photolysis, photocatalysis and photoelectrocatalysis methods in real textile wastewater decolorization. Water Res. \u003cb\u003e98\u003c/b\u003e, 39\u0026ndash;46 (2016). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.watres.2016.04.025\u003c/span\u003e\u003cspan address=\"10.1016/j.watres.2016.04.025\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eH. Lin, W. Peng, M. Zhang, J. Chen, H. Hong, Y. Zhang, A review on anaerobic membrane bioreactors: applications, membrane fouling and future perspectives. Desalination. \u003cb\u003e314\u003c/b\u003e, 169\u0026ndash;188 (2013). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.desal.2012.11.027\u003c/span\u003e\u003cspan address=\"10.1016/j.desal.2012.11.027\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJ. Liu, Q.H. Dai, R.X. Xiao, T.T. Zhou, J.L. Han, B. Fu, Immobilization of ZnIn₂S₄ on sodium alginate foam for efficient hexavalent chromium removal. Int. J. Biol. Macromol. \u003cb\u003e236\u003c/b\u003e, 123848 (2023). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.ijbiomac.2023.123848\u003c/span\u003e\u003cspan address=\"10.1016/j.ijbiomac.2023.123848\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eB. Liu, Z. Li, S. Xu, X. Ren, D. Han, D. Lu, Facile in situ hydrothermal synthesis of BiVO₄/MWCNT nanocomposites as high performance visible-light driven photocatalysts. J. Phys. Chem. Solids. \u003cb\u003e75\u003c/b\u003e, 977\u0026ndash;983 (2014). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.jpcs.2014.07.015\u003c/span\u003e\u003cspan address=\"10.1016/j.jpcs.2014.07.015\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eX. Li, N. Yang, T. Xu, Y. Yang, Y.F. Lv, Enhancing visible-light photocatalytic activity of AgCl photocatalyst by CeO₂ modification for degrading multiple organic pollutants. Nanomaterials. \u003cb\u003e15\u003c/b\u003e, 537 (2025). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.3390/nano15070537\u003c/span\u003e\u003cspan address=\"10.3390/nano15070537\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eX.F. Zhang, C. Han, W.L. Xu, Imaging analysis of scanning electrochemical microscopy in energy catalysis. Chem. Biomol. Imaging. \u003cb\u003e1\u003c/b\u003e, 205\u0026ndash;219 (2023). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1021/cbmi.2c00008\u003c/span\u003e\u003cspan address=\"10.1021/cbmi.2c00008\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eY.J. Chen, J. Hao, Z.H. Yin, Q.H. Wang, Y.T. Zhou, L.P. Jia, H.M. Li, W.L. Liao, K.P. Liu, An accuracy improved ratiometric SERS sensor for rhodamine 6G in chili powder using a metal-organic framework support. RSC Adv. \u003cb\u003e13\u003c/b\u003e, 10135\u0026ndash;10143 (2023). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1039/d3ra00790a\u003c/span\u003e\u003cspan address=\"10.1039/d3ra00790a\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eU. Marta P\u0026eacute;rez-Miana, Javier, J. Res\u0026eacute;ndiz-Ord\u0026oacute;\u0026ntilde;ez, Coronas, Solventless synthesis of ZIF-L and ZIF-8 with hydraulic press and high temperature. Microporous Mesoporous Mater. \u003cb\u003e328\u003c/b\u003e, 111487 (2021). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.micromeso.2021.111487\u003c/span\u003e\u003cspan address=\"10.1016/j.micromeso.2021.111487\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eT.T. Li, Y.J. Fan, X.X. Cen, Y. Wang, B.C. Shiu, H.T. Ren, H.K. Peng, Q. Jiang, C.W. Lou, J.H. Lin, Polypropylene/polyvinyl alcohol/metal-organic framework-based melt-blown electrospun composite membranes for highly efficient filtration of PM\u003csub\u003e2.5\u003c/sub\u003e, Nanomaterials, 10 (2020) 2025. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.3390/nano10102025\u003c/span\u003e\u003cspan address=\"10.3390/nano10102025\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eG.F. Huang, Y.J. Zhang, R.R. Zhang, M.Y. Zhang, L.W. Zhang, Y.F. Xin, Y.Y. Liu, J.F. Chen, Removal of methyl orange and methylene blue by bimetallic zinc/cobalt metal-organic skeleton/carbon nanotubes (Zn/Co-ZIF@CNTs). RSC Adv. \u003cb\u003e15\u003c/b\u003e, 4681\u0026ndash;4692 (2025). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1039/D4RA07021F\u003c/span\u003e\u003cspan address=\"10.1039/D4RA07021F\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eL.H. Feng, X.F. Zhang, Z.K. Jin, J.S. Chen, X. Duan, S.Y. Ma, T.F. Xia, An anionic porous indium-organic framework with nitrogen-rich linker for efficient and selective removal of trace cationic dyes. Molecules. \u003cb\u003e28\u003c/b\u003e, 4980 (2023). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.3390/molecules28134980\u003c/span\u003e\u003cspan address=\"10.3390/molecules28134980\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eP.Q. Li, J.J. Qian, L. Du, Q.H. Zhao, Zinc-tetracarboxylate framework material with nano-cages and one-dimensional channels for excellent selective and effective adsorption of methyl blue dye. RSC Adv. \u003cb\u003e10\u003c/b\u003e, 3539\u0026ndash;3543 (2020). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1039/c9ra08983g\u003c/span\u003e\u003cspan address=\"10.1039/c9ra08983g\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eY. Meng, W.H. Zhou, D.X. Kou, Z.J. Zhou, Y.N. Meng, S.X. Wu, Cu₂ZnSnS₄ decorated CdS nanorods for enhanced visible-light-driven photocatalytic hydrogen production. Int. J. Hydrog Energy. \u003cb\u003e43\u003c/b\u003e, 20408\u0026ndash;20416 (2018). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.ijhydene.2018.09.161\u003c/span\u003e\u003cspan address=\"10.1016/j.ijhydene.2018.09.161\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eI. Muhammad, A.B. Yousaf, F. Muhammad, P. Kasak, Enhanced Z-scheme visible light photocatalytic hydrogen production over α-Bi₂O₃/CZS heterostructure. Int. J. Hydrog Energy. \u003cb\u003e43\u003c/b\u003e, 4256\u0026ndash;4264 (2018). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.ijhydene.2018.01.056\u003c/span\u003e\u003cspan address=\"10.1016/j.ijhydene.2018.01.056\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZ.Y. Fan, Z.L. Wang, Y.Q. Wang, J. Li, Y. Xie, Y. Ling, Y. Chen, In₂S₃-modified ZnIn₂S₄ enhanced photogenerated carrier separation efficiency and photocatalytic hydrogen evolution under visible light. Fuel. \u003cb\u003e373\u003c/b\u003e, 132401 (2024). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/J.FUEL.2024.132401\u003c/span\u003e\u003cspan address=\"10.1016/J.FUEL.2024.132401\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eH. Li, Y.L. Cheng, J.X. Li, T.H. Li, J. Zhu, W.B. Deng, J.J. Zhu, D.L. He, Preparation and adsorption performance study of graphene quantum dots@ZIF-8 composites for highly efficient removal of volatile organic compounds. Nanomaterials. \u003cb\u003e12\u003c/b\u003e, 4008 (2022). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.3390/nano12224008\u003c/span\u003e\u003cspan address=\"10.3390/nano12224008\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eL.L. Dai, M.J. Yao, Z.X. Fu, X. Li, X.M. Zheng, S.Y. Meng, Z. Yuan, K.Y. Cai, H. Yang, Y.L. Zhao, Multifunctional metal-organic framework-based nanoreactor for starvation/oxidation improved indoleamine 2,3-dioxygenase-blockade tumor immunotherapy. Nat. Commun. \u003cb\u003e13\u003c/b\u003e, 2688 (2022). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1038/S41467-022-30436-Y\u003c/span\u003e\u003cspan address=\"10.1038/S41467-022-30436-Y\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eG.L. Zuo, Y.X. Fu, H. Zhou, J. Du, X. Ding, H.Y. Ye, S-scheme MnS/ZnO heterojunction composites for photocatalytic degradation of tetracycline. J. Mater. Sci. : Mater. Electron. \u003cb\u003e36\u003c/b\u003e, 745 (2025). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/S10854-025-14823-X\u003c/span\u003e\u003cspan address=\"10.1007/S10854-025-14823-X\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eA. Das, D.Y. Liu, R.R. Wary, A.S. Vasenko, O.V. Prezhdo, R.G. Nair, Mn-modified ZnO nanoflakes for optimal photoelectrochemical performance under visible light: experimental design and theoretical rationalization. J. Phys. Chem. Lett. \u003cb\u003e14\u003c/b\u003e, 9604\u0026ndash;9611 (2023). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1021/acs.jpclett.3c02730\u003c/span\u003e\u003cspan address=\"10.1021/acs.jpclett.3c02730\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eC. Chang, L.Y. Zhu, S.F. Wang, X.L. Chu, L.F. Yue, A novel mesoporous graphite carbon nitride/BiOI heterojunction for enhancing photocatalytic performance under visible light irradiation. ACS Appl. Mater. Interfaces. \u003cb\u003e6\u003c/b\u003e, 5083\u0026ndash;5093 (2014). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1021/am4057488\u003c/span\u003e\u003cspan address=\"10.1021/am4057488\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eK. Li, M.M. Chen, L. Chen, S.Y. Zhao, W.B. Pan, P. Li, Y.C. Han, Adsorption of tetracycline from aqueous solution by ZIF-8: isotherms, kinetics and thermodynamics. Environ. Res. \u003cb\u003e241\u003c/b\u003e, 117588 (2023). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.envres.2023.117588\u003c/span\u003e\u003cspan address=\"10.1016/j.envres.2023.117588\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJ.H. Ran, H.B. Chen, S.G. Bi, Q.F. Guo, Z.M. Deng, G.M. Cai, D.S. Cheng, X.N. Tang, X. Wang, One-step in-situ growth of zeolitic imidazole frameworks-8 on cotton fabrics for photocatalysis and antimicrobial activity. Cellulose. \u003cb\u003e27\u003c/b\u003e, 10867\u0026ndash;10879 (2020). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/s10570-020-03483-1\u003c/span\u003e\u003cspan address=\"10.1007/s10570-020-03483-1\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eX. Bo, C.R. Yang, M. Chang, D.H. Liu, Structural design of core-shell ZIF-8@NH₂-MIL-125 photocatalyst for synergistic adsorption-photocatalytic degradation of tetracycline hydrochloride. J. Alloys Compd. \u003cb\u003e973\u003c/b\u003e, 172850 (2024). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.jallcom.2023.172850\u003c/span\u003e\u003cspan address=\"10.1016/j.jallcom.2023.172850\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eR.G. Yang, Y.M. Fu, H.N. Wang, D.P. Zhang, Z. Zhou, Y.Z. Cheng, X. Meng, Y.O. He, Z.M. Su, ZIF-8/covalent organic framework for enhanced CO₂ photocatalytic reduction in gas-solid system. Chem. Eng. J. \u003cb\u003e450\u003c/b\u003e, 138040 (2022). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.cej.2022.138040\u003c/span\u003e\u003cspan address=\"10.1016/j.cej.2022.138040\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eQ. Cui, H. Li, F.J. Wang, Z.M. Li, H. Li, Y. Song, H.T. Wu, X.Z. Wang, S.S. Chen, In situ fabrication of ZIF-8 Shell on Polyamidoxime nanofibers for enhanced uranium extraction from seawater through a synergistic effect. Desalination. \u003cb\u003e621\u003c/b\u003e, 119741\u0026ndash;119741 (2025). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/J.DESAL.2025.119741\u003c/span\u003e\u003cspan address=\"10.1016/J.DESAL.2025.119741\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eY.C. Pang, X.H. Zang, H.D. Li, J.Y. Liu, Q.Y. Chang, S.H. Zhang, C. Wang, Z. Wang, Solid-phase microextraction of organophosphorous pesticides from food samples with a nitrogen-doped porous carbon derived from g-C₃N₄ templated MOF as the fiber coating. J. Hazard. Mater. \u003cb\u003e384\u003c/b\u003e, 121430 (2020). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.jhazmat.2019.121430\u003c/span\u003e\u003cspan address=\"10.1016/j.jhazmat.2019.121430\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eX.R. Hu, J.H. Hou, L. Pang, Z.G. Feng, J.H. Liu, H.Y. Feng, Y. Kong, C. Liu, MIL-125@ZIF-8 based solid phase microextraction coating for sensitive determination of organophosphate esters in aqueous environments. Microchim Acta. \u003cb\u003e192\u003c/b\u003e, 269 (2025). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/s00604-025-07127-8\u003c/span\u003e\u003cspan address=\"10.1007/s00604-025-07127-8\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eY.R. Zhu, R. Zhao, Y.T. Xu, W.H. Chen, Z.L. Hu, L.J. Xi, Y.J. Xie, H.S. Hou, T.C. Liu, K. Amine, X.B. Ji, G.Q. Zou, Anion vacancies coupling with heterostructures enable advanced aerogel cathode for ultrafast aqueous zinc-ion storage. Adv. Mater. \u003cb\u003e37\u003c/b\u003e, e2419582 (2025). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1002/adma.202419582\u003c/span\u003e\u003cspan address=\"10.1002/adma.202419582\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eC.C. Guo, R.Y. Zhou, X.R. Liu, R.Y. Tang, W.X. Xi, Y.R. Zhu, Activating the MnS\u003csub\u003e0.5\u003c/sub\u003eSe\u003csub\u003e0.5\u003c/sub\u003e microspheres as high-performance cathode materials for aqueous zinc-ion batteries: insight into in situ electrooxidation behavior and energy storage mechanisms. Small. \u003cb\u003e15\u003c/b\u003e, e2306237\u0026ndash;e2306237 (2023). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1002/smll.202306237\u003c/span\u003e\u003cspan address=\"10.1002/smll.202306237\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZ. Qiao, T. Yan, W. Li, B. Huang, In situ anion exchange synthesis of In₂S₃/In(OH)₃ heterostructures for efficient photocatalytic degradation of MO under solar ligh. New. J. Chem. \u003cb\u003e41\u003c/b\u003e, 3134\u0026ndash;3142 (2017). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1039/c6nj04119a\u003c/span\u003e\u003cspan address=\"10.1039/c6nj04119a\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eG.S. Lekshmi, T. Ramasamy, O. Bazaka, I. Levchenko, K. Bazaka, R. Govindan, M. Mandhakini, Antioxidant, anti-bacterial, and Congo red dye degradation activity of AgₓO-decorated mustard oil-derived rGO nanocomposites. Molecules. \u003cb\u003e27\u003c/b\u003e, 5950 (2022). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.3390/molecules27185950\u003c/span\u003e\u003cspan address=\"10.3390/molecules27185950\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZ.L. Mo, D.Z. Tai, H. Zhang, A. Shahab, A comprehensive review on the adsorption of heavy metals by zeolite imidazole framework (ZIF-8) based nanocomposite in water. Chem. Eng. J. \u003cb\u003e443\u003c/b\u003e, 136320 (2022). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.cej.2022.136320\u003c/span\u003e\u003cspan address=\"10.1016/j.cej.2022.136320\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eH. Yang, S. Hu, H. Zhao, X.F. Luo, Y. Liu, C.F. Deng, Y.L. Yu, T.D. Hu, S.Y. Shan, Y.F. Zhi, H.Y. Su, L.H. Jiang, High-performance Fe-doped ZIF-8 adsorbent for capturing tetracycline from aqueous solution. J. Hazard. Mater. \u003cb\u003e416\u003c/b\u003e, 126046 (2021). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.jhazmat.2021.126046\u003c/span\u003e\u003cspan address=\"10.1016/j.jhazmat.2021.126046\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJ. Wang, K.P. Shi, W.J. Liu, L. Yin, Y. Xu, D.S. Kong, L.X. Ni, Y.R. Yao, S.Y. Li, Y. Zhang, S.G. Yang, H. He, Novel ZIF-8@CHs catalysts for photocatalytic degradation of tetracycline hydrochloride. Chem. Eng. J. \u003cb\u003e461\u003c/b\u003e, 142130 (2023). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.cej.2023.142130\u003c/span\u003e\u003cspan address=\"10.1016/j.cej.2023.142130\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZ.Y. Wang, J.F. Li, Y.Q. Qiao, X.M. Liu, Y.F. Zheng, Z.Y. Li, J. Shen, Y. Zhang, S.L. Zhu, H. Jiang, Y.Q. Liang, Z.D. Cui, P.K. Chu, S.L. Wu, Rapid ferroelectric-photoexcited bacteria-killing of Bi₄Ti₃O₁₂/Ti₃C₂Tₓ nanofiber membranes. Adv. Fiber Mater. \u003cb\u003e5\u003c/b\u003e, 11\u0026ndash;13 (2022). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/s42765-022-00234-8\u003c/span\u003e\u003cspan address=\"10.1007/s42765-022-00234-8\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eN. Kumaresan, M.A.A.S. Sinthiya, K. Ramamurthi, R.R.B. Babu, K. Sethuraman, Visible light driven photocatalytic activity of ZnO/CuO nanocomposites coupled with rGO heterostructures synthesized by solid-state method for RhB dye degradation. Arab. J. Chem. \u003cb\u003e13\u003c/b\u003e, 3910\u0026ndash;3928 (2020). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.arabjc.2019.03.002\u003c/span\u003e\u003cspan address=\"10.1016/j.arabjc.2019.03.002\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eW. Shao, Y.R. Chen, F. Xie, H. Zhang, H.T. Wang, N. Chang, Facile construction of a ZIF-67/AgCl/Ag heterojunction via chemical etching and surface ion exchange strategy for enhanced visible light driven photocatalysis. RSC Adv. \u003cb\u003e10\u003c/b\u003e, 38174\u0026ndash;38183 (2020). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1039/D0RA06842J\u003c/span\u003e\u003cspan address=\"10.1039/D0RA06842J\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eW. Luo, W.Y. Huang, X.Q. Feng, Y. Huang, X.W. Song, H.F. Lin, S.F. Wang, G. Mailhot, The utilization of Fe-doped g-C₃N₄ in a heterogeneous photo-Fenton-like catalytic system: the effect of different parameters and a system mechanism investigation. RSC Adv. \u003cb\u003e10\u003c/b\u003e, 21876\u0026ndash;21886 (2020). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1039/D0RA00993H\u003c/span\u003e\u003cspan address=\"10.1039/D0RA00993H\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eP. Dhiman, G. Sharma, A.N. Alodhayb, A. Kumar, G. Rana, T. Sithole, Z.A. AlOthman, Constructing a visible-active CoFe₂O₄@Bi₂O₃/NiO nanoheterojunction as magnetically recoverable photocatalyst with boosted ofloxacin degradation efficiency. Molecules. \u003cb\u003e27\u003c/b\u003e, 8234 (2022). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.3390/molecules27238234\u003c/span\u003e\u003cspan address=\"10.3390/molecules27238234\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eF. Chen, Q. Yang, J. Sun, F. Yao, S. Wang, Y. Wang, X. Wang, X. Li, C. Niu, D. Wang, G. Zeng, Enhanced photocatalytic degradation of tetracycline by AgI/BiVO₄ heterojunction under visible-light irradiation: mineralization efficiency and mechanism. ACS Appl. Mater. Interfaces. \u003cb\u003e8\u003c/b\u003e, 32887\u0026ndash;32900 (2016). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1021/acsami.6b12278\u003c/span\u003e\u003cspan address=\"10.1021/acsami.6b12278\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eS.H. Miao, H.C. Gao, H.Y. Xia, X.X. Mao, L.J. Zhang, M.Q. Shi, Y.G. Zhang, Accelerated Fenton degradation of azo dye wastewater via a novel Z-scheme CoFeN-g-C₃N₄ heterojunction photocatalyst with excellent charge transfer under visible light irradiation. Dalton Trans. \u003cb\u003e51\u003c/b\u003e, 17243\u0026ndash;17253 (2022). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1039/D2DT02790A\u003c/span\u003e\u003cspan address=\"10.1039/D2DT02790A\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eR.A. Nasr, A.F. El-Sayed, G.M. El Komy, G.T. El-Bassyouni, S.M. Mousa, Modification of photocatalytic activity and antibacterial properties of Mn₂O₃ by Zn ions doping. Sci. Rep. \u003cb\u003e15\u003c/b\u003e, 14325 (2025). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1038/s41598-025-95769-2\u003c/span\u003e\u003cspan address=\"10.1038/s41598-025-95769-2\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eT.A. Alrebdi, R.A. Rezk, S.M. Alghamdi, H.A. Ahmed, F.H. Alkallas, R.A. Pashameah, A.M. Mostafa, E.A. Mwafy, Photocatalytic performance improvement by doping Ag on ZnO/MWCNTs nanocomposite prepared with pulsed laser ablation method based photocatalysts degrading Rhodamine B organic pollutant dye. Membranes. \u003cb\u003e12\u003c/b\u003e, 877 (2022). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.3390/membranes12090877\u003c/span\u003e\u003cspan address=\"10.3390/membranes12090877\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eE. Atinault, V. De Waele, U. Schmidhammer, M. Fattahi, M. Mostafavi, Scavenging of e\u003csub\u003es\u003c/sub\u003e\u003csup\u003e\u0026ndash;\u003c/sup\u003e and \u0026middot;OH radicals in concentrated HCl and NaCl aqueous solutions. Chem. Phys. Lett. \u003cb\u003e460\u003c/b\u003e, 461\u0026ndash;465 (2008). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.cplett.2008.08.047\u003c/span\u003e\u003cspan address=\"10.1016/j.cplett.2008.08.047\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eY.X. Wang, Z.M. Ao, H.Q. Sun, X.G. Duan, S.B. Wang, Activation of peroxymonosulfate by carbonaceous oxygen groups: experimental and density functional theory calculations. Appl. Catal. B: Environ. \u003cb\u003e198\u003c/b\u003e, 295\u0026ndash;302 (2016). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.apcatb.2016.08.025\u003c/span\u003e\u003cspan address=\"10.1016/j.apcatb.2016.08.025\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eT.S. Alkhuraiji, Effect of Co⁶⁰ irradiation on the degradation and mineralization of sulfonated aromatic compounds in aqueous solutions. Chemosphere. \u003cb\u003e228\u003c/b\u003e, 769\u0026ndash;777 (2019). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.chemosphere.2019.05.144\u003c/span\u003e\u003cspan address=\"10.1016/j.chemosphere.2019.05.144\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eY.Q. Yan, X.Y. Zhang, J.H. Wei, M. Chen, J.T. Bi, Y. Bao, Understanding the iron-cobalt synergies in ZSM-5: enhanced peroxymonosulfate activation and organic pollutant degradation. ACS Omega. \u003cb\u003e7\u003c/b\u003e, 17811\u0026ndash;17821 (2022). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1021/acsomega.2c01031\u003c/span\u003e\u003cspan address=\"10.1021/acsomega.2c01031\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZ.M. Dong, R.D. Zhou, L.Y. Xiong, H. Li, Q. Liu, L.Z. Zheng, Z.R. Guo, Z.X. Deng, Preparation of a Ti\u003csub\u003e0.7\u003c/sub\u003eW\u003csub\u003e0.3\u003c/sub\u003eO₂/TiO₂ nanocomposite interfacial photocatalyst and its photocatalytic degradation of phenol pollutants in wastewater. Nanoscale Adv. \u003cb\u003e2\u003c/b\u003e, 425\u0026ndash;437 (2020). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1039/c9na00478e\u003c/span\u003e\u003cspan address=\"10.1039/c9na00478e\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eD. Polak, S. Kamocki, M. Szwast, Evaluation of the potential of metal\u0026ndash;organic compounds ZIF-8 and F300 in a membrane filtration\u0026ndash;adsorption process for the removal of antibiotics from water. Antibiotics. \u003cb\u003e14\u003c/b\u003e, 619 (2025). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.3390/antibiotics14060619\u003c/span\u003e\u003cspan address=\"10.3390/antibiotics14060619\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eM.K. Far, R. Mohebat, M. Ghaedi, M. Tabatabaee, Efficient photocatalytic degradation of malachite green dye from wastewater using facilely synthesized ternary ZIF-8/Ag/Ag₂S nanocomposite: optimization by RSM (CCD), Process Saf. Environ. Prot. \u003cb\u003e190\u003c/b\u003e, 46\u0026ndash;62 (2024). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.psep.2024.08.036\u003c/span\u003e\u003cspan address=\"10.1016/j.psep.2024.08.036\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eH. Liu, J.M. Cao, W.L. Zhang, T. Jiang, G.H. Pan, Y. Wu, The development and synthesis of a CdZnS@metal\u0026ndash;organic framework ZIF-8 for the highly efficient photocatalytic degradation of organic dyes. Molecules. \u003cb\u003e28\u003c/b\u003e, 7904 (2023). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.3390/molecules28237904\u003c/span\u003e\u003cspan address=\"10.3390/molecules28237904\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZ.C. Liu, Y. Zhong, Z.C. Hu, W.Q. Zhang, X.T. Zhang, X. Ji, X.M. Wang, Modification of ZIF-8 nanocomposite by a Gd atom doped TiO₂ for high efficiency photocatalytic degradation of neutral red dye: an experimental and theoretical study. J. Mol. Liq. \u003cb\u003e380\u003c/b\u003e, 121729 (2023). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.molliq.2023.121729\u003c/span\u003e\u003cspan address=\"10.1016/j.molliq.2023.121729\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eY.Q. Jing, Q. Lei, C. Xia, Y. Guan, Y.D. Yang, J.X. He, Y. Yang, Y.H. Zhang, M. Yan, Synthesis of Ag and AgCl co-doped ZIF-8 hybrid photocatalysts with enhanced photocatalytic activity through a synergistic effect. RSC Adv. \u003cb\u003e10\u003c/b\u003e, 698\u0026ndash;704 (2020). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1039/c9ra10100d\u003c/span\u003e\u003cspan address=\"10.1039/c9ra10100d\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eA. Chakraborty, D.A. Islam, H. Acharya, Facile synthesis of CuO nanoparticles deposited zeolitic imidazolate frameworks (ZIF-8) for efficient photocatalytic dye degradation. J. Solid State Chem. \u003cb\u003e269\u003c/b\u003e, 566\u0026ndash;574 (2019). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.jssc.2018.10.036\u003c/span\u003e\u003cspan address=\"10.1016/j.jssc.2018.10.036\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eA. Faraji, N. Mehrdadi, N.M. Mahmoodi, M. Baghdadi, A. Pardakhti, Enhanced photocatalytic activity by synergic action of ZIF-8 and NiFe₂O₄ under visible light irradiation. J. Mol. Struct. (2020). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.molstruc.2020.129028\u003c/span\u003e\u003cspan address=\"10.1016/j.molstruc.2020.129028\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJ.H. He, J. Ye, Y. Zhang, L.B. Kong, X.J. Zhou, Y.H. Ma, Y.F. Yang, Synergistic RGO/Black TiO₂/2D-ZIF-8 Ternary Heterogeneous Composite with Highly Efficient Photocatalytic Activity, ChemistrySelect, \u003cb\u003e5\u003c/b\u003e (2020) 3746\u0026ndash;3755. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1002/slct.201904939\u003c/span\u003e\u003cspan address=\"10.1002/slct.201904939\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eB. Abdollahi, A. Najafidoust, E. Abbasi Asl, M. Sillanpaa, Fabrication of ZIF-8 metal organic framework (MOFs)-based CuO-ZnO photocatalyst with enhanced solar-light-driven property for degradation of organic dyes. Arab. J. Chem. \u003cb\u003e14\u003c/b\u003e, 103444 (2021). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.arabjc.2021.103444\u003c/span\u003e\u003cspan address=\"10.1016/j.arabjc.2021.103444\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJ. Abdi, Synthesis of Ag-doped ZIF-8 photocatalyst with excellent performance for dye degradation and antibacterial activity, Colloids Surf. A: Physicochem Eng. Asp. \u003cb\u003e604\u003c/b\u003e, 125330 (2020). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.colsurfa.2020.125330\u003c/span\u003e\u003cspan address=\"10.1016/j.colsurfa.2020.125330\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eX. Liu, J. Zhang, Y.M. Dong, H.X. Li, Y.M. Xia, H.J. Wang, A facile approach for the synthesis of Z-scheme photocatalyst ZIF-8/g-C₃N₄ with highly enhanced photocatalytic activity under simulated sunlight. New. J. Chem. \u003cb\u003e42\u003c/b\u003e, 12180\u0026ndash;12187 (2018). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1039/c8nj01782d\u003c/span\u003e\u003cspan address=\"10.1039/c8nj01782d\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eN. Chang, Y.R. Chen, F. Xie, Y.P. Liu, H.T. Wang, Facile construction of Z-scheme AgCl/Ag-doped-ZIF-8 heterojunction with narrow band gaps for efficient visible-light photocatalysis. Colloids Surf. A: Physicochem Eng. Asp. \u003cb\u003e616\u003c/b\u003e, 126351 (2021). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.colsurfa.2021.126351\u003c/span\u003e\u003cspan address=\"10.1016/j.colsurfa.2021.126351\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eA. Malik, M. Nath, S. Mohiyuddin, G. Packirisamy, Multifunctional CdSNPs@ZIF-8: potential antibacterial agent against GFP-expressing Escherichia coli and Staphylococcus aureus and efficient photocatalyst for degradation of methylene blue. ACS Omega. \u003cb\u003e3\u003c/b\u003e, 8288\u0026ndash;8308 (2018). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1021/acsomega.8b00664\u003c/span\u003e\u003cspan address=\"10.1021/acsomega.8b00664\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eM.Q. Hu, H. Lou, X.L. Yan, X.Y. Hu, R. Feng, M. Zhou, In-situ fabrication of ZIF-8 decorated layered double oxides for adsorption and photocatalytic degradation of methylene blue. Microporous Mesoporous Mater. \u003cb\u003e271\u003c/b\u003e, 68\u0026ndash;72 (2018). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.micromeso.2018.05.048\u003c/span\u003e\u003cspan address=\"10.1016/j.micromeso.2018.05.048\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eY.H. Si, X.R. Li, G. Yang, X.L. Mie, L.B. Ge, Fabrication of a novel core\u0026ndash;shell CQDs@ZIF-8 composite with enhanced photocatalytic activity. J. Mater. Sci. \u003cb\u003e55\u003c/b\u003e, 13049\u0026ndash;13061 (2020). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/s10853-020-04909-8\u003c/span\u003e\u003cspan address=\"10.1007/s10853-020-04909-8\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eA.J. Vakayil, T.K. Bindu Sharmila, C.S. Sasi Sreesha, Julie Chandra, P.H. Raman Vidya, Fathima Fasna, Water solubility, photoluminescence and photocatalytic activity of ZnS quantum dot sulfonated polystyrene composite. J. Lumin. \u003cb\u003e263\u003c/b\u003e, 120147 (2023). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.jlumin.2023.120147\u003c/span\u003e\u003cspan address=\"10.1016/j.jlumin.2023.120147\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eC.C. Wang, C.J. You, K. Rong, C.Q. Shen, F. Yang, S.J. Li, An S-scheme MIL-101(Fe)-on-BiOCl heterostructure with oxygen vacancies for boosting photocatalytic removal of Cr(VI). Acta Phys. -Chim Sin. \u003cb\u003e40\u003c/b\u003e, 2307045 (2024). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.3866/PKU.WHXB202307045\u003c/span\u003e\u003cspan address=\"10.3866/PKU.WHXB202307045\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eS.J. Li, C.C. Wang, K.X. Dong, P. Zhang, X.B. Chen, X. Li, MIL-101(Fe)/BiOBr S-scheme photocatalyst for promoting photocatalytic abatement of Cr(VI) and enrofloxacin antibiotic: performance and mechanism. Chin. J. Catal. \u003cb\u003e51\u003c/b\u003e, 101\u0026ndash;112 (2023). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/S1872-2067(22)64151-8\u003c/span\u003e\u003cspan address=\"10.1016/S1872-2067(22)64151-8\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eP. Lian, A.M. Qin, Z.S. Liu, H. Ma, L. Liao, K.Y. Zhang, N. Li, Facile synthesis to porous TiO₂ nanostructures at low temperature for efficient visible-light degradation of tetracycline. Nanomaterials. \u003cb\u003e14\u003c/b\u003e, 943 (2024). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.3390/nano14110943\u003c/span\u003e\u003cspan address=\"10.3390/nano14110943\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZ.Y. Zhang, X.Y. Xiao, M.L. Lu, Novel Z-scheme 2D/2D Bi₄O₅Br₂/BiOCl heterojunction with enhanced photocatalytic activity for RhB degradation. J. Chem. Technol. Biotechnol. \u003cb\u003e97\u003c/b\u003e, 1280\u0026ndash;1292 (2022). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1002/jctb.7023\u003c/span\u003e\u003cspan address=\"10.1002/jctb.7023\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZ. Guo, H.X. Hou, J.Y. Zhang, P.L. Cai, J. Lin, Prominent roles of Ni(OH)₂ deposited on ZnIn₂S₄ microspheres in efficient charge separation and photocatalytic H₂ evolution. RSC Adv. \u003cb\u003e11\u003c/b\u003e, 12442\u0026ndash;12448 (2021). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1039/d1ra01648b\u003c/span\u003e\u003cspan address=\"10.1039/d1ra01648b\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJ.F. Zheng, C.Z. Fan, X.M. Li, Enhanced photodegradation of tetracycline hydrochloride by hexameric AgBr/Zn-Al MMO S-scheme heterojunction photocatalysts: low metal leaching, degradation mechanism and intermediates. Chem. Eng. J. \u003cb\u003e446\u003c/b\u003e, 137371 (2022). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.cej.2022.137371\u003c/span\u003e\u003cspan address=\"10.1016/j.cej.2022.137371\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZ.W. Liu, J.J. Wang, S.H. Dong, L.Y. Wang, L. Li, Z.Z. Cao, Y.F. Zhang, L. Cheng, J.C. Yang, Ultrasonic controllable synthesis of sulfur-functionalized metal\u0026ndash;organic frameworks (S-MOFs) and their application in piezo-photocatalytic rapid reduction of hexavalent chromium (Cr), Ultrason. Sonochem, 107 (2024) 106912. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.ultsonch.2024.106912\u003c/span\u003e\u003cspan address=\"10.1016/j.ultsonch.2024.106912\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eY.M. Wang, T.T. Zhang, T.T. Wei, F.Y. Li, L. Xu, Bimetallic phosphide NiₓCo₁₋ₓP decorated flower-like ZnIn₂S₄ for enhanced photocatalytic hydrogen evolution. New. J. Chem. \u003cb\u003e45\u003c/b\u003e, 11261\u0026ndash;11268 (2021). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1039/d1nj02019f\u003c/span\u003e\u003cspan address=\"10.1039/d1nj02019f\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZ.T. Song, L.M. Wang, Construction of Ag/Ag₂S nanoparticles modified CoSₓ/ZnIn₂S₄ heterojunction for boosting photocatalytic organics degradation. J. Alloys Compd. \u003cb\u003e937\u003c/b\u003e, 168419 (2023). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.jallcom.2022.168419\u003c/span\u003e\u003cspan address=\"10.1016/j.jallcom.2022.168419\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eB.Q. Gao, Y. Pan, Q.Q. Chang, Z.H. Xi, H. Yang, Hierarchically Z-scheme photocatalyst of {0 1 0}BiVO₄/Ag/CdS with enhanced performance in synergistic adsorption-photodegradation of fluoroquinolones in water. Chem. Eng. J. \u003cb\u003e435\u003c/b\u003e, 134834 (2022). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.cej.2022.134834\u003c/span\u003e\u003cspan address=\"10.1016/j.cej.2022.134834\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eY.P. Huo, T.L. Yu, Y.Y. Xue, G.S. Zhang, S.X. Song, Y.H. Shao, X.J. Han, Three CoS/CoO microspheres and their mixed matrix membranes for the highly efficient photocatalytic degradation of methyl blue. RSC Adv. \u003cb\u003e14\u003c/b\u003e, 25811\u0026ndash;25819 (2024). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1039/D4RA03261F\u003c/span\u003e\u003cspan address=\"10.1039/D4RA03261F\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eA. Mancuso, N. Blangetti, O. Sacco, F.S. Freyria, B. Bonelli, S. Esposito, D. Sannino, V. Vaiano, Photocatalytic degradation of crystal violet dye under visible light by Fe-doped TiO₂ prepared by reverse-micelle sol\u0026ndash;gel method. Nanomaterials. \u003cb\u003e13\u003c/b\u003e, 270 (2023). \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.3390/nano13020270\u003c/span\u003e\u003cspan address=\"10.3390/nano13020270\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"ZIF-8/MnS, Photocatalytic degradation, Congo red, Mechanism","lastPublishedDoi":"10.21203/rs.3.rs-9420342/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-9420342/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe construction of heterojunctions is a proven method to improve photocatalytic efficiency. Herein, a series of ZIF-8/MnS composites were synthesized and thoroughly characterized. The photocatalytic degradation performance was evaluated under UV irradiation using Congo red (CR) as a model pollutant. The optimized ZIF-8/MnS composite with a Zn:Mn ratio of 10:3 displayed exceptional photocatalytic efficacy, degrading 99.4% of CR within 30 minutes under UV irradiation, surpassing the individual performances of pristine ZIF-8 and MnS. This superior activity is ascribed to the heterojunction interface established between ZIF-8 and MnS, which facilitates efficient charge carrier separation and migration. Through radical trapping experiments, it was determined that \u0026middot;O₂⁻ and h⁺ are the predominant active species, underscoring the potential of ZIF-8/MnS heterojunctions for effective photocatalytic treatment of wastewater. The work provides important insights for designing efficient MOF-based photocatalysts.\u003c/p\u003e","manuscriptTitle":"Solvothermal Construction of ZIF-8/MnS Z-Scheme Heterojunctions for Enhanced Photocatalytic Degradation of Organic Dyes","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-04-24 10:46:58","doi":"10.21203/rs.3.rs-9420342/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"a09d5fb2-4aee-4949-a93e-29c8615c3f9c","owner":[],"postedDate":"April 24th, 2026","published":true,"recentEditorialEvents":[{"type":"editorInvitedReview","content":"","date":"2026-05-14T05:33:59+00:00","index":27,"fulltext":""}],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2026-04-24T10:46:59+00:00","versionOfRecord":[],"versionCreatedAt":"2026-04-24 10:46:58","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-9420342","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-9420342","identity":"rs-9420342","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}