Synthesis, characterisation, and effective photocatalytic degradation applications in organic dye molecules using CdZnS-loaded UIO-66 composites

Synthesis, characterisation, and effective photocatalytic degradation applications in organic dye molecules using CdZnS-loaded UIO-66 composites | 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 Synthesis, characterisation, and effective photocatalytic degradation applications in organic dye molecules using CdZnS-loaded UIO-66 composites Tao Jiang, Guanyu Zhang, Liu Hong, Yun Wu This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4531692/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted 3 You are reading this latest preprint version Abstract One of the primary sources of industrial wastewater is dye wastewater, which is challenging for conventional water treatment methods to properly degrade because of its complex composition, high chromaticity, difficulty being biochemically destroyed, etc. The utilization of photocatalysts in conjunction with light energy, or photocatalytic technology, is thought to be a sustainable approach to treating dye wastewater due to its many benefits, including high degradation efficiency, rapid reaction times, and the absence of secondary contamination. We chose to employ CdZnS as a carrier in this research, together with composite UIO-66. The degradation of the dye methylene blue was carried out using the composite CdZnS@UIO-66 as a photocatalyst, and the results were compared to those of pure CdZnS and pure UIO-66. The findings demonstrated that CdZnS@UIO-66 had a noticeably greater photocatalytic efficiency than the other two. Up to 99.87% of the methylene blue in 50 mL of aqueous solution was degraded in the experimental reaction with a catalyst dosage of 0.03 g, pH of 7, and an initial concentration of 30 mg/L of methylene blue aqueous solution when exposed to visible light for 90 minutes. This indicates excellent photocatalytic efficacy in the visible range, the formation of an interfacial electron transfer phenomenon within the heterojunction, and the use of UIO-66 as an electron acceptor to further enhanced photocatalytic effect is caused by the development of interfacial electron transfer phenomena within the heterojunction and UIO-66 as an electron acceptor, which further promotes the internal photogenerated electron-hole separation. CdZnS UIO-66 Methylene blue Dye wastewater Photocatalytic reaction Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Instruction In China, the efficient treatment of wastewater containing dyes has emerged as a critical issue in the fight against water-related pollution [ 1 ].The majority of organic dyes are substantial water pollutants that are highly problematic to remediate because of their low biodegradability, carcinogenicity, and stability in aerobic digestion [ 2 ]. The discharge of wastewater containing dyes into the environment presents a significant risk to human health and other living organisms [ 3 ].As a result, lowering the concentration of pollutants prior to their discharge into the environment is crucial [ 4 ]. The method of photocatalysis uses a catalyst and light energy to speed up chemical processes. During a photocatalytic reaction, light energy is absorbed and transformed into excited state electrons[ 5 ]. These electrons can then mix with other molecules in solution, such as water or oxygen, to generate oxidizing agents or highly reactive free radicals, which can start a chemical process [ 6 ] .Photocatalysts, such as zinc oxide (ZnO) or titanium dioxide (TiO 2 ), are semiconductor materials that are used in the photocatalytic degradation of dyes [ 7 ].These photocatalysts may form excited state electron and hole pairs in reaction to light by absorbing visible or ultraviolet light [ 8 ].Because photocatalytic oxidation techniques are widely applicable, inexpensive, and simple to operate, they have been employed to investigate the degradation of different dye wastewaters [ 9 ]. We investigated the photocatalytic degradation of dyes in this work. The UIO-66 material is a possible application-oriented metal-organic skeleton (MOF) that is produced by coordinating metal clusters with twelve terephthalic acids [10 11].Its backbone structure can tolerate 1.0 MPa of mechanical pressure, and its crystal structure can be stable at 500°C [12 13].Furthermore, UIO-66 is able to keep its structural stability in a variety of solvents, including acetone, benzene, water, and DMF (N,N-dimethylformamide) [14 15].The primary cause of UiO-66's strong thermal and chemical stability is the coordination effect of their Zr-O bonds and Zr(IV) [ 16 ].One of the most stable series of MOF materials discovered to date is the UiO-66 series [17 18]. Due to its appropriate bandgap of 2.4 eV, cadmium zinc sulfide (Cd0.5Zn0.5S), also known as CdZnS, is a solid solution of CdS and ZnS that exhibits strong transmittance in the visible range and excellent absorption of visible light[ 19 ]. Furthermore, CdZnS is regarded as a promising photocatalyst because its conduction band (CB) edge potential is more negative than the reduction potential of H 2 O/H 2 [ 20 ] .While doping metal elements or compounding with other semiconducting materials might increase CdZnS's photocatalytic activity, it also suffers from photocorrosion and the quick compounding of photogenerated carriers during the photocatalytic process [ 21 ] . In order to increase the photocatalytic performance of the composite photocatalyst, we aim to create a composite material that will create a heterojunction structure between CdZnS particles and the organometallic skeleton UIO-66 [ 22 23 , 24 ]. This material will be able to effectively reduce the electron-hole complexation rate and improve its absorption of visible light [25 26]. Furthermore, it is possible to avert the material's secondary agglomeration and preserve the UIO-66 channels' higher adsorption capabilities [27 28]. Experimental preparation Preparation of UIO-66 Zirconium chloride (233.2 mg; 0.1 mol) and terephthalic acid (166.1 mg; 0.1 mol) were weighed, respectively, and then dissolved in 50 mL of DMF before being added to a tetrafluoroethylene reactor to react for 12 hours at 120°C. Finally, the mixture cooled naturally [29 24]. Following cooling, it was repeatedly cleaned with a DMF and methanol solution before being collected using centrifugation [30 26]. Vacuum-dried at 150°C and kept for 12 hours. The centrifuge tube was prepped, sealed, and put in a desiccator [31 32]. Preparation of CdZnS In a beaker with 20 mL of deionized water, combine 0.18 g (1.0 mmol) of CdCl2-2.5H 2 O, 0.2915 g (1.0 mmol) of zinc acetate, and 0.15 g (2.0 mmol) of TAA [ 33 ] .Stir the mixture for one hour, then move it to a hydrothermal reactor and maintain it at 160°C for 12 hours before allowing it to cool to room temperature. After being repeatedly cleaned with deionized water and anhydrous ethanol, the precipitate Cd0.5Zn0.5S was dried at 70°C for 12 hours, and then it was put away [34 35] . Synthesis of CdZnS@UIO-66 Then, 0.2332 g of zirconium chloride (0.1 mol) and 0.1661 g of terephthalic acid (0.1 mol) were added to 70 mL of methanol solution, mixed, and allowed to dissolve by stirring. The two portions of the 70 mL solution were then combined and placed into a hydrothermal reaction kettle for a duration of 12 hours. Weigh 0.012 g of CdZnS (0.0001 mol) was added to 70 mL of methanol solution and ultrasonically dispersed for 30 minutes [ 36 ] . The above-prepared precipitate was centrifuged, cleaned three times with methanol solution, and then dried for 12 hours at 150°C in a vacuum drying oven. Following drying, the completed product was powdered, put into sample containers, and given the appropriate labels. It was then put through an analytical and characterisation test [ 37 ] . Characterization and photocatalysis experiments The produced materials were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), N2 adsorption-desorption, and ultraviolet-visible-near-infrared diffuse reflectance spectroscopy (UV-Vis-NIR DRS). After adding 20 mg of CdZnS@UIO-66 composite, UIO-66 [38 39], or CdZnS prepared using various techniques to 50 mL of dye solution at a mass concentration of 10 mg/L, the mixture was shaken for 30 minutes away from light. Next, the reaction solution to be tested was exposed to a 300 W xenon lamp to mimic sunlight at a distance of 30 cm (irradiance: 735 W/m 2 ) [40 41]. The UV-Vis spectrophotometer was used to measure the mass concentration of the dye solution at various durations of illumination. Eq. ( 1 ) was then used to compute the degradation or adsorption rate (D,%): $$D/\text{%}=\left[\right({\rho }_{0}-{\rho }_{e})/{\rho }_{0}]\times 100$$ 1 Where: \({\rho }_{0}\) , \({\rho }_{e}\) are the starting and equilibrium mass concentration of the dye at a certain time of light exposure, mg/L, respectively. Results and discussion Comparative XRD patterns of CdZnS, UIO-66, and CdZnS@UIO-66 are displayed in Fig. 1a [17] .The widening phenomena seen in the major diffraction peak of CdZnS suggest that its grains are finer. Although there are some stray peaks that could be solvent molecule residues, the XRD patterns of the composite CdZnS@UIO-66 match those of CdZnS and UIO-66 well, and most of the characteristic peaks can be attributed to them. This suggests that there is a larger proportion of UIO-66 in the composite. Fig. 1.b : Because photon energy is what drives the formation of charges, photocatalysts' range and light-absorbing capacity are essential for photocatalysis. UIO-66, CdZnS, and CdZnS@UIO-66 were examined for their photoabsorption characteristics using ultraviolet-visible (UV-Vis) spectroscopy. The figure shows that UIO-66 exhibits a steady photoresponse with varied degrees in the curves at 200~300 nm. However, at 300 nm, it decreases quickly near the edge of the absorption band, suggesting that semiconductor interband jumps are the cause of UiO-66's absorption. CdZnS, on the other hand, shows more extensive and powerful absorption in the visible and ultraviolet spectrums. And after combining UIO-66 with CdZnS, the composite CdZnS@UIO-66's light absorption ability was much higher than that of UIO-66 in both the UV and visible regions. This is explained by the fact that the two materials have varying capacities for absorbing light, and their composites both increase the complexes' overall capacity for light absorption while also having a large specific surface area and a high molecular weight. On the other hand, light may be completely and efficiently diffusely reflected inside the composite material because of its high specific surface area and characteristic multilayer pore structure. This improves CdZnS@UIO-66's ability to utilize light. Fig. 1.c : Through the use of thermogravimetric analysis, the thermal stability of the backbone structure may be measured by examining how the catalyst's mass changes while the temperature is programmed to rise. It is evident from the figure that UIO-66 experiences two additional notable weight loss processes between 30-800 °C. About 20% of the weight of UIO-66 is lost between 100 and 300 degrees Celsius due to the evaporation of trace water molecules and the removal of certain organic ligands from its mesopores, which is the exact mechanism by which its defects occur. UIO-66 has a significant weight loss at 500 °C, which is a sign that the compound's structure is starting to break down after 600 °C. CdZnS has strong thermal stability, with a mass loss of 6.5% occurring above 800 °C. Up to 350 °C, the composite CdZnS@UIO-66 retains an excellent structure in comparison to pure UIO-66; beyond that point, it exhibits nearly identical conditions to UIO-66. The UIO-66 particles are shown in Figs. 1(e) and (f), which provide statistical analyses of their regular forms, uniform particle sizes, and average grain sizes of 200~300 nm. The experimentally produced CdZnS powders, the majority of which are chrysanthemum-shaped, are displayed in Fig. (e). Particle size distribution is widely distributed, with sizes ranging from 1um to 2um. The scarce CdZnS chrysanthemum-like particles in solution are observed to have unevenly adsorbed numerous layers of UIO-66 in (f). The tiny particles entirely encircled the CdZnS, producing a tight organometallic skeleton shell layer. A crucial characteristic of porous materials is their BET surface area, which is influenced by the size and shape of the pores. More active surface available for reactions to occur results in more reaction sites and adsorption locations, which are provided by a greater BET surface area. Because more reactants will be able to come into touch with the photocatalyst and react as a result, the photocatalytic reaction may be more active. Through N 2 adsorption-desorption studies, the specific surface area and pore size distribution profiles of CdZnS, CdZnS@UIO-66, and pure UIO-66 were ascertained. The adsorption-desorption isotherms of pure UIO-66 and composite CdZnS@UIO-66, as depicted in Fig 2.a and e, exhibit an I-shaped curve characteristic with a prominent adsorption inflection point in the low-pressure region of 0~0.1. At greater relative pressures, a well-shaped plateau appears, indicating microporosity. On the other hand, CdZnS, a macroporous solid material, displays a type III isotherm as seen in Fig 2.c. Adsorbed molecules cluster on the surface near the most gravitationally attractive spots, and the adsorbed material-adsorbed gas contact is comparatively weak. Furthermore, as can be observed in Fig 2.e, the hysteresis loop curves that emerge are of the H 4 type, suggesting that the synthesized composites exhibit some mesopores that resemble those created by the lamellar structure in addition to the microporous structure. Furthermore, Table 1 demonstrates that the composites' BET specific surface area is 989.226 m 2 g -1 , which is much greater than that of CdZnS (12.662 m 2 g -1 ) and only marginally less than that of UIO-66 (1095.452 m 2 g -1 ). The production of CdZnS wrapping by UIO-66 might be the cause. The three-level pore structure of the CdZnS@UIO-66 composites—micropores, mesopores, and macropores is revealed by examining the Barret-JoynerHalenda (BJH) pore size distribution of the composites (Fig 2.f). The findings demonstrate that the multistage pore structure of the CdZnS@UIO-66 composites may speed up mass diffusion and transfer efficiency during the photocatalytic process in addition to reflecting and absorbing incoming light several times. Additional XPS research revealed comprehensive details on the valence and chemical composition of [email protected] seen in Fig 3.a, the XPS measurement scans indicated that the composite sample contained the elements O, N, C, Cd, Zn, S, and Zr. The C1s spectrum of CdZnS@UIO-66 is displayed in Fig 3.b, with two peaks at 531.95 e V and 530. 5 e V corresponding to Zr elements in UIO-66 on the material's surface, as shown in Fig 3.c, and three peaks at 288.7 e V, 286.2 e V, and 284.8 e V corresponding to C-C/C=C, C-N, and O-C-O (which correspond to the functional groups of UIO-66). According to Fig 3.c, the Zr-O functional group and oxygen vacancies in UIO-66 on the material surface are represented by the two peaks at 531.95 e V and 530.5 e V. The XPS spectra of Zr 3d is seen in Fig 3. d, where two prominent peaks can be seen at 185.15 eV and 182.75 eV. These peaks, which match up with Zr 3d 5/2 and Zr 3d 3/2, show that Zr is present in the tetravalent zirconium ion (Zr 4+ ) form . At 185.15 eV, the lesser distinctive peak is located, while at 182.75 eV, the stronger one. The specific surface area and pore size of the UIO-66、CdZnS和CdZnS@UIO-66 materials specific surface area（m 2 /g） diameter of hole (nm) UIO-66 1095.452 5.632 CdZnS 12.662 43.142 CdZnS@UIO-66 989.226 6.985 Discussion of photocatalytic methylene blue properties Fig 4.(a) We conducted experiments on photocatalytic degradation of methylene blue by preparing composites with different mass ratios, as well as UIO-66 and CdZnS before compositing, in which the initial concentration of methylene blue was specified to be 30 mg/L. This allowed us to obtain CdZnS@UIO-66 composites with better catalytic performance. 50 mg of photocatalytic degradation materials were used, and the solution's pH was left unchanged. The findings of photocatalytic methylene blue degradation at various mass ratios are displayed in Fig. 4a. the impact of methylene blue photocatalytic degradation at various mass ratios. The figure illustrates how the CdZnS material rises larger in the light of the 0-10min removal rate curve, and then tends to stabilize the rising process in a linear fashion where the removal rate is proportionate to the time. The remaining material rises faster in the 0~20min removal rate curve, reaching a stable rising state after 20 minutes of passage. The removal rate of 1% composite material for photocatalytic methylene blue degradation reached 98.74% after a 90-minute reaction period; in contrast, the removal rate of UIO-66 material was 82.92%, and the removal rate of CdZnS was only 63.73%. According to the experimental findings, the 1% manufactured composites enhanced the rate of photocatalytic methylene blue degradation and outperformed UIO-66 and CdZnS prior to the composites' synthesis. Fig 4.b: Methylene blue photocatalytic degradation by CdZnS@UIO-66 material dose. The figure shows that the removal rate increased at 20 and 30 milligrams of material, and that at 30 milligrams of material, the removal rate of methylene blue reached 99.87%. This is because light energy cannot be fully utilized when the material dose is modest since the photochemical particles produced by the light source are not entirely transformed into chemical energy. The production of additional active species and an increase in photocatalytic degradation efficiency can be achieved by appropriately increasing the dosage of degradation materials. The UIO-66 composite material was found to contain metal active sites through the previous review and literature, and the multistage pore structure can meet the mass transfer process of macromolecules simultaneously. As a result, by increasing the dosage of the degradation material, the active sites were increased and the material's photocatalytic degradation efficiency was improved. Consequently, we need raise the additive amount of the materials accordingly when adding photocatalytic materials; 30 mg was the chosen additive amount. Fig 4.c: Following thirty minutes of dark adsorption, the experiment proceeded to the photocatalytic degradation stage. At 0~20 minutes, the removal rate rose sharply and quickly; however, after a steady plateau, the removal rate became proportionate to the time. This is because the composite materials' catalytic and adsorptive actions in the methylene blue solution degradation were carried out concurrently at a rate of 0~20 min, which significantly increased the clearance rate. Following that, each sample's adsorption reduced during the photocatalytic degradation process, in which photocatalytic degradation was a key factor. The number of active sites on the material's surface dropped as the reaction time was extended, and this reduced the driving force behind the degradation reaction. As a result, the degradation rate slowed down progressively until it reached the chemical reaction's equilibrium. Following 40 minutes, the removal rates of the samples exhibiting varying concentrations of methylene blue solution showed a decreasing trend. This is because at low concentrations, the dye can quickly occupy the active sites of the material's degradation reaction, improving the removal rate; at higher concentrations, however, the dye must diffuse internally to reach the surface of the degraded material, slowing down the adsorption process due to the spatial site-impedance repulsive force between the solute's molecules. As a result, the removal rate declines. Fig 4.e: Based on the graph, it is evident that the removal rate decreases as the number of experimental cycles increases. This is because the composite material's methylene blue desorption process is not yet complete. Following the fourth cycle, the removal rate decreased steadily, which could be because of the degradation process's chemical equilibrium. The elimination rate of methylene blue from CdZnS@UIO-66 after five rounds of cycling experimentation was found to be as high as 80.33%. This indicates that the composites maintained their strong photocatalytic activity even after many regeneration cycles and shown good stability and reusability. Fig 4.f: We performed the following studies to assess CdZnS@UIO-66's selectivity for methylene blue and learn more about its photocatalytic degradation performance for organic dyes. We chose various dyes with a concentration of 30 mg/L, such as methyl orange (MO), rhodamine B (RB), methylene blue , and reactive brilliant red X-3B, and conducted the photocatalytic degradation test under the conditions of adding 30 mg of CdZnS@UIO-66 and setting the initial pH of the solution to 7. Figure 4f presents the outcomes of the experiment. Following a 30-minute dark reaction and a 90-minute light reaction, the photocatalytic degradation of methyl orange, rhodamine B, methylene blue, and reactive brilliant red X-3B by CdZnS@UIO-66 was 70.25%, 89.62%, 99.87%, and 92.38%, respectively. This suggests that CdZnS@UIO-66 performs well in catalytic degradation for all four dyes and has a high elimination efficiency. The greatest clearance rate of 99.87% was specifically attained for methylene blue. As a result, we can say that CdZnS@UIO-66 has good photocatalytic degradation performance for the treatment of dye wastewater and lacks selectivity for methylene blue. Photocatalytic mechanism of CdZnS semiconductor The production of electron-hole pairs, their separation, and eventually their transport to the catalyst surface are the three processes that, in theory, make up the photocatalytic reaction of semiconductor materials. Based on this, the photogenerated holes and electrons react on various surface adsorption medium, in that order. Photogenerated carriers can excite CdZnS when exposed to photons with energy greater than Eg; however, these carriers are prone to aggregation. Additionally, oxidation and reduction events take place at the forward and reverse band sites, leading to additional reactions and the production of -OH. Basically, -OH is added to water to oxidize organic contaminants and create CO 2 and H 2 O . Photocatalytic mechanism of CdZnS@UIO-66 composites When CdZnS and UIO-66 form a heterojunction, if their conductivity is opposite, electron-hole transport between the two will continue until their Fermi energy levels are equal . Here, UIO-66 and CdZnS combine to produce a space charge area, with one side of UIO-66 being negative and the other positive. The positive and negative charge regions combine to create an integrated electric field that forms a heterojunction. In the conductive band of CdZnS, photogenerated electron-hole pairs are generated in CdZnS. The self-built electric field causes the photogenerated holes to migrate from CdZnS to UIO-66 while the photogenerated electrons remain in CdZnS. This effectively prevents the electron-hole complexation, allowing the electron-hole to participate in the photocatalytic reaction in CdZnS and thereby increasing the rate of photocatalytic reaction. Conclusions To sum up, we have chosen to employ CdZnS as a carrier in this research and have successfully created composites with strong photocatalytic characteristics using UIO-66. This is a unique structure made up of a metal-organic skeleton and three-dimensional CdZnS particles. The composites were built with simultaneous micro-, meso-, and macropores in a multistage pore structure. The photocatalytic efficiency of CdZnS@UIO-66 was demonstrated by the experimental findings to be much greater than that of pure CdZnS and pure UIO-66. In the experimental reaction, the starting concentration of methylene blue aqueous solution was 30 mg/L, the pH was 7, and the catalyst dose was 0.03 g. By exposing 50 mL of aqueous solution to visible light for 90 minutes, the degradation of methylene blue could reach 99.87%, demonstrating the strong photocatalytic effectiveness in the visible light range. The composite was made in an easy manner that increased UIO-66's visible light absorption range, enhanced its photocatalytic activity, and demonstrated the material's viability for use in photocatalytic degradation research. Declarations Acknowledgement This work was financially supported by Nature Science Foundation of Anhui province colleges and universities (No.2023AH052193), Excellent Young Talents Fund Program of Higher Education Institutions of Anhui Province (CN) (grant GXYQ2018072, GXYQ2017065), the National Natural Science Foundation of China (NSFC, Grants 51505121 and 51375139), the Natural Science Foundation of Hefei university (Grants 18ZR17ZDA, 18ZR18ZDA), and the Youth Talent Foundation of Hefei University (No. 16YQ05RC). Author contributions T. J. wrote the main manuscript text and prepared figures 1-7. The author reviewed the manuscript. Competing interests The author declares no competing interests. Data availability All data generated or analyzed during this study are included in this published article (and its supplementary information files). References Ahmadijokani F et al (2020) Superior chemical stability of UiO-66 metal-organic frameworks (MOFs) for selective dye adsorption. Chem Eng J 399:125346 Ahmadijokani F et al (2022) UiO-66 metal–organic frameworks in water treatment: A critical review. Prog Mater Sci 125:100904 Celebi N, Aydin MY, Soysal F, Yıldız N, Salimi K (2020) Core/shell PDA@ UiO-66 metal–organic framework nanoparticles for efficient visible-light photodegradation of organic dyes. ACS Appl Nano Mater 3:11543–11554 Embaby MS, Elwany SD, Setyaningsih W, Saber MR (2018) The adsorptive properties of UiO-66 towards organic dyes: A record adsorption capacity for the anionic dye Alizarin Red S. Chin J Chem Eng 26:731–739 Akyüz D (2021) rGO-TiO2-CdO-ZnO-Ag photocatalyst for enhancing photocatalytic degradation of methylene blue. Opt Mater 116:111090 Bai J, Xie Z, Han G, Diao G (2022) Double-shelled CeO2 coupled CdZnS nanoparticles as an efficient heterojunction visible light photocatalyst for hydrogen evolution. J Alloys Compd 919:165758 Baytar O, Sahin O, Kilicvuran H, Horoz S (2018) Synthesis, structural, optical and photocatalytic properties of Fe-alloyed CdZnS nanoparticles. J Mater Sci: Mater Electron 29:4564–4568 Cinsy N, Geetha R (2023) Characterization and photocatalytic activity of CdZnS nanoparticles incorporated with medicative leaf excerpt. Chalcogenide Lett 20:121–129 Feng C et al (2021) Significantly enhanced photocatalytic hydrogen production performance of g-C3N4/CNTs/CdZnS with carbon nanotubes as the electron mediators. J Mater Sci Technol 80:75–83. https://doi.org/10.1016/j.jmst.2020.11.047 Gayathri K, Vinothkumar K, Mohan S, Geetha Balakrishna R (2024) Manifestation of UiO-66-Zr MOF-enabled photocatalytic membranes for successive separation and degradation of dye mixtures in water remediation. J Environ Chem Eng 12:112490. https://doi.org/10.1016/j.jece.2024.112490 Yuan Y-P et al (2015) Improving photocatalytic hydrogen production of metal–organic framework UiO-66 octahedrons by dye-sensitization. Appl Catal B 168:572–576 Han Y et al (2017) In situ synthesis of titanium doped hybrid metal–organic framework UiO-66 with enhanced adsorption capacity for organic dyes. Inorg Chem Front 4:1870–1880 Zhao D, Cai C (2021) Cerium-based UiO-66 metal-organic framework for synergistic dye adsorption and photodegradation: a discussion of the mechanism. Dyes Pigm 185:108957 Haryanto A, Mukaromah L, Permana Y, Patah A (2021) Photocatalytic activity of CuBDC and UiO-66 MOFs for methyl orange degradation. J Chem Technol Metall 56:791–795 Zhao Q et al (2020) UiO-66-NH2/Cu2O composite as an enhanced visible light photocatalyst for decomposition of organic pollutants. J Photochem Photobiol A 399:112625. https://doi.org/10.1016/j.jphotochem.2020.112625 Konno H, Tsukada A (2022) Size-and ion-selective adsorption of organic dyes from aqueous solutions using functionalized UiO-66 frameworks. Colloids Surf A 651:129749 Li T, Zhang Z, Yang Z (2023) Encapsulation of phosphotungstic acid into UiO-66-(OH)2 for synergistic and rapid photocatalytic degradation of organic pollutants. Mater Lett 348:134699. https://doi.org/10.1016/j.matlet.2023.134699 Zheng M, Yao C, Xu Y (2020) Fe3O4 nanoparticles decorated with UIO-66 Metal–Organic Framework particles and encapsulated in a triazine-based Covalent Organic Framework matrix for photodegradation of anionic dyes. ACS Appl Nano Mater 3:11307–11314 Liu H et al (2022) Modified UiO-66 as photocatalysts for boosting the carbon-neutral energy cycle and solving environmental remediation issues. Coord Chem Rev 458:214428 Horoz S, Baytar O, Sahin O, Kilicvuran H (2018) Photocatalytic degradation of methylene blue with Co alloyed CdZnS nanoparticles. J Mater Sci: Mater Electron 29:1004–1010 Jayaraman V, Palanivel B, Ayappan C, Chellamuthu M, Mani A (2019) CdZnS solid solution supported Ce2Sn2O7 pyrochlore photocatalyst that proves to be an efficient candidate towards the removal of organic pollutants. Sep Purif Technol 224:405–420 Jeon HW et al (2020) Photocatalytic Degradation of Rhodamine B, Methyl Orange and Methylene Blue with CdS and CdZnS/ZnO Catalysts under Visible Light Irradiation. Clean Technol 26:311–320 Aboraia AM et al (2023) A heterostructural MoS2QDs@UiO-66 nanocomposite for the highly efficient photocatalytic degradation of methylene blue under visible light and simulated sunlight††Electronic supplementary information (ESI) available. RSC Adv 13:34598–34609. https://doi.org/10.1039/d3ra06299f . See DOI Yin Y et al (2022) A new type of composite catalyst AmCoPc/UiO-66-NH2 synergistic photocatalytic degradation of dyes. Inorg Chem Commun 145:109914. https://doi.org/10.1016/j.inoche.2022.109914 Mansouri M, Sadeghian S, Mansouri G, Setareshenas N (2021) Enhanced photocatalytic performance of UiO-66-NH2/TiO2 composite for dye degradation. Environ Sci Pollut Res 28:25552–25565 Zhou Y-C et al (2019) Facile fabrication and enhanced photocatalytic performance of visible light responsive UiO-66-NH2/Ag2CO3 composite. Chin J Catal 40:1912–1923. https://doi.org/10.1016/S1872-2067(19)63433-9 Liu H et al (2023) Confinement of Organic Dyes in UiO-66-Type Metal–Organic Frameworks for the Enhanced Synthesis of [1, 2, 5] Thiadiazole [3, 4-g] benzoimidazoles. J Am Chem Soc 145:17588–17596 Yasmeen K et al (2022) Removal of Pb(II) from water samples using surface modified core/shell CdZnS/ZnS QDs as adsorbents: Characterization, adsorption, kinetic and thermodynamic studies. Arab J Chem 15:104224. https://doi.org/10.1016/j.arabjc.2022.104224 Mohammadi A et al (2017) Metal-organic framework Uio-66 for adsorption of methylene blue dye from aqueous solutions. Int J Environ Sci Technol 14:1959–1968 Mousavi DV et al (2021) Adsorption performance of UiO-66 towards organic dyes: Effect of activation conditions. J Mol Liq 321:114487 Ni Q, Feng S, Ke X, Yan Z, Luan J (2023) Multi-dimensional (2D–3D) assembly of BiOI/BiOBr/UiO-66-NH2 composites to form multi-heterojunction structures for synergistic removal of Rhodamine B. J Alloys Compd 935:168103. https://doi.org/10.1016/j.jallcom.2022.168103 Tian H et al (2021) BiOBr@UiO-66 photocatalysts with abundant activated sites for the enhanced photodegradation of rhodamine b under visible light irradiation. Mater Sci Engineering: B 271:115297. https://doi.org/10.1016/j.mseb.2021.115297 Khudhair EM, Khudhair WN, Ammar SH, Mahdi AS (2022) Assembling ZIF-67@ Cd0. 5Zn0. 5S nanocomposites with an enhanced photocatalytic activity. Inorg Chem Commun 142:109639 Kilicvuran H, Sahin O, Baytar O, Horoz S, INTERNATIONAL JOURNAL OF ENGINEERING SCIENCES & RESEARCH TECHNOLOGY CHARACTERIZATION OF Ni Doped CdZnS NANOPARTICLES AND THEIR USE IN METHYLENE BLUE DEGRADATION UNDER VISIBLE LIGHT IRRADIATION Zhang X et al (2023) Construction of 0D/2D CdZnS quantum dots/SnIn4S8 nanosheets heterojunction photocatalysts for boosting photocatalytic performance. Colloids Surf A 664:131184 Mureithi AW et al (2023) 3d (Co and Mn) and 4d (Ag) Transition Metal-Doped ZnO Nanoparticles Anchored on CdZnS for the Photodegradation of Rhodamine B. Crystals 14:41 Palanisamy G et al (2021) An efficient and magnetically recoverable g-C3N4/ZnS/CoFe2O4 nanocomposite for sustainable photodegradation of organic dye under UV–visible light illumination. Environ Res 201:111429 Qi Xm et al (2021) Design of UiO-66@BiOIO3 heterostructural composites with remarkable boosted photocatalytic activities in removing diverse industrial pollutants. J Phys Chem Solids 151:109903. https://doi.org/10.1016/j.jpcs.2020.109903 Van Le D, Nguyen MB, Dang PT, Lee T, Nguyen TD (2022) Synthesis of a UiO-66/g-C3N4 composite using terephthalic acid obtained from waste plastic for the photocatalytic degradation of the chemical warfare agent simulant, methyl paraoxon††Electronic supplementary information (ESI) available: HPLC spectrum of H2BDC, schematic synthesis of UiO-66/g-C3N4, XRD analysis, EDS spectra, SEM images, UV-vis spectra of DMNP, images of DMNP solution, LC-mass spectra of DMNP, photo-stability test, element composition, and a comparison of photocatalytic activity of photocatalysts. See https://doi.org/10.1039/d2ra03483b . RSC Advances 12, 22367–22376, doi:https://doi.org/10.1039/d2ra03483b Sha Z, Chan HSO, Wu J (2015) Ag2CO3/UiO-66(Zr) composite with enhanced visible-light promoted photocatalytic activity for dye degradation. J Hazard Mater 299:132–140. https://doi.org/10.1016/j.jhazmat.2015.06.016 Tan Y et al (2021) A novel UiO-66-NH2/Bi2WO6 composite with enhanced pollutant photodegradation through interface charge transfer. Colloids Surf A 622:126699. https://doi.org/10.1016/j.colsurfa.2021.126699 Additional Declarations No competing interests reported. Cite Share Download PDF Status: Under Review Version 1 posted Editor assigned by journal 11 Jun, 2024 Submission checks completed at journal 11 Jun, 2024 First submitted to journal 05 Jun, 2024 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. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. 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-4531692","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":313268817,"identity":"fea39dee-5a47-4d35-a7d6-1e89c52bd0ab","order_by":0,"name":"Tao Jiang","email":"","orcid":"","institution":"Hefei University","correspondingAuthor":false,"prefix":"","firstName":"Tao","middleName":"","lastName":"Jiang","suffix":""},{"id":313268818,"identity":"103f257b-954c-4285-ae09-23f4a0667d7c","order_by":1,"name":"Guanyu Zhang","email":"","orcid":"","institution":"Hefei University","correspondingAuthor":false,"prefix":"","firstName":"Guanyu","middleName":"","lastName":"Zhang","suffix":""},{"id":313268819,"identity":"12962caf-6498-4ff8-9274-ee2e8f4926d1","order_by":2,"name":"Liu Hong","email":"","orcid":"","institution":"Hefei University","correspondingAuthor":false,"prefix":"","firstName":"Liu","middleName":"","lastName":"Hong","suffix":""},{"id":313268820,"identity":"b2d3ce05-c78d-4936-b06b-27821713cfc8","order_by":3,"name":"Yun Wu","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA2ElEQVRIiWNgGAWjYDACdiDmKQAxehg+gEUOENLCDNJiACLOMM4gUYtEDpFa+JuZj0m8MbCxl5/59mAzbxuDHN+NBMbPBXi0SBxmS5OcY5CWuOF2XiJIi7HkjQRm6Rl4tBgw85hJ8xgcTjCQzjF/DNSSuOFGAhszD2Et/4EOO2MIsqWeWC0HGBtu8IC1JBgQ0gL0S7LlHIPkxA1ncgwb55yTMJx55mGzND4t/O3NB2+8qbCzl28/Y9jwpsxGnu948sHP+LRg2ArEjA0kaBgFo2AUjIJRgA0AADpTQ6NfA6UKAAAAAElFTkSuQmCC","orcid":"","institution":"Hefei University","correspondingAuthor":true,"prefix":"","firstName":"Yun","middleName":"","lastName":"Wu","suffix":""}],"badges":[],"createdAt":"2024-06-05 06:01:46","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-4531692/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-4531692/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":59103579,"identity":"915551f1-05f1-400b-88a9-959be6f14569","added_by":"auto","created_at":"2024-06-26 11:34:40","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":188181,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003e(a)\u003c/strong\u003eXRD patterns of CdZnS, UIO-66 and CdZnS@UIO-66 \u003cstrong\u003e(b)\u003c/strong\u003eultraviolet spectrum of CdZnS, UIO-66 and CdZnS@UIO-66\u003cstrong\u003e (c)\u003c/strong\u003ethermogravimetric analysis of CdZnS, UIO-66 and CdZnS@UIO-66 \u0026nbsp;\u0026nbsp;Scanning electron microscopy (SEM) of \u003cstrong\u003e(e)\u003c/strong\u003e, \u003cstrong\u003e(f)\u003c/strong\u003e UIO-66, \u003cstrong\u003e(g)\u003c/strong\u003e, and \u003cstrong\u003e(h)\u003c/strong\u003e UIO-66mSi-SH\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-4531692/v1/de7e641f942eb0009a7e051f.png"},{"id":59103076,"identity":"e8526a6f-77a9-47b9-a5cf-6d7f0a2f1822","added_by":"auto","created_at":"2024-06-26 11:26:40","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":221945,"visible":true,"origin":"","legend":"\u003cp\u003e(a) (c) (e) N2 adsorption-desorption isotherms and (b) (d) (f) corresponding pore size distribution curves for pure UIO-66,CdZnS and CdZnS@UIO-66 composites\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-4531692/v1/bbf18897bcf6aa987e5bb7c1.png"},{"id":59103080,"identity":"293d9100-547d-4cc1-86d3-8f2cdea77e04","added_by":"auto","created_at":"2024-06-26 11:26:40","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":183519,"visible":true,"origin":"","legend":"\u003cp\u003eX-ray photoelectron spectroscopy (XPS)\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-4531692/v1/395e7abdc5317dce06b7c9d2.png"},{"id":59104126,"identity":"d2347294-10fa-449e-85f0-28d0e1b06cba","added_by":"auto","created_at":"2024-06-26 11:42:40","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":264352,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003e(a) \u003c/strong\u003eComparison of the effects of photocatalytic degradation of methylene blue with different mass ratios \u003cstrong\u003e(b)\u003c/strong\u003e Comparison of different dosages \u003cstrong\u003e(c)\u003c/strong\u003e Initial concentration \u003cstrong\u003e(d)\u003c/strong\u003e PH \u003cstrong\u003e(e) \u003c/strong\u003eNumber of cycles \u003cstrong\u003e(f)\u003c/strong\u003e Type of Dye\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-4531692/v1/c5d4b07feb74956e81372511.png"},{"id":59103077,"identity":"269360e9-1900-47e6-9826-88f3cd72f78b","added_by":"auto","created_at":"2024-06-26 11:26:40","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":132193,"visible":true,"origin":"","legend":"\u003cp\u003eSchematic of electron hole transfer in CdZnS@UIO-66 composites\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-4531692/v1/80b27defe3b284004e3d3def.png"},{"id":59104607,"identity":"b365f496-36d5-418f-91ef-d50dea280e37","added_by":"auto","created_at":"2024-06-26 11:50:41","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1439568,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4531692/v1/0af3677d-8f51-4a9e-91e3-971c25489242.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"Synthesis, characterisation, and effective photocatalytic degradation applications in organic dye molecules using CdZnS-loaded UIO-66 composites","fulltext":[{"header":"Instruction","content":"\u003cp\u003eIn China, the efficient treatment of wastewater containing dyes has emerged as a critical issue in the fight against water-related pollution [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e].The majority of organic dyes are substantial water pollutants that are highly problematic to remediate because of their low biodegradability, carcinogenicity, and stability in aerobic digestion [\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e]. The discharge of wastewater containing dyes into the environment presents a significant risk to human health and other living organisms [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e].As a result, lowering the concentration of pollutants prior to their discharge into the environment is crucial [\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eThe method of photocatalysis uses a catalyst and light energy to speed up chemical processes. During a photocatalytic reaction, light energy is absorbed and transformed into excited state electrons[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]. These electrons can then mix with other molecules in solution, such as water or oxygen, to generate oxidizing agents or highly reactive free radicals, which can start a chemical process [\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e] .Photocatalysts, such as zinc oxide (ZnO) or titanium dioxide (TiO\u003csub\u003e2\u003c/sub\u003e), are semiconductor materials that are used in the photocatalytic degradation of dyes [\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e].These photocatalysts may form excited state electron and hole pairs in reaction to light by absorbing visible or ultraviolet light [\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e].Because photocatalytic oxidation techniques are widely applicable, inexpensive, and simple to operate, they have been employed to investigate the degradation of different dye wastewaters [\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e]. We investigated the photocatalytic degradation of dyes in this work.\u003c/p\u003e \u003cp\u003eThe UIO-66 material is a possible application-oriented metal-organic skeleton (MOF) that is produced by coordinating metal clusters with twelve terephthalic acids [10 11].Its backbone structure can tolerate 1.0 MPa of mechanical pressure, and its crystal structure can be stable at 500\u0026deg;C [12 13].Furthermore, UIO-66 is able to keep its structural stability in a variety of solvents, including acetone, benzene, water, and DMF (N,N-dimethylformamide) [14 15].The primary cause of UiO-66's strong thermal and chemical stability is the coordination effect of their Zr-O bonds and Zr(IV) [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e].One of the most stable series of MOF materials discovered to date is the UiO-66 series [17 18].\u003c/p\u003e \u003cp\u003eDue to its appropriate bandgap of 2.4 eV, cadmium zinc sulfide (Cd0.5Zn0.5S), also known as CdZnS, is a solid solution of CdS and ZnS that exhibits strong transmittance in the visible range and excellent absorption of visible light[\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e]. Furthermore, CdZnS is regarded as a promising photocatalyst because its conduction band (CB) edge potential is more negative than the reduction potential of H\u003csub\u003e2\u003c/sub\u003eO/H\u003csub\u003e2\u003c/sub\u003e [\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e] .While doping metal elements or compounding with other semiconducting materials might increase CdZnS's photocatalytic activity, it also suffers from photocorrosion and the quick compounding of photogenerated carriers during the photocatalytic process [\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e] .\u003c/p\u003e \u003cp\u003eIn order to increase the photocatalytic performance of the composite photocatalyst, we aim to create a composite material that will create a heterojunction structure between CdZnS particles and the organometallic skeleton UIO-66 [\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e, \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e]. This material will be able to effectively reduce the electron-hole complexation rate and improve its absorption of visible light [25 26]. Furthermore, it is possible to avert the material's secondary agglomeration and preserve the UIO-66 channels' higher adsorption capabilities [27 28].\u003c/p\u003e"},{"header":"Experimental preparation","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e\n \u003ch2\u003ePreparation of UIO-66\u003c/h2\u003e\n \u003cp\u003eZirconium chloride (233.2 mg; 0.1 mol) and terephthalic acid (166.1 mg; 0.1 mol) were weighed, respectively, and then dissolved in 50 mL of DMF before being added to a tetrafluoroethylene reactor to react for 12 hours at 120\u0026deg;C. Finally, the mixture cooled naturally [29 24]. Following cooling, it was repeatedly cleaned with a DMF and methanol solution before being collected using centrifugation [30 26]. Vacuum-dried at 150\u0026deg;C and kept for 12 hours. The centrifuge tube was prepped, sealed, and put in a desiccator [31 32].\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec4\" class=\"Section2\"\u003e\n \u003ch2\u003ePreparation of CdZnS\u003c/h2\u003e\n \u003cp\u003eIn a beaker with 20 mL of deionized water, combine 0.18 g (1.0 mmol) of CdCl2-2.5H\u003csub\u003e2\u003c/sub\u003eO, 0.2915 g (1.0 mmol) of zinc acetate, and 0.15 g (2.0 mmol) of TAA [\u003cspan class=\"CitationRef\"\u003e33\u003c/span\u003e] .Stir the mixture for one hour, then move it to a hydrothermal reactor and maintain it at 160\u0026deg;C for 12 hours before allowing it to cool to room temperature. After being repeatedly cleaned with deionized water and anhydrous ethanol, the precipitate Cd0.5Zn0.5S was dried at 70\u0026deg;C for 12 hours, and then it was put away [34 35] .\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec5\" class=\"Section2\"\u003e\n \u003ch2\u003eSynthesis of CdZnS@UIO-66\u003c/h2\u003e\n \u003cp\u003eThen, 0.2332 g of zirconium chloride (0.1 mol) and 0.1661 g of terephthalic acid (0.1 mol) were added to 70 mL of methanol solution, mixed, and allowed to dissolve by stirring. The two portions of the 70 mL solution were then combined and placed into a hydrothermal reaction kettle for a duration of 12 hours. Weigh 0.012 g of CdZnS (0.0001 mol) was added to 70 mL of methanol solution and ultrasonically dispersed for 30 minutes [\u003cspan class=\"CitationRef\"\u003e36\u003c/span\u003e] .\u003c/p\u003e\n \u003cp\u003eThe above-prepared precipitate was centrifuged, cleaned three times with methanol solution, and then dried for 12 hours at 150\u0026deg;C in a vacuum drying oven. Following drying, the completed product was powdered, put into sample containers, and given the appropriate labels. It was then put through an analytical and characterisation test [\u003cspan class=\"CitationRef\"\u003e37\u003c/span\u003e] .\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec6\" class=\"Section2\"\u003e\n \u003ch2\u003eCharacterization and photocatalysis experiments\u003c/h2\u003e\n \u003cp\u003eThe produced materials were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), N2 adsorption-desorption, and ultraviolet-visible-near-infrared diffuse reflectance spectroscopy (UV-Vis-NIR DRS). After adding 20 mg of CdZnS@UIO-66 composite, UIO-66 [38 39], or CdZnS prepared using various techniques to 50 mL of dye solution at a mass concentration of 10 mg/L, the mixture was shaken for 30 minutes away from light. Next, the reaction solution to be tested was exposed to a 300 W xenon lamp to mimic sunlight at a distance of 30 cm (irradiance: 735 W/m\u003csup\u003e2\u003c/sup\u003e) [40 41]. The UV-Vis spectrophotometer was used to measure the mass concentration of the dye solution at various durations of illumination. Eq.\u0026nbsp;(\u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e) was then used to compute the degradation or adsorption rate (D,%):\u003c/p\u003e\n \u003cdiv id=\"Equ1\" class=\"Equation\"\u003e\n \u003cdiv class=\"mathdisplay\" id=\"FileID_Equ1\" name=\"EquationSource\"\u003e$$D/\\text{%}=\\left[\\right({\\rho }_{0}-{\\rho }_{e})/{\\rho }_{0}]\\times 100$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e1\u003c/div\u003e\u003c/div\u003e\u003cp\u003eWhere: \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\({\\rho }_{0}\\)\u003c/span\u003e\u003c/span\u003e,\u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\({\\rho }_{e}\\)\u003c/span\u003e\u003c/span\u003e are the starting and equilibrium mass concentration of the dye at a certain time of light exposure, mg/L, respectively.\u003c/p\u003e\u003c/div\u003e"},{"header":"Results and discussion","content":"\u003cp\u003eComparative XRD patterns of CdZnS, UIO-66, and CdZnS@UIO-66 are displayed in Fig. 1a\u0026nbsp;[17]\u0026nbsp;.The widening phenomena seen in the major diffraction peak of CdZnS suggest that its grains are finer. Although there are some stray peaks that could be solvent molecule residues, the XRD patterns of the composite CdZnS@UIO-66 match those of CdZnS and UIO-66 well, and most of the characteristic peaks can be attributed to them. This suggests that there is a larger proportion of UIO-66 in the composite.\u003c/p\u003e\n\u003cp\u003eFig. 1.b : Because photon energy is what drives the formation of charges, photocatalysts\u0026apos; range and light-absorbing capacity are essential for photocatalysis. UIO-66, CdZnS, and CdZnS@UIO-66 were examined for their photoabsorption characteristics using ultraviolet-visible (UV-Vis) spectroscopy. The figure shows that UIO-66 exhibits a steady photoresponse with varied degrees in the curves at 200~300 nm. However, at 300 nm, it decreases quickly near the edge of the absorption band, suggesting that semiconductor interband jumps are the cause of UiO-66\u0026apos;s absorption. CdZnS, on the other hand, shows more extensive and powerful absorption in the visible and ultraviolet spectrums. And after combining UIO-66 with CdZnS, the composite CdZnS@UIO-66\u0026apos;s light absorption ability was much higher than that of UIO-66 in both the UV and visible regions. This is explained by the fact that the two materials have varying capacities for absorbing light, and their composites both increase the complexes\u0026apos; overall capacity for light absorption while also having a large specific surface area and a high molecular weight. On the other hand, light may be completely and efficiently diffusely reflected inside the composite material because of its high specific surface area and characteristic multilayer pore structure. This improves CdZnS@UIO-66\u0026apos;s ability to utilize light.\u003c/p\u003e\n\u003cp\u003eFig. 1.c :\u0026nbsp;Through the use of thermogravimetric analysis, the thermal stability of the backbone structure may be measured by examining how the catalyst\u0026apos;s mass changes while the temperature is programmed to rise. It is evident from the figure that UIO-66 experiences two additional notable weight loss processes between 30-800 \u0026deg;C. About 20% of the weight of UIO-66 is lost between 100 and 300 degrees Celsius due to the evaporation of trace water molecules and the removal of certain organic ligands from its mesopores, which is the exact mechanism by which its defects occur. UIO-66 has a significant weight loss at 500 \u0026deg;C, which is a sign that the compound\u0026apos;s structure is starting to break down after 600 \u0026deg;C. CdZnS has strong thermal stability, with a mass loss of 6.5% occurring above 800 \u0026deg;C. Up to 350 \u0026deg;C, the composite CdZnS@UIO-66 retains an excellent structure in comparison to pure UIO-66; beyond that point, it exhibits nearly identical conditions to UIO-66.\u003c/p\u003e\n\u003cp\u003eThe UIO-66 particles are shown in Figs. 1(e) and (f), which provide statistical analyses of their regular forms, uniform particle sizes, and average grain sizes of 200~300 nm. The experimentally produced CdZnS powders, the majority of which are chrysanthemum-shaped, are displayed in Fig. (e). Particle size distribution is widely distributed, with sizes ranging from 1um to 2um. The scarce CdZnS chrysanthemum-like particles in solution are observed to have unevenly adsorbed numerous layers of UIO-66 in (f). The tiny particles entirely encircled the CdZnS, producing a tight organometallic skeleton shell layer.\u003c/p\u003e\n\u003cp\u003eA crucial characteristic of porous materials is their BET surface area, which is influenced by the size and shape of the pores. More active surface available for reactions to occur results in more reaction sites and adsorption locations, which are provided by a greater BET surface area. Because more reactants will be able to come into touch with the photocatalyst and react as a result, the photocatalytic reaction may be more active. Through N\u003csub\u003e2\u003c/sub\u003e adsorption-desorption studies, the specific surface area and pore size distribution profiles of CdZnS, CdZnS@UIO-66, and pure UIO-66 were ascertained.\u003c/p\u003e\n\u003cp\u003eThe adsorption-desorption isotherms of pure UIO-66 and composite CdZnS@UIO-66, as depicted in Fig 2.a and e, exhibit an I-shaped curve characteristic with a prominent adsorption inflection point in the low-pressure region of 0~0.1. At greater relative pressures, a well-shaped plateau appears, indicating microporosity. On the other hand, CdZnS, a macroporous solid material, displays a type III isotherm as seen in Fig 2.c. Adsorbed molecules cluster on the surface near the most gravitationally attractive spots, and the adsorbed material-adsorbed gas contact is comparatively weak.\u003c/p\u003e\n\u003cp\u003eFurthermore, as can be observed in Fig 2.e, the hysteresis loop curves that emerge are of the H\u003csub\u003e4\u003c/sub\u003e type, suggesting that the synthesized composites exhibit some mesopores that resemble those created by the lamellar structure in addition to the microporous structure. Furthermore, Table 1 demonstrates that the composites\u0026apos; BET specific surface area is 989.226 m\u003csup\u003e2\u003c/sup\u003eg\u003csup\u003e-1\u003c/sup\u003e, which is much greater than that of CdZnS (12.662 m\u003csup\u003e2\u003c/sup\u003eg\u003csup\u003e-1\u003c/sup\u003e) and only marginally less than that of UIO-66 (1095.452 m\u003csup\u003e2\u003c/sup\u003eg\u003csup\u003e-1\u003c/sup\u003e). The production of CdZnS wrapping by UIO-66 might be the cause. The three-level pore structure of the CdZnS@UIO-66 composites\u0026mdash;micropores, mesopores, and macropores is revealed by examining the Barret-JoynerHalenda (BJH) pore size distribution of the composites (Fig 2.f). The findings demonstrate that the multistage pore structure of the CdZnS@UIO-66 composites may speed up mass diffusion and transfer efficiency during the photocatalytic process in addition to reflecting and absorbing incoming light several times.\u003c/p\u003e\n\u003cp\u003eAdditional XPS research revealed comprehensive details on the valence and chemical composition of [email protected] seen in Fig 3.a, the XPS measurement scans indicated that the composite sample contained the elements O, N, C, Cd, Zn, S, and Zr. The C1s spectrum of CdZnS@UIO-66 is displayed in Fig 3.b, with two peaks at 531.95 e V and 530. 5 e V corresponding to Zr elements in UIO-66 on the material\u0026apos;s surface, as shown in Fig 3.c, and three peaks at 288.7 e V, 286.2 e V, and 284.8 e V corresponding to C-C/C=C, C-N, and O-C-O (which correspond to the functional groups of UIO-66). According to Fig 3.c, the Zr-O functional group and oxygen vacancies in UIO-66 on the material surface are represented by the two peaks at 531.95 e V and 530.5 e V. The XPS spectra of Zr 3d is seen in Fig 3. d, where two prominent peaks can be seen at 185.15 eV and 182.75 eV. These peaks, which match up with Zr 3d 5/2 and Zr 3d 3/2, show that Zr is present in the tetravalent zirconium ion (Zr \u003csup\u003e4+\u003c/sup\u003e) form . At 185.15 eV, the lesser distinctive peak is located, while at 182.75 eV, the stronger one.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe specific surface area and pore size of the UIO-66、CdZnS和CdZnS@UIO-66\u003c/p\u003e\n\u003ctable border=\"1\" cellspacing=\"0\" cellpadding=\"0\"\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd width=\"33.57400722021661%\" valign=\"top\"\u003e\n \u003cp\u003ematerials\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"33.2129963898917%\" valign=\"top\"\u003e\n \u003cp\u003especific surface area（m\u003csup\u003e2\u003c/sup\u003e/g）\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"33.2129963898917%\" valign=\"top\"\u003e\n \u003cp\u003ediameter of hole (nm)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"33.57400722021661%\" valign=\"top\"\u003e\n \u003cp\u003eUIO-66\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"33.2129963898917%\" valign=\"top\"\u003e\n \u003cp\u003e1095.452\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"33.2129963898917%\" valign=\"top\"\u003e\n \u003cp\u003e5.632\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"33.57400722021661%\" valign=\"top\"\u003e\n \u003cp\u003eCdZnS\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"33.2129963898917%\" valign=\"top\"\u003e\n \u003cp\u003e12.662\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"33.2129963898917%\" valign=\"top\"\u003e\n \u003cp\u003e43.142\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"33.57400722021661%\" valign=\"top\"\u003e\n \u003cp\u003eCdZnS@UIO-66\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"33.2129963898917%\" valign=\"top\"\u003e\n \u003cp\u003e989.226\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"33.2129963898917%\" valign=\"top\"\u003e\n \u003cp\u003e6.985\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n\u003c/table\u003e\n\u003cp\u003e\u0026nbsp;\u003cstrong\u003eDiscussion of photocatalytic methylene blue properties\u003c/strong\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eFig 4.(a) We conducted experiments on photocatalytic degradation of methylene blue by preparing composites with different mass ratios, as well as UIO-66 and CdZnS before compositing, in which the initial concentration of methylene blue was specified to be 30 mg/L. This allowed us to obtain CdZnS@UIO-66 composites with better catalytic performance. 50 mg of photocatalytic degradation materials were used, and the solution\u0026apos;s pH was left unchanged. The findings of photocatalytic methylene blue degradation at various mass ratios are displayed in Fig. 4a. the impact of methylene blue photocatalytic degradation at various mass ratios. The figure illustrates how the CdZnS material rises larger in the light of the 0-10min removal rate curve, and then tends to stabilize the rising process in a linear fashion where the removal rate is proportionate to the time. The remaining material rises faster in the 0~20min removal rate curve, reaching a stable rising state after 20 minutes of passage. The removal rate of 1% composite material for photocatalytic methylene blue degradation reached 98.74% after a 90-minute reaction period; in contrast, the removal rate of UIO-66 material was 82.92%, and the removal rate of CdZnS was only 63.73%. According to the experimental findings, the 1% manufactured composites enhanced the rate of photocatalytic methylene blue degradation and outperformed UIO-66 and CdZnS prior to the composites\u0026apos; synthesis.\u003c/p\u003e\n\u003cp\u003eFig 4.b: Methylene blue photocatalytic degradation by CdZnS@UIO-66 material dose. The figure shows that the removal rate increased at 20 and 30 milligrams of material, and that at 30 milligrams of material, the removal rate of methylene blue reached 99.87%. This is because light energy cannot be fully utilized when the material dose is modest since the photochemical particles produced by the light source are not entirely transformed into chemical energy. The production of additional active species and an increase in photocatalytic degradation efficiency can be achieved by appropriately increasing the dosage of degradation materials. The UIO-66 composite material was found to contain metal active sites through the previous review and literature, and the multistage pore structure can meet the mass transfer process of macromolecules simultaneously. As a result, by increasing the dosage of the degradation material, the active sites were increased and the material\u0026apos;s photocatalytic degradation efficiency was improved. Consequently, we need raise the additive amount of the materials accordingly when adding photocatalytic materials; 30 mg was the chosen additive amount.\u003c/p\u003e\n\u003cp\u003eFig 4.c: Following thirty minutes of dark adsorption, the experiment proceeded to the photocatalytic degradation stage. At 0~20 minutes, the removal rate rose sharply and quickly; however, after a steady plateau, the removal rate became proportionate to the time. This is because the composite materials\u0026apos; catalytic and adsorptive actions in the methylene blue solution degradation were carried out concurrently at a rate of 0~20 min, which significantly increased the clearance rate. Following that, each sample\u0026apos;s adsorption reduced during the photocatalytic degradation process, in which photocatalytic degradation was a key factor. The number of active sites on the material\u0026apos;s surface dropped as the reaction time was extended, and this reduced the driving force behind the degradation reaction. As a result, the degradation rate slowed down progressively until it reached the chemical reaction\u0026apos;s equilibrium. Following 40 minutes, the removal rates of the samples exhibiting varying concentrations of methylene blue solution showed a decreasing trend. This is because at low concentrations, the dye can quickly occupy the active sites of the material\u0026apos;s degradation reaction, improving the removal rate; at higher concentrations, however, the dye must diffuse internally to reach the surface of the degraded material, slowing down the adsorption process due to the spatial site-impedance repulsive force between the solute\u0026apos;s molecules. As a result, the removal rate declines.\u003c/p\u003e\n\u003cp\u003eFig 4.e: \u0026nbsp;Based on the graph, it is evident that the removal rate decreases as the number of experimental cycles increases. This is because the composite material\u0026apos;s methylene blue desorption process is not yet complete. Following the fourth cycle, the removal rate decreased steadily, which could be because of the degradation process\u0026apos;s chemical equilibrium. The elimination rate of methylene blue from CdZnS@UIO-66 after five rounds of cycling experimentation was found to be as high as 80.33%. This indicates that the composites maintained their strong photocatalytic activity even after many regeneration cycles and shown good stability and reusability.\u003c/p\u003e\n\u003cp\u003eFig 4.f: \u0026nbsp;We performed the following studies to assess CdZnS@UIO-66\u0026apos;s selectivity for methylene blue and learn more about its photocatalytic degradation performance for organic dyes. We chose various dyes with a concentration of 30 mg/L, such as methyl orange (MO), rhodamine B (RB), methylene blue , and reactive brilliant red X-3B, and conducted the photocatalytic degradation test under the conditions of adding 30 mg of CdZnS@UIO-66 and setting the initial pH of the solution to 7. Figure 4f presents the outcomes of the experiment.\u003c/p\u003e\n\u003cp\u003eFollowing a 30-minute dark reaction and a 90-minute light reaction, the photocatalytic degradation of methyl orange, rhodamine B, methylene blue, and reactive brilliant red X-3B by CdZnS@UIO-66 was 70.25%, 89.62%, 99.87%, and 92.38%, respectively. This suggests that CdZnS@UIO-66 performs well in catalytic degradation for all four dyes and has a high elimination efficiency. The greatest clearance rate of 99.87% was specifically attained for methylene blue. As a result, we can say that CdZnS@UIO-66 has good photocatalytic degradation performance for the treatment of dye wastewater and lacks selectivity for methylene blue.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003ePhotocatalytic mechanism of CdZnS semiconductor\u003c/strong\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe production of electron-hole pairs, their separation, and eventually their transport to the catalyst surface are the three processes that, in theory, make up the photocatalytic reaction of semiconductor materials. Based on this, the photogenerated holes and electrons react on various surface adsorption medium, in that order. Photogenerated carriers can excite CdZnS when exposed to photons with energy greater than Eg; however, these carriers are prone to aggregation. Additionally, oxidation and reduction events take place at the forward and reverse band sites, leading to additional reactions and the production of -OH. Basically, -OH is added to water to oxidize organic contaminants and create CO\u003csub\u003e2\u003c/sub\u003e and H\u003csub\u003e2\u003c/sub\u003eO .\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003ePhotocatalytic mechanism of CdZnS@UIO-66 composites\u003c/strong\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eWhen CdZnS and UIO-66 form a heterojunction, if their conductivity is opposite, electron-hole transport between the two will continue until their Fermi energy levels are equal . Here, UIO-66 and CdZnS combine to produce a space charge area, with one side of UIO-66 being negative and the other positive. The positive and negative charge regions combine to create an integrated electric field that forms a heterojunction. In the conductive band of CdZnS, photogenerated electron-hole pairs are generated in CdZnS. The self-built electric field causes the photogenerated holes to migrate from CdZnS to UIO-66 while the photogenerated electrons remain in CdZnS. This effectively prevents the electron-hole complexation, allowing the electron-hole to participate in the photocatalytic reaction in CdZnS and thereby increasing the rate of photocatalytic reaction.\u003c/p\u003e"},{"header":"Conclusions","content":"\u003cp\u003eTo sum up, we have chosen to employ CdZnS as a carrier in this research and have successfully created composites with strong photocatalytic characteristics using UIO-66. This is a unique structure made up of a metal-organic skeleton and three-dimensional CdZnS particles. The composites were built with simultaneous micro-, meso-, and macropores in a multistage pore structure. The photocatalytic efficiency of CdZnS@UIO-66 was demonstrated by the experimental findings to be much greater than that of pure CdZnS and pure UIO-66. In the experimental reaction, the starting concentration of methylene blue aqueous solution was 30 mg/L, the pH was 7, and the catalyst dose was 0.03 g. By exposing 50 mL of aqueous solution to visible light for 90 minutes, the degradation of methylene blue could reach 99.87%, demonstrating the strong photocatalytic effectiveness in the visible light range. The composite was made in an easy manner that increased UIO-66's visible light absorption range, enhanced its photocatalytic activity, and demonstrated the material's viability for use in photocatalytic degradation research.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgement\u003c/strong\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThis work was financially supported by Nature Science Foundation of Anhui province colleges and universities (No.2023AH052193), Excellent Young Talents Fund Program of Higher Education Institutions of Anhui Province (CN) (grant GXYQ2018072, GXYQ2017065), the National Natural Science Foundation of China (NSFC, Grants 51505121 and 51375139), the Natural Science Foundation of Hefei university (Grants 18ZR17ZDA, 18ZR18ZDA), and the Youth Talent Foundation of Hefei University (No. 16YQ05RC).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contributions\u003c/strong\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eT. J. wrote the main manuscript text and prepared figures 1-7. The author reviewed the manuscript.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting interests\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe author declares no competing interests.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eData availability\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAll data generated or analyzed during this study are included in this published article (and its supplementary information files).\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eAhmadijokani F et al (2020) Superior chemical stability of UiO-66 metal-organic frameworks (MOFs) for selective dye adsorption. Chem Eng J 399:125346\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eAhmadijokani F et al (2022) UiO-66 metal\u0026ndash;organic frameworks in water treatment: A critical review. Prog Mater Sci 125:100904\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eCelebi N, Aydin MY, Soysal F, Yıldız N, Salimi K (2020) Core/shell PDA@ UiO-66 metal\u0026ndash;organic framework nanoparticles for efficient visible-light photodegradation of organic dyes. ACS Appl Nano Mater 3:11543\u0026ndash;11554\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eEmbaby MS, Elwany SD, Setyaningsih W, Saber MR (2018) The adsorptive properties of UiO-66 towards organic dyes: A record adsorption capacity for the anionic dye Alizarin Red S. Chin J Chem Eng 26:731\u0026ndash;739\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eAky\u0026uuml;z D (2021) rGO-TiO2-CdO-ZnO-Ag photocatalyst for enhancing photocatalytic degradation of methylene blue. Opt Mater 116:111090\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eBai J, Xie Z, Han G, Diao G (2022) Double-shelled CeO2 coupled CdZnS nanoparticles as an efficient heterojunction visible light photocatalyst for hydrogen evolution. J Alloys Compd 919:165758\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eBaytar O, Sahin O, Kilicvuran H, Horoz S (2018) Synthesis, structural, optical and photocatalytic properties of Fe-alloyed CdZnS nanoparticles. J Mater Sci: Mater Electron 29:4564\u0026ndash;4568\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eCinsy N, Geetha R (2023) Characterization and photocatalytic activity of CdZnS nanoparticles incorporated with medicative leaf excerpt. Chalcogenide Lett 20:121\u0026ndash;129\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eFeng C et al (2021) Significantly enhanced photocatalytic hydrogen production performance of g-C3N4/CNTs/CdZnS with carbon nanotubes as the electron mediators. J Mater Sci Technol 80:75\u0026ndash;83. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.jmst.2020.11.047\u003c/span\u003e\u003cspan address=\"10.1016/j.jmst.2020.11.047\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eGayathri K, Vinothkumar K, Mohan S, Geetha Balakrishna R (2024) Manifestation of UiO-66-Zr MOF-enabled photocatalytic membranes for successive separation and degradation of dye mixtures in water remediation. J Environ Chem Eng 12:112490. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.jece.2024.112490\u003c/span\u003e\u003cspan address=\"10.1016/j.jece.2024.112490\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eYuan Y-P et al (2015) Improving photocatalytic hydrogen production of metal\u0026ndash;organic framework UiO-66 octahedrons by dye-sensitization. Appl Catal B 168:572\u0026ndash;576\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHan Y et al (2017) In situ synthesis of titanium doped hybrid metal\u0026ndash;organic framework UiO-66 with enhanced adsorption capacity for organic dyes. Inorg Chem Front 4:1870\u0026ndash;1880\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZhao D, Cai C (2021) Cerium-based UiO-66 metal-organic framework for synergistic dye adsorption and photodegradation: a discussion of the mechanism. Dyes Pigm 185:108957\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHaryanto A, Mukaromah L, Permana Y, Patah A (2021) Photocatalytic activity of CuBDC and UiO-66 MOFs for methyl orange degradation. J Chem Technol Metall 56:791\u0026ndash;795\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZhao Q et al (2020) UiO-66-NH2/Cu2O composite as an enhanced visible light photocatalyst for decomposition of organic pollutants. J Photochem Photobiol A 399:112625. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.jphotochem.2020.112625\u003c/span\u003e\u003cspan address=\"10.1016/j.jphotochem.2020.112625\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKonno H, Tsukada A (2022) Size-and ion-selective adsorption of organic dyes from aqueous solutions using functionalized UiO-66 frameworks. Colloids Surf A 651:129749\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLi T, Zhang Z, Yang Z (2023) Encapsulation of phosphotungstic acid into UiO-66-(OH)2 for synergistic and rapid photocatalytic degradation of organic pollutants. Mater Lett 348:134699. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.matlet.2023.134699\u003c/span\u003e\u003cspan address=\"10.1016/j.matlet.2023.134699\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZheng M, Yao C, Xu Y (2020) Fe3O4 nanoparticles decorated with UIO-66 Metal\u0026ndash;Organic Framework particles and encapsulated in a triazine-based Covalent Organic Framework matrix for photodegradation of anionic dyes. ACS Appl Nano Mater 3:11307\u0026ndash;11314\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLiu H et al (2022) Modified UiO-66 as photocatalysts for boosting the carbon-neutral energy cycle and solving environmental remediation issues. Coord Chem Rev 458:214428\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHoroz S, Baytar O, Sahin O, Kilicvuran H (2018) Photocatalytic degradation of methylene blue with Co alloyed CdZnS nanoparticles. J Mater Sci: Mater Electron 29:1004\u0026ndash;1010\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJayaraman V, Palanivel B, Ayappan C, Chellamuthu M, Mani A (2019) CdZnS solid solution supported Ce2Sn2O7 pyrochlore photocatalyst that proves to be an efficient candidate towards the removal of organic pollutants. Sep Purif Technol 224:405\u0026ndash;420\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJeon HW et al (2020) Photocatalytic Degradation of Rhodamine B, Methyl Orange and Methylene Blue with CdS and CdZnS/ZnO Catalysts under Visible Light Irradiation. Clean Technol 26:311\u0026ndash;320\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eAboraia AM et al (2023) A heterostructural MoS2QDs@UiO-66 nanocomposite for the highly efficient photocatalytic degradation of methylene blue under visible light and simulated sunlight\u0026dagger;\u0026dagger;Electronic supplementary information (ESI) available. RSC Adv 13:34598\u0026ndash;34609. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1039/d3ra06299f\u003c/span\u003e\u003cspan address=\"10.1039/d3ra06299f\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e. See DOI\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eYin Y et al (2022) A new type of composite catalyst AmCoPc/UiO-66-NH2 synergistic photocatalytic degradation of dyes. Inorg Chem Commun 145:109914. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.inoche.2022.109914\u003c/span\u003e\u003cspan address=\"10.1016/j.inoche.2022.109914\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMansouri M, Sadeghian S, Mansouri G, Setareshenas N (2021) Enhanced photocatalytic performance of UiO-66-NH2/TiO2 composite for dye degradation. Environ Sci Pollut Res 28:25552\u0026ndash;25565\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZhou Y-C et al (2019) Facile fabrication and enhanced photocatalytic performance of visible light responsive UiO-66-NH2/Ag2CO3 composite. Chin J Catal 40:1912\u0026ndash;1923. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/S1872-2067(19)63433-9\u003c/span\u003e\u003cspan address=\"10.1016/S1872-2067(19)63433-9\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLiu H et al (2023) Confinement of Organic Dyes in UiO-66-Type Metal\u0026ndash;Organic Frameworks for the Enhanced Synthesis of [1, 2, 5] Thiadiazole [3, 4-g] benzoimidazoles. J Am Chem Soc 145:17588\u0026ndash;17596\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eYasmeen K et al (2022) Removal of Pb(II) from water samples using surface modified core/shell CdZnS/ZnS QDs as adsorbents: Characterization, adsorption, kinetic and thermodynamic studies. Arab J Chem 15:104224. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.arabjc.2022.104224\u003c/span\u003e\u003cspan address=\"10.1016/j.arabjc.2022.104224\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMohammadi A et al (2017) Metal-organic framework Uio-66 for adsorption of methylene blue dye from aqueous solutions. Int J Environ Sci Technol 14:1959\u0026ndash;1968\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMousavi DV et al (2021) Adsorption performance of UiO-66 towards organic dyes: Effect of activation conditions. J Mol Liq 321:114487\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eNi Q, Feng S, Ke X, Yan Z, Luan J (2023) Multi-dimensional (2D\u0026ndash;3D) assembly of BiOI/BiOBr/UiO-66-NH2 composites to form multi-heterojunction structures for synergistic removal of Rhodamine B. J Alloys Compd 935:168103. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.jallcom.2022.168103\u003c/span\u003e\u003cspan address=\"10.1016/j.jallcom.2022.168103\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eTian H et al (2021) BiOBr@UiO-66 photocatalysts with abundant activated sites for the enhanced photodegradation of rhodamine b under visible light irradiation. Mater Sci Engineering: B 271:115297. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.mseb.2021.115297\u003c/span\u003e\u003cspan address=\"10.1016/j.mseb.2021.115297\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKhudhair EM, Khudhair WN, Ammar SH, Mahdi AS (2022) Assembling ZIF-67@ Cd0. 5Zn0. 5S nanocomposites with an enhanced photocatalytic activity. Inorg Chem Commun 142:109639\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKilicvuran H, Sahin O, Baytar O, Horoz S, INTERNATIONAL JOURNAL OF ENGINEERING SCIENCES \u0026amp; RESEARCH TECHNOLOGY CHARACTERIZATION OF Ni Doped CdZnS NANOPARTICLES AND THEIR USE IN METHYLENE BLUE DEGRADATION UNDER VISIBLE LIGHT IRRADIATION\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZhang X et al (2023) Construction of 0D/2D CdZnS quantum dots/SnIn4S8 nanosheets heterojunction photocatalysts for boosting photocatalytic performance. Colloids Surf A 664:131184\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMureithi AW et al (2023) 3d (Co and Mn) and 4d (Ag) Transition Metal-Doped ZnO Nanoparticles Anchored on CdZnS for the Photodegradation of Rhodamine B. Crystals 14:41\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003ePalanisamy G et al (2021) An efficient and magnetically recoverable g-C3N4/ZnS/CoFe2O4 nanocomposite for sustainable photodegradation of organic dye under UV\u0026ndash;visible light illumination. Environ Res 201:111429\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eQi Xm et al (2021) Design of UiO-66@BiOIO3 heterostructural composites with remarkable boosted photocatalytic activities in removing diverse industrial pollutants. J Phys Chem Solids 151:109903. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.jpcs.2020.109903\u003c/span\u003e\u003cspan address=\"10.1016/j.jpcs.2020.109903\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eVan Le D, Nguyen MB, Dang PT, Lee T, Nguyen TD (2022) Synthesis of a UiO-66/g-C3N4 composite using terephthalic acid obtained from waste plastic for the photocatalytic degradation of the chemical warfare agent simulant, methyl paraoxon\u0026dagger;\u0026dagger;Electronic supplementary information (ESI) available: HPLC spectrum of H2BDC, schematic synthesis of UiO-66/g-C3N4, XRD analysis, EDS spectra, SEM images, UV-vis spectra of DMNP, images of DMNP solution, LC-mass spectra of DMNP, photo-stability test, element composition, and a comparison of photocatalytic activity of photocatalysts. See \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1039/d2ra03483b\u003c/span\u003e\u003cspan address=\"10.1039/d2ra03483b\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e. \u003cem\u003eRSC Advances\u003c/em\u003e 12, 22367\u0026ndash;22376, doi:https://doi.org/10.1039/d2ra03483b\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eSha Z, Chan HSO, Wu J (2015) Ag2CO3/UiO-66(Zr) composite with enhanced visible-light promoted photocatalytic activity for dye degradation. J Hazard Mater 299:132\u0026ndash;140. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.jhazmat.2015.06.016\u003c/span\u003e\u003cspan address=\"10.1016/j.jhazmat.2015.06.016\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eTan Y et al (2021) A novel UiO-66-NH2/Bi2WO6 composite with enhanced pollutant photodegradation through interface charge transfer. Colloids Surf A 622:126699. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.colsurfa.2021.126699\u003c/span\u003e\u003cspan address=\"10.1016/j.colsurfa.2021.126699\" 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":false,"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":"transition-metal-chemistry","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"tmch","sideBox":"Learn more about [Transition Metal Chemistry](http://link.springer.com/journal/11243)","snPcode":"11243","submissionUrl":"https://submission.nature.com/new-submission/11243/3","title":"Transition Metal Chemistry","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"CdZnS, UIO-66, Methylene blue, Dye wastewater, Photocatalytic reaction","lastPublishedDoi":"10.21203/rs.3.rs-4531692/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4531692/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eOne of the primary sources of industrial wastewater is dye wastewater, which is challenging for conventional water treatment methods to properly degrade because of its complex composition, high chromaticity, difficulty being biochemically destroyed, etc. The utilization of photocatalysts in conjunction with light energy, or photocatalytic technology, is thought to be a sustainable approach to treating dye wastewater due to its many benefits, including high degradation efficiency, rapid reaction times, and the absence of secondary contamination. We chose to employ CdZnS as a carrier in this research, together with composite UIO-66. The degradation of the dye methylene blue was carried out using the composite CdZnS@UIO-66 as a photocatalyst, and the results were compared to those of pure CdZnS and pure UIO-66. The findings demonstrated that CdZnS@UIO-66 had a noticeably greater photocatalytic efficiency than the other two. Up to 99.87% of the methylene blue in 50 mL of aqueous solution was degraded in the experimental reaction with a catalyst dosage of 0.03 g, pH of 7, and an initial concentration of 30 mg/L of methylene blue aqueous solution when exposed to visible light for 90 minutes. This indicates excellent photocatalytic efficacy in the visible range, the formation of an interfacial electron transfer phenomenon within the heterojunction, and the use of UIO-66 as an electron acceptor to further enhanced photocatalytic effect is caused by the development of interfacial electron transfer phenomena within the heterojunction and UIO-66 as an electron acceptor, which further promotes the internal photogenerated electron-hole separation.\u003c/p\u003e","manuscriptTitle":"Synthesis, characterisation, and effective photocatalytic degradation applications in organic dye molecules using CdZnS-loaded UIO-66 composites","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-06-26 11:26:35","doi":"10.21203/rs.3.rs-4531692/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"editorAssigned","content":"","date":"2024-06-11T17:56:21+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2024-06-11T16:40:12+00:00","index":"","fulltext":""},{"type":"submitted","content":"Transition Metal Chemistry","date":"2024-06-05T06:00:34+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"transition-metal-chemistry","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"tmch","sideBox":"Learn more about [Transition Metal Chemistry](http://link.springer.com/journal/11243)","snPcode":"11243","submissionUrl":"https://submission.nature.com/new-submission/11243/3","title":"Transition Metal Chemistry","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"72e52b33-37d2-43b8-8838-303973a9b49e","owner":[],"postedDate":"June 26th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[],"tags":[],"updatedAt":"2024-06-26T11:26:36+00:00","versionOfRecord":[],"versionCreatedAt":"2024-06-26 11:26:35","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-4531692","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4531692","identity":"rs-4531692","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}