Thiazolo[5,4-d]thiazole-Based CMPs as Bifunctional Photocatalysts for H₂O₂ Production and Organic Pollutant Degradation

Thiazolo[5,4-d]thiazole-Based CMPs as Bifunctional Photocatalysts for H₂O₂ Production and Organic Pollutant Degradation | 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 Thiazolo[5,4-d]thiazole-Based CMPs as Bifunctional Photocatalysts for H₂O₂ Production and Organic Pollutant Degradation Yuting Ren, Mingyue Wang, Shuangjie Zhang, Chunhua Yuan, Jianmei Zhou, and 2 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7940600/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 06 Jan, 2026 Read the published version in Research on Chemical Intermediates → Version 1 posted 9 You are reading this latest preprint version Abstract Two donor-acceptor (D-A)-type conjugated microporous polymers (CMPs), TT-PA and TT-BPA, are successfully synthesized based on thiazolo[5,4- d ]thiazole (TzTz) as the acceptor unit. The rigid plane of TzTz enables a close and effective π-π stacking between polymer layers, which is beneficial for the transport of charges between layers and the improvement of photocatalytic performance. The high-density S and N atoms in the TzTz units can act as Lewis base sites to adsorb O₂ molecules. Subsequently, TzTz transfers the photogenerated electrons to the adsorbed O₂, generating ·O₂⁻, which is conducive to the 2e - oxygen reduction reaction (ORR) pathway for the photocatalytic production of H₂O₂ and the degradation of the pollutant Rhodamine B (RhB). The PL, EIS and photocurrent data indicate that TT-PA has a lower charge recombination rate and higher charge separation efficiency, stemming from the appropriate size and electron-attracting ability of triphenylamine. Therefore, the combination of TzTz and triphenylamine in TT-PA is the "golden combination" for achieving the best D-A effect, pore structure and photocatalytic performance due to the best D/A ratio. This study gives insights into the design of CMP photocatalyst. Donor-acceptor Conjugated microporous polymers Photocatalysis H2O2 Photodegradation of RhB Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 1. Introduction Hydrogen peroxide (H 2 O 2 ) is a clean, environmentally friendly oxidizing agent that plays significant roles in the chemical industry[ 1 ], healthcare, and water treatment. It is in high demand, with an estimated 4 million tons of H 2 O 2 being used annually worldwide, and that number is predicted to rise to 5.7 million tons in 2027. Conventional anthraquinone and electrochemical methods are typically used in the industrial synthesis of H 2 O 2 , but these processes have a number of disadvantages, including the potential of explosion, the production of hazardous byproducts, and significant energy consumption[ 2 , 3 ]. With noble metal-based catalysts (such as Pd, Au, and Pt), H 2 O 2 can be directly produced from H 2 and O 2 . However, their high cost makes this process unsuitable for scaling up to commercial production[ 4 – 6 ]. Photocatalytic technology exhibits promising application potential in H 2 O 2 synthesis because of its low energy consumption, high efficiency, and ease of operation[ 7 – 9 ]. Under light, two-electron oxygen reduction and two-electron water oxidation are typically used to achieve photocatalytic H 2 O 2 production on semiconductors[ 10 , 11 ]. Among them, a variety of porous organic polymers (POPs), such as metal-organic frameworks (MOFs)[ 12 , 13 ], covalent organic frameworks (COFs)[ 14 ], and CMPs[ 15 – 17 ], have been developed as promising organic semiconductors for the photocatalytic preparation of H 2 O 2 . The molecular-level optimization of CMPs' chemical structure, material composition, and optoelectronic characteristics is made possible by readily available building blocks and comparatively straightforward synthesis techniques. Because of their low cost, customized properties, and ease of preparation, CMPs[ 18 ] have attracted great interest in many fields due to their extensive surface area, robust structure, and the nature of the three-dimensional conjugated framework. And, by designing the D-A structure through molecular engineering, the photocatalytic H 2 O 2 yield of CMP can be significantly increased. Pan et al. recently develop a series of CMPs using a D-A-A type system[ 19 ], and their photocatalytic efficiencies exceed more than twice that of the D-A polymer. The D-A1-A2 structure by Liao et al.[ 20 ] can significantly improve the photocatalytic performance of CMP photocatalysts. D-π-A and D-π-A-A structures[ 21 ] have independently studied for the simultaneous H 2 O 2 evolution accompanied by pollutant degradation. Enhancing conjugation within the molecular structure facilitates electron transfer, which in turn improves photocatalytic performance. Our laboratory is dedicated to introduce TzTz units into porous organic polymers (POPs)[ 22 ], whose photocatalytic performance is enhanced by promoting charge separation and increasing active sites. And the rigid planar TzTz structure has strong electron acceptor properties and excellent light-absorbing capacity[ 23 , 24 ]. Additionally, high electron and hole mobility is provided by significant p-p stacking and orbital overlap in the solid state of CMPs. Therefore, building upon our previous work and the promising properties of the TzTz unit, we herein design and synthesize two novel D-A type CMPs, namely TT-PA and TT-BPA, using TzTz as the universal acceptor core but coupling it with two different donors (triphenylamine and biphenylamine, respectively). We systematically investigate how the subtle change in the donor unit impacts the polymer's porosity, optoelectronic properties, and ultimately, its photocatalytic efficiency for both H₂O₂ production and pollutant degradation. This comparative study provides deep insights into the structure-property relationship for designing high-performance CMP photocatalysts. 2. Experimental 2.1. Materials 4,4',4''-nitrilotribenzaldehyde, 4',4''',4'''''-nitrilotris(([1,1'-biphenyl]-4-carbaldehyde)), dithiooxamide, N,N -Dimethylformamide(DMF), para-benzoquinone (pBQ), silver nitrate (AgNO 3 ), L-histidine (L-his), ethylenediaminetetraacetic acid disodium salt (EDTA-2Na), 2,2,6,6-tetramethylpiperidine oxide (TEMPO), isopropyl alcohol (IPA), and other common solvents were purchased from commercial suppliers (Adamas, Shanghai, China and Leyan, Shanghai, China) without further purification. 2.2. Synthesis Synthesis of TT-PA: 4,4',4''-nitrilotribenzaldehyde (500 mg, 1.52 mmol), dithiooxamide (291.9 mg, 2.43 mmol) in 10 mL of DMF solution were heated at 160°C for 3 days under N 2 protection. After the reaction mixture was cooled to room temperature, the crude polymer was then diafiltrated 3 times with methanol. After that, the polymer was washed thoroughly with CHCl 3 , methanol Soxhlet extraction for 24 hours. Finally, the product was dried under vacuum at 70°C for 24 h to obtain an orange powder (582.6 mg, 74% yield). Synthesis of TT-BPA: Under N 2 protection, 4',4''',4'''''-nitrilotris(([1,1'-biphenyl]-4-carbaldehyde)) (500 mg, 0.90 mmol), dithiooxamide (172.4 mg, 1.43 mmol) were heated in 10 mL of DMF solution at 160°C for 3 days. After the reaction mixture was cooled to room temperature, the crude polymer was then diafiltrated 3 times with ethanol. After that, the polymer was thoroughly washed with methanol, CHCl 3 , and anhydrous ethanol Soxhlet extraction for 24 hours. Finally, the product was dried under vacuum at 70°C for 24 h to obtain a yellow powder (490.6 mg, 73% yield). 2.3. Characterization Fourier-transformed infrared (FT-IR) spectra were recorded on dried KBr disks in transmission mode using Bruker VERTEX 70 FTIR spectrometer. Solid-state cross-polarization magic angle spinning (CP/MAS) 13 C NMR spectra were obtained on a 400 MHz Bruker-500 NMR spectrometer. Polymer morphologies were investigated with a Zeiss SIGMA 500 field emission scanning electron microscope (SEM). Additionally, elemental mapping was performed using a BRUKER XFlash 6130. Before measurement, the samples were sputter coated with gold. Detailed morphological and structural characterizations were performed using a high-resolution transmission electron microscope (HR-TEM, JEOL, Tokyo, Japan). Powder X-ray diffraction (PXRD) patterns were performed on an X-ray diffraction spectrometer (Bruker AXS GmbH, Germany). The samples were degassed in a vacuum at 150 °C for 6 h before measurement. Thermo-gravimetric analysis (TGA) was conducted on NETZSCH 209 F3. The samples were heated at 10 °C/min under a nitrogen atmosphere up to 800 °C. X-ray photoelectron spectroscopy (XPS) spectra were recorded using an ESCALAB 250 Xi XPS system of Thermo Scientific, where the base pressure in analysis chamber was 1.5×10 − 9 mbar and the X-ray spot was 500 µm. Ultraviolet–visible spectra were measured on a UV-VIS-NIR spectrophotometer (Cary-100, Agilent Technologies Inc., Santa Clara, CA, USA) at room temperature. Surface area, N 2 adsorption isotherms (77 K), and pore size distributions were measured using the micromeritics ASAP 2460 surface area and porosity analyzer. 2.4. Photoelectrochemical Measurement Electrochemical measurements were measured on a CHI760E electrochemical workstation in a three-electrode system using photocatalyst-coated indium-tin oxide (ITO) glass as the working electrode, an Ag/AgCl electrode as the reference electrode, and a platinum flake as the counter electrode. Electrochemical impedance spectroscopy (EIS), transient photocurrent measurements, and Mott–Schottky analysis were conducted in a 0.2 M Na 2 SO 4 aqueous solution. 2.5. Photocatalytic H 2 O 2 Synthesis The detailed experimental procedure was as follows: the photocatalyst was dispersed in 30 mL of pure water, it was stirred with oxygen for 30 min to reach the oxygen saturation state under dark conditions. The catalyst was then exposed to light under a 300 W Xe lamp for 60 min. At a given time, a certain amount of reaction solution (1.0 mL) was collected and filtered with a 0.22 µm filter membrane. The H 2 O 2 concentration was determined by the iodometry method at 351 nm. Finally, the concentration of H 2 O 2 was calculated from the fitted curve. 2.6. Photodegradation of RhB For the degradation of RhB, CMPs were dispersed in an aqueous solution of RhB (50 mL, 10 mg L -1 ), and the mixture was stirred for 30 min in the darkness to obtain adsorption–desorption equilibrium. After that, the solution was irradiated with a 300 W Xe lamp. At defined time intervals, an appropriate amount of suspension was filtered through a filter membrane to remove solid particles and absorbance of the filtrate at 554 nm was obtained by a UV–Vis spectrophotometer. The RhB removal efficiency was calculated using the following equation: $$\:\text{Removal\:efficiency}\left(\text{\%}\right)\text{=}\frac{{\text{c}}_{\text{0}}\text{-}\text{c}}{{\text{c}}_{\text{0}}}\text{×100\%}$$ where \(\:\text{c}\) 0 denotes the initial concentration of RhB and \(\:\text{c}\) denotes the concentration of RhB at each irradiated time interval. 3. Results and Discussion 3.1. Synthesis and Characterization The condensation of dithiooxamide with aldehyde groups formed the TzTz rings (Scheme 1 ). Both of them were stable in water and insoluble in common organic solvents. The aromaticity and rigidity of the TzTz ring enabled CMPs to have excellent thermal stability. TGA demonstrated that severe decomposition commencing at about 400°C for two samples (Figure S2). The weight loss below 300°C might be ascribed to the removal of water or other solvent molecules adsorbed on the sample. The successful synthesis of TT-PA and TT-BPA was confirmed by the solid-state 13 C NMR spectra (Fig. 1 a). The peaks at 167 ppm and 165 ppm were assigned to the carbon atoms of the C = N groups in the TzTz moiety of TT-PA and TT-BPA, respectively. The peak at 151 ppm were carbon-carbon double bonds in the TzTz structure. The FT-IR spectra (Fig. 1 b, c) showed the disappearance of the N-H stretching vibration peak at 3291 cm⁻¹ (from-NH₂ in DTO) and the C = O stretching vibration peak at 1684 cm⁻¹ (from -CHO in TFPA or TFBA)[ 25 ], concurrently with the emergence of a new distinctive peak at 1620 cm⁻¹ (C = N stretching vibration), indicating that -NH 2 reacted with -CHO to produce an imine bond (C = N). This also proved the formation of the TzTz ring and CMPs[ 26 ]. The PXRD of TT-PA and TT-BPA (Figure S3) indicated that broad 2θ peaks at roughly 18° or 24° was a typical feature π-π stacking intercalation of the CMPs[ 20 ]. The rigid planarity of TzTz enabled π-π stacking between the polymer layers, which was beneficial for the transfer of charges between the layers and the photocatalytic improvement of CMPs. TT-PA and TT-BPA's porosity was assessed using nitrogen adsorption isotherm tests at 77 K (Figure S4-6). Type IV isotherms were used to describe the adsorption curves. When compared to TT-BPA (27.63 m²/g), TT-PA's BET specific surface area (112.78 m²/g) was significantly greater. Adsorption-averaged pore size (6.75 nm) and desorption-averaged pore size (2.78 nm) of TT-PA were greater than those of TT-BPA (6.23 and 2.64 nm, respectively), according to NL-DFT calculations. Apparently, the smaller triphenylamine combined with TzTz could generate a more favorable pore structure, providing a more advantageous environment for the adsorption and diffusion of reactants (O₂, H₂O) and the desorption of products (H₂O₂). XPS was used to further evaluate the materials' chemical states and bonding topologies (Fig. 2 ). The XPS spectra of TT-PA and TT-BPA suggested that the elements C, N, O, and S were the most prevalent in all samples. TT-PA's C 1s spectrum (Fig. 2 b) conformed to four peaks that corresponded to C-C (284.8 eV), C = C (286.0 eV), C-N (287.5 eV), and C = N (291.6 eV), respectively. In a similar vein, TT-BPA (Fig. 2 f) displayed four peaks at 284.8, 285.6, 286.0, and 291.5 eV that correspond to C-C, C = C, C-N, and C = N[ 27 , 28 ], respectively. The fitted peaks at 400.1 eV (or 400.5 eV) in the high-resolution XPS spectra of the N 1s (Fig. 2 c, g) belonged to C -N, while the peak at 399.2 eV (or 399.5 eV) belonged to C = N[ 29 , 30 ]. These characterization investigations demonstrated the effective synthesis of TT-PA and TT-BPA. The S and N atoms on the surface of the CMPs could act as Lewis base sites to adsorb O₂ molecules, thereby reducing the activation energy barrier for O₂ reduction and facilitating the 2e⁻ ORR pathway for the generation of H₂O₂ over the 4e⁻ pathway for the generation of H₂O. Figure 3 showed the morphologies of TT-PA and TT-BPA. Both materials were nearly spherical in shape and connected to each other to form layered structures. The particle size of TT-PA was smaller than that of TT-BPA. This explained the reason why the pore diameter and specific surface area of TT-PA were larger. There were ordered or disordered microporous structures between lamellar structures, which were crucial characteristics of conjugated microporous polymers for the storage and transportation of molecules. 3.2. Photoelectric Property Studies The well-defined D-A structures and favorable π-π stacking, as confirmed above, were anticipated to facilitate the separation and transport of photogenerated charge carriers. To validate this hypothesis and correlate the molecular structure with photocatalytic activity, we systematically investigated the optoelectronic properties of TT-PA and TT-BPA. The optical absorption properties of TT-PA and TT-BPA were characterized by UV–Vis DRS. According to Fig. 4 a, TT-PA and TT-BPA exhibited broad absorption range, indicating excellent light absorption properties. From which the bandgap (Fig. 4 b) of the valence band (VB) and the conduction band (CB) calculated using the Kubelka-Munk function to be 2.16 eV and 2.28 eV for TT-PA and TT-BPA, respectively[ 31 ]. In TT-PA (Fig. 4 c) and TT-BPA (Figure S8), the corresponding flat-band potentials relative were 0.92 V and 1.06 V, respectively, according to the Mott-Schottky plots[ 32 ]. The slopes of the curves for both photocatalytic materials were positive, indicating that they were n-type semiconductors[ 33 ], which facilitated the rapid transfer and transportation of photogenerated electrons in CMP, thereby enhancing the separation efficiency of photogenerated carriers. The band structure diagrams (Fig. 4 d) showed that both CMPs possessed conduction band potentials that were more negative than the potential required for the direct 2e⁻ ORR pathway (E = + 0.68 V vs. NHE for H₂O₂ production)[ 34 ]. In order to study the separation efficiency of photogenerated charge and the migration rate of photogenerated carriers in the two CMPs, photoluminescence spectroscopy (PL), the electrochemical impedance spectroscopy (EIS) and photocurrent response of the samples were measured. As seen in Fig. 5 a, TT-BPA exhibited stronger photoluminescence, meaning that the photogenerated electron-hole pairs were more likely to be compounded, thereby lowering the photocatalytic activity[ 35 ]. The EIS tests revealed that TT-PA had smaller Nyquist semicircle diameters than TT-BPA, as illustrated in Fig. 5 b. This suggested that TT-PA had a better interfacial charge transfer process and a reduced interfacial carrier transport resistance[ 36 ]. Furthermore, the results of the transient photocurrent measurement (I-t) confirmed that TT-PA had a higher carrier separation efficiency[ 37 ]. The visible response photocurrent of TT-PA was noticeably higher than that of TT-BPA (Fig. 5 c). Therefore, the electron transfer impedance was smaller, the transmission was faster, and the efficiency of photogenerated carrier separation was higher in TT-PA. 3.3. Theoretical studies Density flood theory (DFT) simulations were used to examine the pre-molecular orbitals of two CMPs model fragments in order to gain a better understanding of how structural units affect the photovoltaic characteristics of CMPs (Fig. 6 ). According to molecular simulations, TT-BPA's lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) energy levels were found in the acceptor unit of the TzTz structure and the anisotropic triangular π-conjugated structural unit, respectively. These findings were consistent with the results of the simulated surface electrostatic potential (ESP). The remarkable charge separation efficiency seen in TT-PA might have been largely attributed to the non-overlapping energy level distribution, which successfully inhibited the recombination of photogenerated holes and electrons[ 38 , 39 ]. 3.4. Photocatalytic Performance in H 2 O 2 Production The photocatalytic H 2 O 2 production performance of the CMPs were carried out under visible light irradiation. As shown in Fig. 7 a, the H 2 O 2 yield of TT-PA was higher than that of TT-BPA. TT-PA and TT-BPA showed the highest rates of hydrogen peroxide production in an O 2 environment (2470.20 µmol g -1 h -1 and 2041.46 µmol g -1 h -1 , respectively) compared with air or nitrogen conditions, suggesting that the pathway for H₂O₂ generation was 2e - ORR pathway. Furthermore, the stability and recyclability of TT-PA and TT-BPA (Fig. 7 b) were conducted to evaluate long-time photocatalytic durability. After four consecutive cycles, the photocatalytic H 2 O 2 production rate fluctuated only slightly, indicating that the material had good recyclability. As shown in Fig. 7 c, the solar-to-chemical conversion (SCC) efficiency of TT-PA was 0.41%, and that of TT-BPA was 0.38%, both of which exceeded the efficiency of natural synthetic plants (≈ 0.1%)[ 40 ] and most of reported photocatalysts (Figure S9a and Table S1 ). Figure 7 d illustrated the maximum apparent quantum yield (AQY) values of TT-PA and TT-BPA were 0.55% and 0.49%, respectively. The specific data were shown in Table S2, Figure S9b illustrated TT-PA had advantages in the photocatalytic H 2 O 2 production process. Mechanism Study of H 2 O 2 Production Capture experiments were used to investigate the primary active species in the reaction system. AgNO 3 , pBQ, EDTA-2Na, and L-his were chosen to absorb electrons (e⁻), superoxide radicals (⋅O₂⁻), holes (h⁺), and hydroxyl radicals (⋅OH), respectively (Figure S9c). The H₂O₂ yield dropped from 2470.21 µmol to 172.35 µmol upon the addition of pBQ to the reaction system, indicating that ·O₂⁻ was the primary active species in the ORR pathway. Thus H 2 O 2 was mainly generated through the ORR pathway[ 34 , 41 ]. (The TT-BPA capture experiment could be found in Figure S9d.) Photodegradation of RhB The mechanism study in section 3.5 revealed that superoxide radicals (·O₂⁻) were the primary active species in the photocatalytic system of TT-PA and TT-BPA. Notably, ·O₂⁻ was also a potent oxidant for the decomposition of organic pollutants. This common active species prompted us to explore the application of these CMPs in photocatalytic environmental remediation. We selected Rhodamine B (RhB), a refractory organic dye, as a model pollutant to evaluate the photodegradation performance of TT-PA and TT-BPA. During the degaration process, the color of the RhB solution changed from pink to colorless (Figure S11). The degradation data demonstrated that TT-PA had superior photodegradation performance over TT-BPA. The photodegradation efficiency of TT-PA (0.3 g L -1 ) on RhB (10 mg L -1 ) was 99.81% at 30 minutes (Figure S12a). In contrast, the photodegradation efficiency of TT-BPA was 99.81% at almost 70 minutes (Figure S13a). In another control experiment, we changed the amounts of TT-PA and TT-BPA catalysts to 5 mg, 10 mg, 15 mg, and 20 mg. The highest degradation efficiency (99.0%) was attained in 30 minutes at the amount of 20 mg (0.4 g L -1 ) of TT-PA (Figure S12b), which was more than twice as fast as that of TT-BPA (Figure S13b). The impact of pH on the catalyst's ability was depicted in Figure S12c and S13c. TT-PA and TT-BPA had the best absorption at pH = 3. Furthermore, after four consecutive cycles, the catalytic performance of TT-PA and TT-BPA decreased very little (Figure S12f and S13f). 4. Conclusions In summary, we have successfully synthesized two TzTz-based D-A CMPs, TT-PA and TT-BPA, via a straightforward catalyst-free condensation reaction. A comprehensive comparison demonstrated that the donor unit, in conjunction with the TzTz acceptor, played a decisive role in steering the material's properties. TT-PA, incorporating the triphenylamine donor, exhibited a superior combination of larger specific surface area, more efficient charge separation and transfer, and consequently, enhanced photocatalytic performance. The yield of H 2 O 2 produced by TT-PA photocatalysis was 2470.20 µmol g -1 h -1 , and it degraded 99.81% of RhB within 30 minutes. Furthermore, they were stable and recyclable. Declarations Author Contribution Yuting Ren: Formal analysis, Writing-original draft. Mingyue Wang: Data curation. Shuangjie Zhang: Software. Chunhua Yuan: Supervision. Jianmei Zhou: Methodology. Dongmei Li: Writing-review & editing, Funding acquisition, Conceptualization. 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Cite Share Download PDF Status: Published Journal Publication published 06 Jan, 2026 Read the published version in Research on Chemical Intermediates → Version 1 posted Editorial decision: Revision requested 29 Nov, 2025 Reviews received at journal 29 Nov, 2025 Reviews received at journal 27 Nov, 2025 Reviewers agreed at journal 13 Nov, 2025 Reviewers agreed at journal 11 Nov, 2025 Reviewers invited by journal 11 Nov, 2025 Editor assigned by journal 27 Oct, 2025 Submission checks completed at journal 27 Oct, 2025 First submitted to journal 24 Oct, 2025 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. 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09:24:25","extension":"html","order_by":21,"title":"","display":"","copyAsset":false,"role":"acdc-reference","size":122715,"visible":true,"origin":"","legend":"","description":"","filename":"earlyproof.html","url":"https://assets-eu.researchsquare.com/files/rs-7940600/v1/faffe70566668e9d892958f8.html"},{"id":96599869,"identity":"22c4aa52-aafe-4e28-9001-5dee6cfe8ab7","added_by":"auto","created_at":"2025-11-24 08:18:43","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":485753,"visible":true,"origin":"","legend":"\u003cp\u003e(a)The solid-state \u003csup\u003e13\u003c/sup\u003eC CPMAS NMR spectra of TT-PA and TT-BPA; FT-IR spectra of TT-PA (b) and TT-BPA (c).\u003c/p\u003e","description":"","filename":"floatimage2.png","url":"https://assets-eu.researchsquare.com/files/rs-7940600/v1/1fd475aa1ba9745e505a14f8.png"},{"id":96605846,"identity":"c9e0c553-ddf1-4639-967a-520d0a94c88a","added_by":"auto","created_at":"2025-11-24 09:24:12","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":603314,"visible":true,"origin":"","legend":"\u003cp\u003eXPS survey spectrum and high-resolution XPS spectra of C 1s, N 1s and S 2p for TT-PA(a–d) and TT-BPA(e-h).\u003c/p\u003e","description":"","filename":"floatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-7940600/v1/7e7ccb38037c832cd29fc46c.png"},{"id":96599872,"identity":"b05e0c60-fa2d-41c6-a320-6f70716508f4","added_by":"auto","created_at":"2025-11-24 08:18:43","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":962611,"visible":true,"origin":"","legend":"\u003cp\u003eSEM images of samples: (a, b) TT-PA, (d, e) TT-BPA. TEM images of samples: (c)TT-PA, (f)TT-BPA.\u003c/p\u003e","description":"","filename":"floatimage4.png","url":"https://assets-eu.researchsquare.com/files/rs-7940600/v1/91ed13f7739ce3acdbfa4379.png"},{"id":96599870,"identity":"4c640ee5-238e-4b41-8bc5-8f96f78fe024","added_by":"auto","created_at":"2025-11-24 08:18:43","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":403524,"visible":true,"origin":"","legend":"\u003cp\u003e(a) UV-Vis DRS of TT-PA and TT-BPA. (b) The bandgap determined from the Kubelka–Munk-transformed reflectance spectrum of TT-PA and TT-BPA. (c) Mott–Schottky plots of TT-PA. (d) Energy band positions of TT-PA and TT-BPA.\u003c/p\u003e","description":"","filename":"floatimage5.png","url":"https://assets-eu.researchsquare.com/files/rs-7940600/v1/c05080a2d341f0c7a739fd81.png"},{"id":96599871,"identity":"822e974f-afdf-4229-8f8e-66b2593a853d","added_by":"auto","created_at":"2025-11-24 08:18:43","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":348434,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Photoluminescence spectra of TT-PA and TT-BPA. (b) The EIS Nyquist plots of TT-PA and TT-BPA. (c)Transient photocurrent response measurements of TT-PA and TT-BPA.\u003c/p\u003e","description":"","filename":"floatimage6.png","url":"https://assets-eu.researchsquare.com/files/rs-7940600/v1/5a0dac9d2867bb74d28cb1ca.png"},{"id":96605498,"identity":"3fcad5ae-d099-4383-826b-ff55fe73f376","added_by":"auto","created_at":"2025-11-24 09:23:16","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":290451,"visible":true,"origin":"","legend":"\u003cp\u003eHOMO and LUMO orbit distribution and ESP maps of (a) TT-PA and (b) TT-BPA\u003c/p\u003e","description":"","filename":"floatimage7.png","url":"https://assets-eu.researchsquare.com/files/rs-7940600/v1/8dccc77679f0a4962d80cdc6.png"},{"id":96599875,"identity":"3111d1dc-376c-41d4-b440-becd5770f8b6","added_by":"auto","created_at":"2025-11-24 08:18:43","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":453063,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Time-dependent H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e using visible light for TT-PA. (b) Cycling stability for TT-PA and TT-BPA. (c) SCC of TT-PA and TT-BPA. (d) AQY at different wavelengths of TT-PA.\u003c/p\u003e","description":"","filename":"floatimage8.png","url":"https://assets-eu.researchsquare.com/files/rs-7940600/v1/69de7265a9959eccd9ebdc5c.png"},{"id":100069290,"identity":"df8013d9-fa52-44ef-a613-56288de6ac6d","added_by":"auto","created_at":"2026-01-12 16:12:41","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":4181416,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-7940600/v1/1b5e3d2f-d971-4c87-82be-e75170b2285c.pdf"},{"id":96599881,"identity":"b3755a5d-dc68-4e93-8c87-d85e20ac68e7","added_by":"auto","created_at":"2025-11-24 08:18:44","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":6758524,"visible":true,"origin":"","legend":"","description":"","filename":"supplementalmaterials.docx","url":"https://assets-eu.researchsquare.com/files/rs-7940600/v1/7f032d8d3b2dd4790c5010c4.docx"},{"id":96605578,"identity":"65d41962-4ff4-469b-ba7c-06018e32e349","added_by":"auto","created_at":"2025-11-24 09:23:32","extension":"png","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":297940,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eScheme 1.\u003c/strong\u003eSynthetic routes of TT-PA and TT-BPA.\u003c/p\u003e","description":"","filename":"Onlinefloatimage1.png","url":"https://assets-eu.researchsquare.com/files/rs-7940600/v1/b9e2e5df6a704064783f859f.png"}],"financialInterests":"No competing interests reported.","formattedTitle":"Thiazolo[5,4-d]thiazole-Based CMPs as Bifunctional Photocatalysts for H₂O₂ Production and Organic Pollutant Degradation","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eHydrogen peroxide (H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e) is a clean, environmentally friendly oxidizing agent that plays significant roles in the chemical industry[\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e], healthcare, and water treatment. It is in high demand, with an estimated 4\u0026nbsp;million tons of H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e being used annually worldwide, and that number is predicted to rise to 5.7\u0026nbsp;million tons in 2027. Conventional anthraquinone and electrochemical methods are typically used in the industrial synthesis of H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e, but these processes have a number of disadvantages, including the potential of explosion, the production of hazardous byproducts, and significant energy consumption[\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e, \u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e]. With noble metal-based catalysts (such as Pd, Au, and Pt), H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e can be directly produced from H\u003csub\u003e2\u003c/sub\u003e and O\u003csub\u003e2\u003c/sub\u003e. However, their high cost makes this process unsuitable for scaling up to commercial production[\u003cspan additionalcitationids=\"CR5\" citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e].\u003c/p\u003e\u003cp\u003ePhotocatalytic technology exhibits promising application potential in H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e synthesis because of its low energy consumption, high efficiency, and ease of operation[\u003cspan additionalcitationids=\"CR8\" citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e]. Under light, two-electron oxygen reduction and two-electron water oxidation are typically used to achieve photocatalytic H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e production on semiconductors[\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e, \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e]. Among them, a variety of porous organic polymers (POPs), such as metal-organic frameworks (MOFs)[\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e, \u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e], covalent organic frameworks (COFs)[\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e], and CMPs[\u003cspan additionalcitationids=\"CR16\" citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e], have been developed as promising organic semiconductors for the photocatalytic preparation of H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e. The molecular-level optimization of CMPs' chemical structure, material composition, and optoelectronic characteristics is made possible by readily available building blocks and comparatively straightforward synthesis techniques. Because of their low cost, customized properties, and ease of preparation, CMPs[\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e] have attracted great interest in many fields due to their extensive surface area, robust structure, and the nature of the three-dimensional conjugated framework. And, by designing the D-A structure through molecular engineering, the photocatalytic H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e yield of CMP can be significantly increased. Pan et al. recently develop a series of CMPs using a D-A-A type system[\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e], and their photocatalytic efficiencies exceed more than twice that of the D-A polymer. The D-A1-A2 structure by Liao et al.[\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e] can significantly improve the photocatalytic performance of CMP photocatalysts. D-π-A and D-π-A-A structures[\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e] have independently studied for the simultaneous H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e evolution accompanied by pollutant degradation. Enhancing conjugation within the molecular structure facilitates electron transfer, which in turn improves photocatalytic performance.\u003c/p\u003e\u003cp\u003eOur laboratory is dedicated to introduce TzTz units into porous organic polymers (POPs)[\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e], whose photocatalytic performance is enhanced by promoting charge separation and increasing active sites. And the rigid planar TzTz structure has strong electron acceptor properties and excellent light-absorbing capacity[\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e, \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e]. Additionally, high electron and hole mobility is provided by significant p-p stacking and orbital overlap in the solid state of CMPs.\u003c/p\u003e\u003cp\u003eTherefore, building upon our previous work and the promising properties of the TzTz unit, we herein design and synthesize two novel D-A type CMPs, namely TT-PA and TT-BPA, using TzTz as the universal acceptor core but coupling it with two different donors (triphenylamine and biphenylamine, respectively). We systematically investigate how the subtle change in the donor unit impacts the polymer's porosity, optoelectronic properties, and ultimately, its photocatalytic efficiency for both H₂O₂ production and pollutant degradation. This comparative study provides deep insights into the structure-property relationship for designing high-performance CMP photocatalysts.\u003c/p\u003e"},{"header":"2. Experimental","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e\u003ch2\u003e2.1. Materials\u003c/h2\u003e\u003cp\u003e4,4',4''-nitrilotribenzaldehyde, 4',4''',4'''''-nitrilotris(([1,1'-biphenyl]-4-carbaldehyde)), dithiooxamide, N,N -Dimethylformamide(DMF), para-benzoquinone (pBQ), silver nitrate (AgNO\u003csub\u003e3\u003c/sub\u003e), L-histidine (L-his), ethylenediaminetetraacetic acid disodium salt (EDTA-2Na), 2,2,6,6-tetramethylpiperidine oxide (TEMPO), isopropyl alcohol (IPA), and other common solvents were purchased from commercial suppliers (Adamas, Shanghai, China and Leyan, Shanghai, China) without further purification.\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec4\" class=\"Section2\"\u003e\u003ch2\u003e2.2. Synthesis\u003c/h2\u003e\u003cp\u003eSynthesis of TT-PA: 4,4',4''-nitrilotribenzaldehyde (500 mg, 1.52 mmol), dithiooxamide (291.9 mg, 2.43 mmol) in 10 mL of DMF solution were heated at 160\u0026deg;C for 3 days under N\u003csub\u003e2\u003c/sub\u003e protection. After the reaction mixture was cooled to room temperature, the crude polymer was then diafiltrated 3 times with methanol. After that, the polymer was washed thoroughly with CHCl\u003csub\u003e3\u003c/sub\u003e, methanol Soxhlet extraction for 24 hours. Finally, the product was dried under vacuum at 70\u0026deg;C for 24 h to obtain an orange powder (582.6 mg, 74% yield).\u003c/p\u003e\u003cp\u003eSynthesis of TT-BPA: Under N\u003csub\u003e2\u003c/sub\u003e protection, 4',4''',4'''''-nitrilotris(([1,1'-biphenyl]-4-carbaldehyde)) (500 mg, 0.90 mmol), dithiooxamide (172.4 mg, 1.43 mmol) were heated in 10 mL of DMF solution at 160\u0026deg;C for 3 days. After the reaction mixture was cooled to room temperature, the crude polymer was then diafiltrated 3 times with ethanol. After that, the polymer was thoroughly washed with methanol, CHCl\u003csub\u003e3\u003c/sub\u003e, and anhydrous ethanol Soxhlet extraction for 24 hours. Finally, the product was dried under vacuum at 70\u0026deg;C for 24 h to obtain a yellow powder (490.6 mg, 73% yield).\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec5\" class=\"Section2\"\u003e\u003ch2\u003e2.3. Characterization\u003c/h2\u003e\u003cp\u003eFourier-transformed infrared (FT-IR) spectra were recorded on dried KBr disks in transmission mode using Bruker VERTEX 70 FTIR spectrometer. Solid-state cross-polarization magic angle spinning (CP/MAS) \u003csup\u003e13\u003c/sup\u003eC NMR spectra were obtained on a 400 MHz Bruker-500 NMR spectrometer. Polymer morphologies were investigated with a Zeiss SIGMA 500 field emission scanning electron microscope (SEM). Additionally, elemental mapping was performed using a BRUKER XFlash 6130. Before measurement, the samples were sputter coated with gold. Detailed morphological and structural characterizations were performed using a high-resolution transmission electron microscope (HR-TEM, JEOL, Tokyo, Japan). Powder X-ray diffraction (PXRD) patterns were performed on an X-ray diffraction spectrometer (Bruker AXS GmbH, Germany). The samples were degassed in a vacuum at 150 \u0026deg;C for 6 h before measurement. Thermo-gravimetric analysis (TGA) was conducted on NETZSCH 209 F3. The samples were heated at 10 \u0026deg;C/min under a nitrogen atmosphere up to 800 \u0026deg;C. X-ray photoelectron spectroscopy (XPS) spectra were recorded using an ESCALAB 250 Xi XPS system of Thermo Scientific, where the base pressure in analysis chamber was 1.5\u0026times;10\u003csup\u003e\u0026minus;\u0026thinsp;9\u003c/sup\u003e mbar and the X-ray spot was 500 \u0026micro;m. Ultraviolet\u0026ndash;visible spectra were measured on a UV-VIS-NIR spectrophotometer (Cary-100, Agilent Technologies Inc., Santa Clara, CA, USA) at room temperature. Surface area, N\u003csub\u003e2\u003c/sub\u003e adsorption isotherms (77 K), and pore size distributions were measured using the micromeritics ASAP 2460 surface area and porosity analyzer.\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec6\" class=\"Section2\"\u003e\u003ch2\u003e2.4. Photoelectrochemical Measurement\u003c/h2\u003e\u003cp\u003eElectrochemical measurements were measured on a CHI760E electrochemical workstation in a three-electrode system using photocatalyst-coated indium-tin oxide (ITO) glass as the working electrode, an Ag/AgCl electrode as the reference electrode, and a platinum flake as the counter electrode. Electrochemical impedance spectroscopy (EIS), transient photocurrent measurements, and Mott\u0026ndash;Schottky analysis were conducted in a 0.2 M Na\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e aqueous solution.\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec7\" class=\"Section2\"\u003e\u003ch2\u003e2.5. Photocatalytic H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e Synthesis\u003c/h2\u003e\u003cp\u003eThe detailed experimental procedure was as follows: the photocatalyst was dispersed in 30 mL of pure water, it was stirred with oxygen for 30 min to reach the oxygen saturation state under dark conditions. The catalyst was then exposed to light under a 300 W Xe lamp for 60 min. At a given time, a certain amount of reaction solution (1.0 mL) was collected and filtered with a 0.22 \u0026micro;m filter membrane. The H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e concentration was determined by the iodometry method at 351 nm. Finally, the concentration of H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e was calculated from the fitted curve.\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec8\" class=\"Section2\"\u003e\u003ch2\u003e2.6. Photodegradation of RhB\u003c/h2\u003e\u003cp\u003eFor the degradation of RhB, CMPs were dispersed in an aqueous solution of RhB (50 mL, 10 mg L\u003csup\u003e-1\u003c/sup\u003e), and the mixture was stirred for 30 min in the darkness to obtain adsorption\u0026ndash;desorption equilibrium. After that, the solution was irradiated with a 300 W Xe lamp. At defined time intervals, an appropriate amount of suspension was filtered through a filter membrane to remove solid particles and absorbance of the filtrate at 554 nm was obtained by a UV\u0026ndash;Vis spectrophotometer. The RhB removal efficiency was calculated using the following equation:\u003cdiv id=\"Equa\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equa\" name=\"EquationSource\"\u003e\n$$\\:\\text{Removal\\:efficiency}\\left(\\text{\\%}\\right)\\text{=}\\frac{{\\text{c}}_{\\text{0}}\\text{-}\\text{c}}{{\\text{c}}_{\\text{0}}}\\text{\u0026times;100\\%}$$\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e\u003cp\u003ewhere \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:\\text{c}\\)\u003c/span\u003e\u003c/span\u003e\u003csub\u003e0\u003c/sub\u003e denotes the initial concentration of RhB and \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:\\text{c}\\)\u003c/span\u003e\u003c/span\u003e denotes the concentration of RhB at each irradiated time interval.\u003c/p\u003e\u003c/div\u003e"},{"header":"3. Results and Discussion","content":"\u003cdiv id=\"Sec10\" class=\"Section2\"\u003e\u003ch2\u003e3.1. Synthesis and Characterization\u003c/h2\u003e\u003cp\u003eThe condensation of dithiooxamide with aldehyde groups formed the TzTz rings (Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). Both of them were stable in water and insoluble in common organic solvents. The aromaticity and rigidity of the TzTz ring enabled CMPs to have excellent thermal stability. TGA demonstrated that severe decomposition commencing at about 400\u0026deg;C for two samples (Figure S2). The weight loss below 300\u0026deg;C might be ascribed to the removal of water or other solvent molecules adsorbed on the sample.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eThe successful synthesis of TT-PA and TT-BPA was confirmed by the solid-state \u003csup\u003e13\u003c/sup\u003eC NMR spectra (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea). The peaks at 167 ppm and 165 ppm were assigned to the carbon atoms of the C\u0026thinsp;=\u0026thinsp;N groups in the TzTz moiety of TT-PA and TT-BPA, respectively. The peak at 151 ppm were carbon-carbon double bonds in the TzTz structure. The FT-IR spectra (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb, c) showed the disappearance of the N-H stretching vibration peak at 3291 cm⁻\u0026sup1; (from-NH₂ in DTO) and the C\u0026thinsp;=\u0026thinsp;O stretching vibration peak at 1684 cm⁻\u0026sup1; (from -CHO in TFPA or TFBA)[\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e], concurrently with the emergence of a new distinctive peak at 1620 cm⁻\u0026sup1; (C\u0026thinsp;=\u0026thinsp;N stretching vibration), indicating that -NH\u003csub\u003e2\u003c/sub\u003e reacted with -CHO to produce an imine bond (C\u0026thinsp;=\u0026thinsp;N). This also proved the formation of the TzTz ring and CMPs[\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e].\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eThe PXRD of TT-PA and TT-BPA (Figure S3) indicated that broad 2θ peaks at roughly 18\u0026deg; or 24\u0026deg; was a typical feature π-π stacking intercalation of the CMPs[\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e]. The rigid planarity of TzTz enabled π-π stacking between the polymer layers, which was beneficial for the transfer of charges between the layers and the photocatalytic improvement of CMPs.\u003c/p\u003e\u003cp\u003eTT-PA and TT-BPA's porosity was assessed using nitrogen adsorption isotherm tests at 77 K (Figure S4-6). Type IV isotherms were used to describe the adsorption curves. When compared to TT-BPA (27.63 m\u0026sup2;/g), TT-PA's BET specific surface area (112.78 m\u0026sup2;/g) was significantly greater. Adsorption-averaged pore size (6.75 nm) and desorption-averaged pore size (2.78 nm) of TT-PA were greater than those of TT-BPA (6.23 and 2.64 nm, respectively), according to NL-DFT calculations. Apparently, the smaller triphenylamine combined with TzTz could generate a more favorable pore structure, providing a more advantageous environment for the adsorption and diffusion of reactants (O₂, H₂O) and the desorption of products (H₂O₂).\u003c/p\u003e\u003cp\u003eXPS was used to further evaluate the materials' chemical states and bonding topologies (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e). The XPS spectra of TT-PA and TT-BPA suggested that the elements C, N, O, and S were the most prevalent in all samples. TT-PA's C 1s spectrum (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb) conformed to four peaks that corresponded to C-C (284.8 eV), C\u0026thinsp;=\u0026thinsp;C (286.0 eV), C-N (287.5 eV), and C\u0026thinsp;=\u0026thinsp;N (291.6 eV), respectively. In a similar vein, TT-BPA (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ef) displayed four peaks at 284.8, 285.6, 286.0, and 291.5 eV that correspond to C-C, C\u0026thinsp;=\u0026thinsp;C, C-N, and C\u0026thinsp;=\u0026thinsp;N[\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e, \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e], respectively. The fitted peaks at 400.1 eV (or 400.5 eV) in the high-resolution XPS spectra of the N 1s (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec, g) belonged to C -N, while the peak at 399.2 eV (or 399.5 eV) belonged to C\u0026thinsp;=\u0026thinsp;N[\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e, \u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e]. These characterization investigations demonstrated the effective synthesis of TT-PA and TT-BPA. The S and N atoms on the surface of the CMPs could act as Lewis base sites to adsorb O₂ molecules, thereby reducing the activation energy barrier for O₂ reduction and facilitating the 2e⁻ ORR pathway for the generation of H₂O₂ over the 4e⁻ pathway for the generation of H₂O.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eFigure \u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e showed the morphologies of TT-PA and TT-BPA. Both materials were nearly spherical in shape and connected to each other to form layered structures. The particle size of TT-PA was smaller than that of TT-BPA. This explained the reason why the pore diameter and specific surface area of TT-PA were larger. There were ordered or disordered microporous structures between lamellar structures, which were crucial characteristics of conjugated microporous polymers for the storage and transportation of molecules.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec11\" class=\"Section2\"\u003e\u003ch2\u003e3.2. Photoelectric Property Studies\u003c/h2\u003e\u003cp\u003eThe well-defined D-A structures and favorable π-π stacking, as confirmed above, were anticipated to facilitate the separation and transport of photogenerated charge carriers. To validate this hypothesis and correlate the molecular structure with photocatalytic activity, we systematically investigated the optoelectronic properties of TT-PA and TT-BPA.\u003c/p\u003e\u003cp\u003eThe optical absorption properties of TT-PA and TT-BPA were characterized by UV\u0026ndash;Vis DRS. According to Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea, TT-PA and TT-BPA exhibited broad absorption range, indicating excellent light absorption properties. From which the bandgap (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eb) of the valence band (VB) and the conduction band (CB) calculated using the Kubelka-Munk function to be 2.16 eV and 2.28 eV for TT-PA and TT-BPA, respectively[\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e]. In TT-PA (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ec) and TT-BPA (Figure S8), the corresponding flat-band potentials relative were 0.92 V and 1.06 V, respectively, according to the Mott-Schottky plots[\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e]. The slopes of the curves for both photocatalytic materials were positive, indicating that they were n-type semiconductors[\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e], which facilitated the rapid transfer and transportation of photogenerated electrons in CMP, thereby enhancing the separation efficiency of photogenerated carriers. The band structure diagrams (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ed) showed that both CMPs possessed conduction band potentials that were more negative than the potential required for the direct 2e⁻ ORR pathway (E\u0026thinsp;=\u0026thinsp;+\u0026thinsp;0.68 V vs. NHE for H₂O₂ production)[\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e].\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eIn order to study the separation efficiency of photogenerated charge and the migration rate of photogenerated carriers in the two CMPs, photoluminescence spectroscopy (PL), the electrochemical impedance spectroscopy (EIS) and photocurrent response of the samples were measured. As seen in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ea, TT-BPA exhibited stronger photoluminescence, meaning that the photogenerated electron-hole pairs were more likely to be compounded, thereby lowering the photocatalytic activity[\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e]. The EIS tests revealed that TT-PA had smaller Nyquist semicircle diameters than TT-BPA, as illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eb. This suggested that TT-PA had a better interfacial charge transfer process and a reduced interfacial carrier transport resistance[\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e]. Furthermore, the results of the transient photocurrent measurement (I-t) confirmed that TT-PA had a higher carrier separation efficiency[\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e]. The visible response photocurrent of TT-PA was noticeably higher than that of TT-BPA (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ec). Therefore, the electron transfer impedance was smaller, the transmission was faster, and the efficiency of photogenerated carrier separation was higher in TT-PA.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec12\" class=\"Section2\"\u003e\u003ch2\u003e3.3. Theoretical studies\u003c/h2\u003e\u003cp\u003eDensity flood theory (DFT) simulations were used to examine the pre-molecular orbitals of two CMPs model fragments in order to gain a better understanding of how structural units affect the photovoltaic characteristics of CMPs (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e). According to molecular simulations, TT-BPA's lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) energy levels were found in the acceptor unit of the TzTz structure and the anisotropic triangular π-conjugated structural unit, respectively. These findings were consistent with the results of the simulated surface electrostatic potential (ESP). The remarkable charge separation efficiency seen in TT-PA might have been largely attributed to the non-overlapping energy level distribution, which successfully inhibited the recombination of photogenerated holes and electrons[\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e, \u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e].\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec13\" class=\"Section2\"\u003e\u003ch2\u003e3.4. Photocatalytic Performance in H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e Production\u003c/h2\u003e\u003cp\u003eThe photocatalytic H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e production performance of the CMPs were carried out under visible light irradiation. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ea, the H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e yield of TT-PA was higher than that of TT-BPA. TT-PA and TT-BPA showed the highest rates of hydrogen peroxide production in an O\u003csub\u003e2\u003c/sub\u003e environment (2470.20 \u0026micro;mol g\u003csup\u003e-1\u003c/sup\u003e h\u003csup\u003e-1\u003c/sup\u003e and 2041.46 \u0026micro;mol g\u003csup\u003e-1\u003c/sup\u003e h\u003csup\u003e-1\u003c/sup\u003e, respectively) compared with air or nitrogen conditions, suggesting that the pathway for H₂O₂ generation was 2e\u003csup\u003e-\u003c/sup\u003e ORR pathway.\u003c/p\u003e\u003cp\u003eFurthermore, the stability and recyclability of TT-PA and TT-BPA (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003eb) were conducted to evaluate long-time photocatalytic durability. After four consecutive cycles, the photocatalytic H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e production rate fluctuated only slightly, indicating that the material had good recyclability. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ec, the solar-to-chemical conversion (SCC) efficiency of TT-PA was 0.41%, and that of TT-BPA was 0.38%, both of which exceeded the efficiency of natural synthetic plants (\u0026asymp;\u0026thinsp;0.1%)[\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e] and most of reported photocatalysts (Figure S9a and Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e). Figure\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ed illustrated the maximum apparent quantum yield (AQY) values of TT-PA and TT-BPA were 0.55% and 0.49%, respectively. The specific data were shown in Table S2, Figure S9b illustrated TT-PA had advantages in the photocatalytic H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e production process.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eMechanism Study of H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e Production\u003c/p\u003e\u003cp\u003eCapture experiments were used to investigate the primary active species in the reaction system. AgNO\u003csub\u003e3\u003c/sub\u003e, pBQ, EDTA-2Na, and L-his were chosen to absorb electrons (e⁻), superoxide radicals (\u0026sdot;O₂⁻), holes (h⁺), and hydroxyl radicals (\u0026sdot;OH), respectively (Figure S9c). The H₂O₂ yield dropped from 2470.21 \u0026micro;mol to 172.35 \u0026micro;mol upon the addition of pBQ to the reaction system, indicating that \u0026middot;O₂⁻ was the primary active species in the ORR pathway. Thus H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e was mainly generated through the ORR pathway[\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e, \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e]. (The TT-BPA capture experiment could be found in Figure S9d.)\u003c/p\u003e\u003cp\u003ePhotodegradation of RhB\u003c/p\u003e\u003cp\u003eThe mechanism study in section 3.5 revealed that superoxide radicals (\u0026middot;O₂⁻) were the primary active species in the photocatalytic system of TT-PA and TT-BPA. Notably, \u0026middot;O₂⁻ was also a potent oxidant for the decomposition of organic pollutants. This common active species prompted us to explore the application of these CMPs in photocatalytic environmental remediation. We selected Rhodamine B (RhB), a refractory organic dye, as a model pollutant to evaluate the photodegradation performance of TT-PA and TT-BPA.\u003c/p\u003e\u003cp\u003eDuring the degaration process, the color of the RhB solution changed from pink to colorless (Figure S11). The degradation data demonstrated that TT-PA had superior photodegradation performance over TT-BPA. The photodegradation efficiency of TT-PA (0.3 g L\u003csup\u003e-1\u003c/sup\u003e) on RhB (10 mg L\u003csup\u003e-1\u003c/sup\u003e) was 99.81% at 30 minutes (Figure S12a). In contrast, the photodegradation efficiency of TT-BPA was 99.81% at almost 70 minutes (Figure S13a). In another control experiment, we changed the amounts of TT-PA and TT-BPA catalysts to 5 mg, 10 mg, 15 mg, and 20 mg. The highest degradation efficiency (99.0%) was attained in 30 minutes at the amount of 20 mg (0.4 g L\u003csup\u003e-1\u003c/sup\u003e) of TT-PA (Figure S12b), which was more than twice as fast as that of TT-BPA (Figure S13b). The impact of pH on the catalyst's ability was depicted in Figure S12c and S13c. TT-PA and TT-BPA had the best absorption at pH\u0026thinsp;=\u0026thinsp;3. Furthermore, after four consecutive cycles, the catalytic performance of TT-PA and TT-BPA decreased very little (Figure S12f and S13f).\u003c/p\u003e\u003c/div\u003e"},{"header":"4. Conclusions","content":"\u003cp\u003eIn summary, we have successfully synthesized two TzTz-based D-A CMPs, TT-PA and TT-BPA, via a straightforward catalyst-free condensation reaction. A comprehensive comparison demonstrated that the donor unit, in conjunction with the TzTz acceptor, played a decisive role in steering the material's properties. TT-PA, incorporating the triphenylamine donor, exhibited a superior combination of larger specific surface area, more efficient charge separation and transfer, and consequently, enhanced photocatalytic performance. The yield of H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e produced by TT-PA photocatalysis was 2470.20 \u0026micro;mol g\u003csup\u003e-1\u003c/sup\u003e h\u003csup\u003e-1\u003c/sup\u003e, and it degraded 99.81% of RhB within 30 minutes. Furthermore, they were stable and recyclable.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eYuting Ren: Formal analysis, Writing-original draft. Mingyue Wang: Data curation. Shuangjie Zhang: Software. Chunhua Yuan: Supervision. Jianmei Zhou: Methodology. Dongmei Li: Writing-review \u0026amp; editing, Funding acquisition, Conceptualization. Zhongzhen Tian: Funding acquisition, Project administration.\u003c/p\u003e\u003ch2\u003eAcknowledgements\u003c/h2\u003e\u003cp\u003eThis work was supported by the Natural Science Foundation of Inner Mongolia Autonomous Region (Grant number 2024MS02004, 2025MS02002).\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eS. Shaybanizadeh, R. Luque, A. Najafi Chermahini. 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Molecular engineering of donor-acceptor-type conjugated microporous polymers for dual effective photocatalytic production of hydrogen and hydrogen peroxide, Mater. Horiz. 12 (2025) 5917\u0026ndash;5928. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttp://doi.org/10.1039/D5MH00735F\u003c/span\u003e\u003cspan address=\"10.1039/D5MH00735F\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e.\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"},{"header":"Scheme ","content":"\u003cp\u003eScheme 1 is available in the Supplementary Files section.\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"research-on-chemical-intermediates","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"rint","sideBox":"Learn more about [Research on Chemical Intermediates](http://link.springer.com/journal/11164)","snPcode":"11164","submissionUrl":"https://submission.nature.com/new-submission/11164/3","title":"Research on Chemical Intermediates","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Donor-acceptor, Conjugated microporous polymers, Photocatalysis, H2O2, Photodegradation of RhB","lastPublishedDoi":"10.21203/rs.3.rs-7940600/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-7940600/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eTwo donor-acceptor (D-A)-type conjugated microporous polymers (CMPs), TT-PA and TT-BPA, are successfully synthesized based on thiazolo[5,4-\u003cem\u003ed\u003c/em\u003e]thiazole (TzTz) as the acceptor unit. The rigid plane of TzTz enables a close and effective π-π stacking between polymer layers, which is beneficial for the transport of charges between layers and the improvement of photocatalytic performance. The high-density S and N atoms in the TzTz units can act as Lewis base sites to adsorb O₂ molecules. Subsequently, TzTz transfers the photogenerated electrons to the adsorbed O₂, generating \u0026middot;O₂⁻, which is conducive to the 2e\u003csup\u003e-\u003c/sup\u003e oxygen reduction reaction (ORR) pathway for the photocatalytic production of H₂O₂ and the degradation of the pollutant Rhodamine B (RhB). The PL, EIS and photocurrent data indicate that TT-PA has a lower charge recombination rate and higher charge separation efficiency, stemming from the appropriate size and electron-attracting ability of triphenylamine. Therefore, the combination of TzTz and triphenylamine in TT-PA is the \"golden combination\" for achieving the best D-A effect, pore structure and photocatalytic performance due to the best D/A ratio. This study gives insights into the design of CMP photocatalyst.\u003c/p\u003e","manuscriptTitle":"Thiazolo[5,4-d]thiazole-Based CMPs as Bifunctional Photocatalysts for H₂O₂ Production and Organic Pollutant Degradation","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-11-24 08:18:39","doi":"10.21203/rs.3.rs-7940600/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-11-30T02:49:40+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-11-29T17:45:48+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-11-27T13:08:23+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"41118156724608599633541704953616721233","date":"2025-11-13T12:37:51+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"250929408397819717696562584312601061900","date":"2025-11-12T01:46:35+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-11-12T01:36:22+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-10-27T14:55:03+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-10-27T14:53:50+00:00","index":"","fulltext":""},{"type":"submitted","content":"Research on Chemical Intermediates","date":"2025-10-24T12:22:31+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"research-on-chemical-intermediates","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"rint","sideBox":"Learn more about [Research on Chemical Intermediates](http://link.springer.com/journal/11164)","snPcode":"11164","submissionUrl":"https://submission.nature.com/new-submission/11164/3","title":"Research on Chemical Intermediates","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"5630eaef-d6dc-4766-b783-3477688198d0","owner":[],"postedDate":"November 24th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2026-01-12T16:03:27+00:00","versionOfRecord":{"articleIdentity":"rs-7940600","link":"https://doi.org/10.1007/s11164-025-05899-5","journal":{"identity":"research-on-chemical-intermediates","isVorOnly":false,"title":"Research on Chemical Intermediates"},"publishedOn":"2026-01-06 15:58:05","publishedOnDateReadable":"January 6th, 2026"},"versionCreatedAt":"2025-11-24 08:18:39","video":"","vorDoi":"10.1007/s11164-025-05899-5","vorDoiUrl":"https://doi.org/10.1007/s11164-025-05899-5","workflowStages":[]},"version":"v1","identity":"rs-7940600","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7940600","identity":"rs-7940600","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}