MOF-Derived Bimetallic Catalysts for Simultaneous Irradiation Degradation and Hydrogen Evolution: Synergistic Oxidation-Reduction Processes

MOF-Derived Bimetallic Catalysts for Simultaneous Irradiation Degradation and Hydrogen Evolution: Synergistic Oxidation-Reduction Processes | 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 Article MOF-Derived Bimetallic Catalysts for Simultaneous Irradiation Degradation and Hydrogen Evolution: Synergistic Oxidation-Reduction Processes Liuxuan Cao, Yaqi Wu, Yalan Deng, Haipeng Xiao, Ruowen Ma, Huifang Miao, and 2 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6876542/v1 This work is licensed under a CC BY 4.0 License Status: Under Revision Version 1 posted 11 You are reading this latest preprint version Abstract Electron beam (EB) irradiation technology for organic pollutant degradation primarily exploits oxidizing radicals, while concurrently generated reducing radicals remain underutilized. These reducing species represent not only wasted energy but also impair degradation efficiency through radical neutralization. To overcome this limitation, we developed a synergistic catalyst designed to simultaneously harness both irradiation-driven oxidative and reductive free radicals. Mechanistic studies reveal that hafnium doping facilitates the valence conversion of iron from a purely divalent state (Fe²⁺) to a mixed Fe²⁺/Fe³⁺ state. This mixed-valence iron subsequently mediates free radical generation during water radiolysis through redox cycling between its divalent and trivalent states. Compared to EB irradiation alone, this catalytic system achieves 98% removal of the target pollutant (methyl orange), representing a 5-fold efficiency enhancement. Concurrently, hydrogen production efficiency increases nearly 5-fold. This work establishes a new paradigm for integrated pollutant degradation and energy harvesting. Physical sciences/Chemistry/Catalysis/Catalyst synthesis Physical sciences/Chemistry/Materials chemistry/Metal–organic frameworks Electron beam irradiation bimetallic catalyst irradiation degradation irradiation hydrogen production Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 1. Introduction With the rapid development of industry, the types and quantities of toxic, hazardous, and refractory organic pollutants in wastewater discharged from sectors such as textiles, papermaking, pharmaceuticals, and coking have become increasingly complex and abundant 1 , 2 . Conventional biochemical and physicochemical treatment methods can no longer meet increasingly stringent effluent discharge standards, because they are sensitive to solution conditions and bring secondary pollution 3 . As an advanced oxidation process, electron beam irradiation efficiently degrades contaminants in wastewater ‌without producing secondary chemical byproducts or residues‌ 4, 5 . This technology has demonstrated significant advantages in environmental remediation applications 6, 7 . In recent years, its applications have expanded to various pollutant treatment scenarios, ‌particularly in removing contaminants from textile dyeing wastewater 8,9 ‌degrading organochlorine compounds in antibiotic and pharmaceutical wastewater‌ 10 − 12 , and ‌reducing Chemical Oxygen Demand (COD) 13 − 15 ‌. The substantial energy demand constrains this technology's widespread deployment. The radiolysis of water to produce hydrogen provides a possible approach for energy harvesting. During electron beam (EB) treatment of aqueous solutions, a substantial yield of reactive species is generated, including hydroxyl radicals (·OH), hydrated electrons (e⁻ₐq), superoxide radicals (·O₂⁻). Ionizing radiation can excite water molecules to simultaneously produce hydrated electrons and hydrogen radicals, enabling synergistic hydrogen evolution-confirming water radiolysis as a viable radiation-to-energy conversion pathway 16 . However, the current process of radiation organic degradation of pollutants is primarily dependent on oxidizing radical 17 , 18 . For instance, Khaneghah 19 et al. comprehensively analyzed the mechanisms by which electron beam irradiation degrades contaminants in cereal-based food products. Their review explicitly details the interaction between high-energy electron beams and water molecules to generate hydroxyl radicals (·OH), while thoroughly elaborating on how these radicals degrade mycotoxins and disrupt microbial organic structures through oxidative reactions ultimately achieving highly efficient decontamination. Li et al. 20 utilized superoxide (·O 2 − ) to combine rechargeable carbon-based supercapacitors with the redox groups-based O 2 , effectively transferring electrons onto O 2 to form ·O 2 − radicals. They achieved excellent O 2 activation electron transfer efficiency, achieving complete mineralization of diverse organic pollutants. A key challenge in energy recovery lies in efficiently harnessing reducing free radicals—generated during organic pollutant oxidation—for concurrent hydrogen production. Nevertheless, conventional degradation catalysts predominantly optimize oxidative radical reactions without facilitating radiolytic hydrogen generation. Since the concurrently generated reductive radicals remain underutilized 19 , this inefficiency not only constitutes resource wastage and diminishes energy utilization, but also allows reductive radicals to quench oxidative species, thereby compromising degradation efficacy. This limitation could potentially be addressed by composite catalyst systems. For instance, Yang et al. designed a composite photocatalyst UPC-HOF-6/Mn 2 O 3 /Pt by anchoring Mn 2 O 3 with oxidation ability and Pt with reduction ability at the oxidation sites and reduction sites respectively, achieving rapid separation of photogenerated electron-hole pairs. This material exhibited excellent photocatalytic activity 21 . Zhou et al. meticulously designed a model system consisting of metal and heterobimetallic catalysts for the electrochemical CO 2 reduction reaction. During the reaction process, the intramolecular electrostatic field promotes the redistribution of electrons, enabling the bimetallic structure to simultaneously utilize the reducing CO 2 − radical and the oxidative intermediate in the CO 2 reduction process, resulting in a 10-fold increase in catalytic activity. At the same time, inert Zn 2+ was introduced to replace some Co 2+ to optimize the charge distribution, verifying that non-active metals have a regulatory effect on radical reactions. 22 . Despite their proven efficacy in the fields of photocatalysis and electrocatalysis, they have not yet been adapted for irradiation applications. 23 , 24 In this paper, we successfully developed a multifunctional composite catalyst for simultaneous methyl orange (MO) degradation and radiolytic hydrogen production. Using UiO-66 as the metal-organic framework (MOF) precursor, we synthesized a series of metal-incorporated derivatives through systematic compositional tuning. Catalytic performance was quantitatively assessed via pollutant degradation efficiency and H₂ evolution rates. Mechanistic investigations verified dual-reaction pathways and established an optimized protocol for synergistic contaminant removal and energy recovery. This integrated strategy provides new mechanistic insights for combined environmental remediation and renewable energy systems. 2. Experimental methods 2.1 Synthesis process of Fe@C MOF Typically, 0.75 g terephthalic acid (BDC), 1.21 g FeCl 3 and 1.8 mL NaOH aq (2M) were dissolved in 10 mL dimethylformamide (DMF). Than sonicated the mixed solution until a homogeneous solution was obtained. The solution was sealed in a stainless-steel autoclave and placed in an oven preheated at 100 ℃ for 18 h. The mixture was cooled to room temperature naturally and rinsed with fresh DMF and deionized water three times by centrifugation (8000 rpm, 3 min) to remove the residual reactant and DMF. Finally, the product was dried under vacuum at 60 ℃. In addition, because the material is difficult to dry, it can be coated on a petri dish to increase the specific surface area, and then ground after drying. Finally, The ground sample is placed in a tube furnace, where the temperature is raised to 750 ℃ (5 K/min) and held for 2 hours, and then cooled to room temperature, the Fe@C samples was obtained 25 . 2.2 Synthesis process of UIO-66 MOF In a typical preparation, 600 mg (1.88 mmol) of HfCl 4 and 348 mg (2.08 mmol) of BDC were dissolved in 20 mL of DMF. Then sonicated until a homogeneous solution was obtained. The solution was sealed in a 100 mL Teflon-lined stainless-steel autoclave and placed in an oven preheated at 100°C for 24 h. The mixture was cooled to room temperature naturally and rinsed with fresh DMF three times by centrifugation (8000 rpm, 3 min) to remove the residual reactant and DMF. Finally, the UIO-66 was dried under vacuum at 60°C. 2.3 Synthesis process of UIF MOF The synthesis of UIF MOF followed a modified UiO-66 protocol, wherein Fe@C nanoparticles were introduced as the iron source during crystallization to generate Fe-active sites while maintaining structural integrity. 3. Results and discussion 3.1 Characterization of the catalysts To characterize the morphology of the synthesized materials, we conducted comprehensive electron microscopy analysis using both scanning (SEM) and transmission (TEM) techniques. Figure 1 a shows that the Fe@C MOF exhibits a heterogeneous morphology consisting of irregularly sized nanosheets and nanoparticles. In striking contrast, the UIO-66 MOF (Fig. 1 b) displays highly uniform nanospheres with smooth surfaces. The third-step synthesized UIF material retained the spherical morphology of its UIO-66 precursor but exhibited significantly reduced particle size (Fig. 1 c). TEM imaging (Fig. 1 d) confirmed the solid spherical structure of the UIF samples, while the absence of discernible lattice fringes in HRTEM analysis indicates their amorphous nature. Elemental mapping (Fig. 1 g) confirmed the homogeneous distribution of Fe, Hf, N, C, and O throughout the nanospheres, providing conclusive evidence for the successful incorporation of iron into the UIO framework and the formation of UIF. To analyze the structure, crystal phase, and chemical composition, we performed a series of systematic characterizations. As shown in Fig. 2 a, the powder X-ray diffraction (PXRD) pattern of UIO-66 exhibits a characteristic weak diffraction peak at 8°, corresponding to its porous framework structure and consistent with literature reports 20 . The XRD pattern of the Fe@C sample matches the standard FeO reference (PDF#46-1312), confirming its oxide nature. FTIR spectroscopy (Fig. 2 b) was used to identify organic functional groups, revealing characteristic absorption bands between 3700 − 475 cm⁻¹ for all samples. Distinct peaks were observed at 1590 cm⁻¹ and 1420 cm⁻¹ (attributed to -COO groups), along with 750 cm − 1 and 480 cm − 1 (corresponding to Hf-O vibrations) 20 . Notably, UIF exhibited identical IR spectra before and after irradiation, suggesting preserved metal coordination environments. The irradiated UIO-66 spectrum agreed with previous studies 26 , 27 . XPS Survey Spectrum (Fig. S1 ) confirmed UIF's composition (Hf, Fe, C, O), with Hf showing more changes in value states in UIF compared to UIO-66 (Fig. S2), attributed to Hf incorporation and Hf-Fe synergy. Similarly, due to the incorporation of the Hf element, the Fe element exhibited a state where both divalent and trivalent forms coexisted. While PXRD/FTIR showed minimal changes, XPS clearly tracked the valence state evolution from Fe 2+ species in Fe@C to mixed Fe 2+ /Fe 3+ in UIF (Fig. 2 c). High-resolution XPS of the Fe 2p region revealed four deconvoluted peaks (Fig. 2 c and S3): 710.9 eV (Fe Fe 2p₃ / ₂), 724.9 eV (Fe 2p₁ / ₂), and satellite features at 719.3 eV and 732.4 eV. The coexistence of Fe 3+ (713.8 eV, 725.9 eV) and Fe 2+ (710.7 eV, 723.9 eV) was evident, with a 2:1 ratio 25 , 28 . Brunauer-Emmett-Teller (BET) measurements were performed to characterize pore structures. As shown in Fig. S4, UIF samples exhibit significantly increased N₂ adsorption capacity and typical Type IV isotherms. Hysteresis loops occurred at relative pressures (P/P0) of 0.85-1.0, indicating mesopore formation. Barret-Joyner-Halenda (BJH) pore size distribution further confirmed mesoporous characteristics (Fig. S5). The UIF sample possesses BET specific surface area (646.6 m² g − 1 ), thus providing more active sites for enhanced catalytic performance. 3.2 Catalyst performance of different systems Methyl orange (MO) solution (50 mg/L) was selected as the model pollutant to evaluate the catalytic degradation performance, consistent with previous studies 29 . Prior to irradiation (0 kGy), an initial decrease in MO concentration was observed due to catalyst adsorption. Subsequently, the MO concentration exhibited a gradual reduction with increasing irradiation dose, following the reaction kinetics described by Eq. (S1) 29 . Comparative studies revealed the superior performance of UIF catalyst, achieving the highest degradation rate constant (k) among all tested materials (Fig. 3 a). Under 1.2 kGy irradiation with 5 mg UIF catalyst, the degradation efficiency reached 0.9788, corresponding to a 98% removal rate - significantly exceeding the performance of UIO-66 (0.8342) and Fe@C (0.8315) under identical conditions. Notably, UIF enhanced the radiation degradation efficiency from 19.8% (EB alone) to 97.8% (Fig. S6). The enhanced performance stems from two key factors: (1) retention of UIO-66's strong adsorption capacity, and (2) improved radiation degradation through Fe incorporation. The optimized UIF material exhibited a k value of 1.4867 - approximately 8-fold higher than irradiation alone (0.1841). This improvement confirms that Fe introduction creates additional catalytic active sites, while the Fe-Hf synergistic effect further enhances catalytic efficiency. To evaluate catalyst stability under irradiation and assess potential secondary contamination from irradiated wastewater, ion leaching concentrations and cycling tests were measured (Fig. 3 b and S7). At 1.2 kGy irradiation, UIO-66 exhibited minimal leaching, confirming its inherent stability. Remarkably, the Fe-doped UIF material demonstrated even lower iron leaching (0.145 mg/L), indicating that Fe incorporation enhances irradiation stability. Cycling tests demonstrated the material's stability, maintaining 30% MO removal after three consecutive irradiation-centrifugation cycles. To evaluate the impact of irradiation dose on catalytic performance, we systematically compared the degradation efficiency of all three materials across incrementally increased doses (1.2–4.8 kGy). As shown in Fig. S8, UIF consistently outperformed both catalyst-free irradiation and other materials throughout this dose range. Further demonstrating UIF's advantages, we conducted comparative studies at lower irradiation doses (Fig. S9). These results reveal that both UIF and UIO-66 achieve significantly enhanced degradation efficiency under low-dose irradiation conditions when compared to Fe@C or catalyst-free systems. We next investigated catalyst concentration effects on MO removal efficiency and rate constants (k) for UIF samples (Fig. 3 c). Results demonstrate that increasing catalyst concentration significantly enhances degradation performance under fixed conditions, achieving near-complete MO removal (99.6%). Concurrently, we evaluated dose-response relationships across varying catalyst concentrations (Fig. S10). To evaluate catalyst performance across wastewater's typical pH range, we systematically tested degradation efficiency under varied pH conditions. Initial measurements revealed the MO solution's native pH of 5.30 (weakly acidic). Using HCl and NaOH solutions, we adjusted the system to pH 2.69 (acidic), 8.09 (weakly alkaline), and 10.62 (strongly alkaline). As demonstrated in Fig. 3 d, acidic conditions significantly enhanced MO degradation efficiency. This pH-dependence arises from hydroxyl radical (·OH) consumption through reaction with hydroxide ions (OH − ) in alkaline media Eq. (S2), thereby inhibiting MO degradation at higher pH values 30 . These findings confirm ·OH's pivotal role in the catalytic mechanism, with potential supplementary contributions from hydrated electrons 31 . Under 1.2 kGy irradiation at acidic pH, ion leaching measurements (Fig. S11) showed 0.268 mg/L Hf and 0.087 mg/L Fe, both well below wastewater discharge limits. Notably, pH-dependent leaching trends were observed, suggesting pH-mediated effects on both catalyst stability and radiation efficiency. According to the reported literature, MOF materials have unique advantages in hydrogen production by irradiation decomposition due to their diverse frameworks and topological structures. We evaluated the hydrogen generation performance of our catalysts. Figure 4 a demonstrates the electron-beam dose dependence of H₂ evolution for all three catalysts. Results confirm that our MOF materials significantly accelerate radiolytic hydrogen production compared to pure water across 1–30 kGy, with near-linear H₂ yield escalation versus absorbed dose (Fig. 4 b). The enhancement of irradiation dose contributes to the release of H 2 . This is also consistent with the results reported in the literature, which UiO-66 can be synthesized using various organic linkers and is shown to exhibit a wide variation in water absorption capacity and hydrogen bonding, underlying the fact that the advanced and unique UiO-66 topologies play a vital role 32 – 34 . Notably, at low catalyst concentrations (5 g·L − 1 ), where gamma dose absorption by solids is negligible in radiation equivalence calculations, UIF exhibited 5-fold enhancement over pure water. The maximum radiolytic yield reached G value is 1.17 × 10 − 7 mol J − 1 (Fig. 4 b), We have reason to think that more efficient and faster H 2 generation rate can be obtained under electron beam irradiation. The change in H 2 concentration (as shown in Fig. 4 c) shows that an increase in catalyst concentration from 1 g L − 1 to 10 g L − 1 accelerates H 2 release. Radiation chemical efficiency was quantified via G-values (H₂ molecules per 100 eV absorbed energy). Using water decomposition Gibbs free energy (237 kJ·mol⁻¹) and Eq. (S3)²⁰, we calculated the radiation-to-hydrogen (RTH) efficiency. The energy conversion efficiency of rays-to- hydrogen (RTH) in neat water is measured to be ~ 0.3%, a fairly uncompetitive value. In contrast, this study dramatically improved the RTH efficiency at very low metal concentrations (~ 5 g L − 1 ) by using a UIF water interface system, achieving the highest conversion efficiency (~ 1.11%). Although existing materials such as oxides and zeolites have shown the ability to promote the release of radiolytic H 2 . However, when the concentration is relatively low, or even much higher than the concentration of UIF, the RTH value is lower than that of UIF, as shown in Table S1 35,36 . This establishes MOFs as prime candidates for radiolytic water splitting, distinct from photolytic/electrolytic processes. Reusability studies demonstrated UIF's practical viability. After four irradiation-recovery cycles (cumulative 120 kGy), it retained 35.7% initial G-value efficiency (0.4% RTH; Fig. S12), confirming robust radiation stability. 3.3 Mechanism of degradation and hydrogen production To elucidate the respective contributions of adsorption and catalytic degradation to contaminant removal, we systematically evaluated the adsorption capacities of different catalyst materials. Experiments were conducted using 1.0 g L − 1 catalyst in 50 mg L − 1 MO solution. The adsorption kinetics were analyzed using both pseudo-first-order and pseudo-second-order models Eq. (S4-S5) 20 , 37 , 38 , with the pseudo-second-order model 39 providing the best fit to the experimental data (see kinetic parameters in Table S2). With the increase of the catalyst content, the adsorption rate increases and the adsorption capacity decreases, almost reaching equilibrium adsorption at 12h. The adsorption capacity qe of UIF was 91.62 mg g − 1 , which was significantly higher than that of UIO-66 (71.44 mg g − 1 ) and Fe@C (28.84 mg g − 1 ) Current literature primarily attributes radiolytic degradation mechanisms to hydroxyl radical (·OH) generation via water radiolysis. To elucidate ·OH's specific role in MO decomposition, we conducted radical quenching experiments using 1 vol % tert-butanol (a selective ·OH scavenger). As shown in Fig. 5 a, Fe@C exhibited significant suppression of degradation kinetics (13.5% reduction in k-value) upon scavenger addition, confirming ·OH's dominant role in its catalytic mechanism. In contrast, UIF and UiO-66 displayed negligible reactivity changes under identical quenching conditions. In addition, the EPR (Electron Paramagnetic Resonance) test of hydroxyl radicals was conducted using DMPO (5, 5-dimethyl-1-pyrroline-N-oxide) as the spin trap agent 38 . The addition of UIF further enhanced the DMPO/OH signal compared with Fe@C (Fig. 5 c). These collective findings establish that the bimetallic composition in UIF synergistically promotes ·OH production during irradiation. Decades of research confirm that high-energy radiation generates H₂ primarily through water ionization/excitation pathways involving solvated electrons (e sol − ) and hydrogen atoms H, as described by Eq. (S6-S9) 20 . To verify e sol − 's dominant contribution to H₂ production in UIF, we employed Cd 2+ as a selective scavenger for solvated electrons 40 , 41 . Control experiments were conducted using Cd 2+ solutions with volume ratios of 0.002, 0.02, 0.2, 0.4 and 0.6 respectively, and the results are shown in Fig. 5 b. The results show that with the increase of Cd 2+ concentration, the volume of H 2 shows a decreasing trend, which further proves the key role of e sol − radicals in hydrogen production. Complementary electron paramagnetic resonance (EPR) studies using TEMPO (2,2,6,6-tetramethylpiperidin-1-oxyl) revealed near-complete signal quenching when UIF was present (Fig. 5 d). This indicates abundant low-energy electron generation during irradiation, leading to TEMPO reduction via electron transfer. To further reveal its catalytic mechanism, we analyzed the changes in the valence states of elements and the possible free radical reactions. The XPS spectra of Fe and Hf before and after EB radiation are shown in Fig. S13. Notable valence shifts occurred in iron species, where both FeFe 2+ and Fe 3+ exhibited substantial transformations. It can be seen that EB radiation provides sufficient Fe 2+ for the generation of ·OH. It is reported that the H 2 O 2 produced by irradiated water can convert Fe 2+ and Fe 3+ into each other to form active substances, as shown in Eq. (S10-11) 37 . In addition, the Hf element also changes significantly. After irradiation, while the peaks of the oxides of the Hf element decrease, some peaks also disappear accordingly. Therefore, it is reasonable to believe that there may be electron transfer between iron and Hf metals. The synergistic coexistence of Fe and Hf in UIF facilitates: Enhanced coordination in aqueous matrices under irradiation Improved catalytic efficiency for pollutant degradation and mineralization Concurrent clean H₂ energy production. This bifunctional capability positions UIF as a promising technology for environmental remediation with energy co-generation benefits. 4. Conclusions In summary, we reported MOF-derived Fe-Hf bimetallic catalysts exhibits exceptional radiation-driven catalytic activity for methyl orange (MO) degradation and hydrogen evolution performance. Mechanistic evidence confirms that, by facilitating the transition of iron valence from divalent to mixed (Fe²⁺/Fe³⁺), hafnium doping allows iron to participate in redox cycling that drives free radical generation in water radiolysis. At the same time, Fe-Hf bimetallic catalysts boost the production of hydrated electron during the water radiolysis process. Bimetallic catalysts mediate the concomitant formation of oxidative and reductive free radicals in aqueous radiolysis systems. This capability facilitates energy recovery during organic contaminant remediation while providing a platform to engineer integrated redox reaction architectures. Declarations CRediT authorship contribution statement The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Declaration of Competing Interest The authors declare no competing financial interest. Data availability Data will be made available on requst. Appendix A. Supplementary data The Supporting Information is available free of charge on the Energy Storage Materials website. Acknowledgments This work was supported by the National Natural Science Foundation of China (12175188), Nuclear energy development and research projects (HNKF202228(30)), the Fundamental Research Funds for the Central Universities of China (20720210051), XMU Training Program of Innovation and Entrepreneurship for Undergraduates (2021X1173). References Seung, J. P. et al. 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Additional Declarations There is no conflict of interest Supplementary Files SupportingInformation.docx MOF-Derived Bimetallic Catalysts for Simultaneous Irradiation Degradation and Hydrogen Evolution: Synergistic Oxidation-Reduction Processes GraphicalAbstracts.docx Cite Share Download PDF Status: Under Revision Version 1 posted Editorial decision: revise 14 Jul, 2025 Review # 3 received at journal 11 Jul, 2025 Review # 1 received at journal 09 Jul, 2025 Review # 2 received at journal 02 Jul, 2025 Reviewer # 3 agreed at journal 27 Jun, 2025 Reviewer # 2 agreed at journal 23 Jun, 2025 Reviewer # 1 agreed at journal 23 Jun, 2025 Reviewers invited by journal 23 Jun, 2025 Submission checks completed at journal 13 Jun, 2025 Editor assigned by journal 12 Jun, 2025 First submitted to journal 12 Jun, 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. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-6876542","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":474977357,"identity":"7df7e717-271a-423b-989e-7ae89a3f4f01","order_by":0,"name":"Liuxuan Cao","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA3UlEQVRIiWNgGAWjYHACxgMJYJr5AIR/gAg9UC1sCSRogVA8BsRp4W8/fODAw7bDif2ze75J3WxjkOO7kcD4uQCPFokzaQkHEtvSEmfcObvZOLeNwVjyRgKz9Aw8WgwYcgyAWmwSG27kbnwM1JK44UYCGzMPPi38b0BaJBLn38h5cBiopZ6wFgmoLRtu5DCCbEkwIKRF4sazhAMJ59KMN95IMzbOOSdhOPPMw2ZpfFr4+5MPPvxRdlh23o3kZ9I5ZTbyfMeTD37GpwXDViBmbCBBwygYBaNgFIwCbAAAqWBSfIeR5AQAAAAASUVORK5CYII=","orcid":"https://orcid.org/0000-0002-7788-5826","institution":"College of Energy, Xiamen University","correspondingAuthor":true,"prefix":"","firstName":"Liuxuan","middleName":"","lastName":"Cao","suffix":""},{"id":474977358,"identity":"12e10b47-cbd4-4af4-bfe9-9a761fb46fd2","order_by":1,"name":"Yaqi Wu","email":"","orcid":"","institution":"College of Chemistry and Chemical Engineering, Xiamen University","correspondingAuthor":false,"prefix":"","firstName":"Yaqi","middleName":"","lastName":"Wu","suffix":""},{"id":474977359,"identity":"f8ea5a3f-8fb8-4d27-a4df-2adf80786deb","order_by":2,"name":"Yalan Deng","email":"","orcid":"","institution":"College of Energy, Xiamen University","correspondingAuthor":false,"prefix":"","firstName":"Yalan","middleName":"","lastName":"Deng","suffix":""},{"id":474977360,"identity":"c2d65f91-0e69-4a26-8262-7a2150483356","order_by":3,"name":"Haipeng Xiao","email":"","orcid":"","institution":"College of Energy, Xiamen University","correspondingAuthor":false,"prefix":"","firstName":"Haipeng","middleName":"","lastName":"Xiao","suffix":""},{"id":474977361,"identity":"1bd34e55-58de-4c01-84e6-a5b05937f257","order_by":4,"name":"Ruowen Ma","email":"","orcid":"","institution":"College of Energy, Xiamen University","correspondingAuthor":false,"prefix":"","firstName":"Ruowen","middleName":"","lastName":"Ma","suffix":""},{"id":474977362,"identity":"9e851883-337f-4219-8288-2db77a87a2f3","order_by":5,"name":"Huifang Miao","email":"","orcid":"","institution":"College of Energy, Xiamen University","correspondingAuthor":false,"prefix":"","firstName":"Huifang","middleName":"","lastName":"Miao","suffix":""},{"id":474977363,"identity":"c96cf71d-e043-4755-ba09-77b1900b6e0b","order_by":6,"name":"Zhong-Qun Tian","email":"","orcid":"","institution":"","correspondingAuthor":false,"prefix":"","firstName":"Zhong-Qun","middleName":"","lastName":"Tian","suffix":""},{"id":474977364,"identity":"9b54d46a-7aed-4996-a625-c739d1e9f531","order_by":7,"name":"Wei Guo","email":"","orcid":"","institution":"Biosafety Research Center Yangtze River Delta in Zhangjiagang","correspondingAuthor":false,"prefix":"","firstName":"Wei","middleName":"","lastName":"Guo","suffix":""}],"badges":[],"createdAt":"2025-06-12 05:05:16","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6876542/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6876542/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":85556469,"identity":"9a069a5d-66a8-44d3-af58-b290d2e1b4a9","added_by":"auto","created_at":"2025-06-27 11:16:16","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":267060,"visible":true,"origin":"","legend":"\u003cp\u003e(a) The SEM image of Fe@C MOFs precursor. (b) the SEM images of the UIO-66 sample. (c) the SEM images of the UIF sample. (d)the TEM and HRTEM images of the UIF sample. (g) the TEM-Mapping images of the UIF sample.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-6876542/v1/4803837e2242c31b2ed1049b.png"},{"id":85556999,"identity":"05f24898-a8af-4e9e-87b3-7b40cee11b58","added_by":"auto","created_at":"2025-06-27 11:24:16","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":79137,"visible":true,"origin":"","legend":"\u003cp\u003e(a) The PXRD patterns Fe@C, UIO-66 and UIF, (b) the FTIR spectra of the UIF, UIO-66 and the Fe@C, (c) XPS spectrum of Fe elements in Fe@C and UIF materials.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-6876542/v1/f227b790a74196b593e2d5d5.png"},{"id":85556468,"identity":"dc45bc00-5842-43fb-b14d-f809440c603a","added_by":"auto","created_at":"2025-06-27 11:16:16","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":142251,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Comparison of methyl orange removal rate and corresponding k value of different catalysts under the same irradiation condition. (b) Comparison of ion leaching rates with different catalysts under the same conditions. (c) Effect of UIF catalyst concentration on methyl orange removal rate and corresponding k value. (d) Effect of UIF catalyst on removal rate of methyl orange at different pH.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-6876542/v1/f278bc4056d6f4e9003b520c.png"},{"id":85556466,"identity":"a1d8956b-6bd5-41b5-9aab-1bf0a85bc296","added_by":"auto","created_at":"2025-06-27 11:16:16","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":61998,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Effects of different catalysts on hydrogen production under different irradiation doses. (b) G value of different catalysts for hydrogen production under the same conditions. (c) Effect of catalyst concentration on hydrogen production.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-6876542/v1/aac592b74023ef147dd1b039.png"},{"id":85557218,"identity":"71e44f23-4a5e-4f13-9978-d63ecea04c1c","added_by":"auto","created_at":"2025-06-27 11:32:17","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":160998,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Effects of different catalysts on hydrogen production under different irradiation doses; (b) G value of different catalysts for hydrogen production under the same conditions; (c) Effect of catalyst concentration on hydrogen production.\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-6876542/v1/1e531e689949da414d0da65d.png"},{"id":85557688,"identity":"b8f8a26b-72a5-401d-911f-011b83cd831d","added_by":"auto","created_at":"2025-06-27 11:40:17","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1319607,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6876542/v1/40bca6f5-594b-4e78-b309-4afc8647b29a.pdf"},{"id":85556481,"identity":"315d5541-a51d-4f5c-955a-fae6c1a49f70","added_by":"auto","created_at":"2025-06-27 11:16:17","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":11364010,"visible":true,"origin":"","legend":"MOF-Derived Bimetallic Catalysts for Simultaneous Irradiation Degradation and Hydrogen Evolution: Synergistic Oxidation-Reduction Processes","description":"","filename":"SupportingInformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-6876542/v1/4f64b74276a20e2a3624d0ab.docx"},{"id":85556473,"identity":"d0cf9b1b-b609-46f3-beca-3f95d9c2d07d","added_by":"auto","created_at":"2025-06-27 11:16:17","extension":"docx","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":2459667,"visible":true,"origin":"","legend":"","description":"","filename":"GraphicalAbstracts.docx","url":"https://assets-eu.researchsquare.com/files/rs-6876542/v1/f3084db2f462a99dd1ac43a0.docx"}],"financialInterests":"There is no conflict of interest","formattedTitle":"MOF-Derived Bimetallic Catalysts for Simultaneous Irradiation Degradation and Hydrogen Evolution: Synergistic Oxidation-Reduction Processes","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eWith the rapid development of industry, the types and quantities of toxic, hazardous, and refractory organic pollutants in wastewater discharged from sectors such as textiles, papermaking, pharmaceuticals, and coking have become increasingly complex and abundant\u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e,\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e. Conventional biochemical and physicochemical treatment methods can no longer meet increasingly stringent effluent discharge standards, because they are sensitive to solution conditions and bring secondary pollution\u003csup\u003e\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u003c/sup\u003e. As an advanced oxidation process, electron beam irradiation efficiently degrades contaminants in wastewater \u0026zwnj;without producing secondary chemical byproducts or residues\u0026zwnj;\u003csup\u003e4,\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e\u003c/sup\u003e. This technology has demonstrated significant advantages in environmental remediation applications\u003csup\u003e6,\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e\u003c/sup\u003e. In recent years, its applications have expanded to various pollutant treatment scenarios, \u0026zwnj;particularly in removing contaminants from textile dyeing wastewater\u003csup\u003e8,9\u003c/sup\u003e \u0026zwnj;degrading organochlorine compounds in antibiotic and pharmaceutical wastewater\u0026zwnj;\u003csup\u003e10\u0026thinsp;\u0026minus;\u0026thinsp;12\u003c/sup\u003e, and \u0026zwnj;reducing Chemical Oxygen Demand (COD)\u003csup\u003e13\u0026thinsp;\u0026minus;\u0026thinsp;15\u003c/sup\u003e\u0026zwnj;. The substantial energy demand constrains this technology's widespread deployment.\u003c/p\u003e \u003cp\u003eThe radiolysis of water to produce hydrogen provides a possible approach for energy harvesting. During electron beam (EB) treatment of aqueous solutions, a substantial yield of reactive species is generated, including hydroxyl radicals (\u0026middot;OH), hydrated electrons (e⁻ₐq), superoxide radicals (\u0026middot;O₂⁻). Ionizing radiation can excite water molecules to simultaneously produce hydrated electrons and hydrogen radicals, enabling synergistic hydrogen evolution-confirming water radiolysis as a viable radiation-to-energy conversion pathway\u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u003c/sup\u003e. However, the current process of radiation organic degradation of pollutants is primarily dependent on oxidizing radical\u003csup\u003e\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e17\u003c/span\u003e,\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e18\u003c/span\u003e\u003c/sup\u003e. For instance, Khaneghah\u003csup\u003e\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u003c/sup\u003e et al. comprehensively analyzed the mechanisms by which electron beam irradiation degrades contaminants in cereal-based food products. Their review explicitly details the interaction between high-energy electron beams and water molecules to generate hydroxyl radicals (\u0026middot;OH), while thoroughly elaborating on how these radicals degrade mycotoxins and disrupt microbial organic structures through oxidative reactions ultimately achieving highly efficient decontamination. Li et al.\u003csup\u003e\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e20\u003c/span\u003e\u003c/sup\u003e utilized superoxide (\u0026middot;O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e) to combine rechargeable carbon-based supercapacitors with the redox groups-based O\u003csub\u003e2\u003c/sub\u003e, effectively transferring electrons onto O\u003csub\u003e2\u003c/sub\u003e to form \u0026middot;O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e radicals. They achieved excellent O\u003csub\u003e2\u003c/sub\u003e activation electron transfer efficiency, achieving complete mineralization of diverse organic pollutants.\u003c/p\u003e \u003cp\u003eA key challenge in energy recovery lies in efficiently harnessing reducing free radicals\u0026mdash;generated during organic pollutant oxidation\u0026mdash;for concurrent hydrogen production. Nevertheless, conventional degradation catalysts predominantly optimize oxidative radical reactions without facilitating radiolytic hydrogen generation. Since the concurrently generated reductive radicals remain underutilized\u003csup\u003e\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u003c/sup\u003e, this inefficiency not only constitutes resource wastage and diminishes energy utilization, but also allows reductive radicals to quench oxidative species, thereby compromising degradation efficacy. This limitation could potentially be addressed by composite catalyst systems. For instance, Yang et al. designed a composite photocatalyst UPC-HOF-6/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Pt by anchoring Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e with oxidation ability and Pt with reduction ability at the oxidation sites and reduction sites respectively, achieving rapid separation of photogenerated electron-hole pairs. This material exhibited excellent photocatalytic activity\u003csup\u003e\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e21\u003c/span\u003e\u003c/sup\u003e. Zhou et al. meticulously designed a model system consisting of metal and heterobimetallic catalysts for the electrochemical CO\u003csub\u003e2\u003c/sub\u003e reduction reaction. During the reaction process, the intramolecular electrostatic field promotes the redistribution of electrons, enabling the bimetallic structure to simultaneously utilize the reducing CO\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e radical and the oxidative intermediate in the CO\u003csub\u003e2\u003c/sub\u003e reduction process, resulting in a 10-fold increase in catalytic activity. At the same time, inert Zn\u003csup\u003e2+\u003c/sup\u003e was introduced to replace some Co\u003csup\u003e2+\u003c/sup\u003e to optimize the charge distribution, verifying that non-active metals have a regulatory effect on radical reactions.\u003csup\u003e\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e22\u003c/span\u003e\u003c/sup\u003e. Despite their proven efficacy in the fields of photocatalysis and electrocatalysis, they have not yet been adapted for irradiation applications.\u003csup\u003e\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e23\u003c/span\u003e,\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e24\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eIn this paper, we successfully developed a multifunctional composite catalyst for simultaneous methyl orange (MO) degradation and radiolytic hydrogen production. Using UiO-66 as the metal-organic framework (MOF) precursor, we synthesized a series of metal-incorporated derivatives through systematic compositional tuning. Catalytic performance was quantitatively assessed via pollutant degradation efficiency and H₂ evolution rates. Mechanistic investigations verified dual-reaction pathways and established an optimized protocol for synergistic contaminant removal and energy recovery. This integrated strategy provides new mechanistic insights for combined environmental remediation and renewable energy systems.\u003c/p\u003e"},{"header":"2. Experimental methods","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1 Synthesis process of Fe@C MOF\u003c/h2\u003e \u003cp\u003eTypically, 0.75 g terephthalic acid (BDC), 1.21 g FeCl\u003csub\u003e3\u003c/sub\u003e and 1.8 mL NaOH aq (2M) were dissolved in 10 mL dimethylformamide (DMF). Than sonicated the mixed solution until a homogeneous solution was obtained. The solution was sealed in a stainless-steel autoclave and placed in an oven preheated at 100 ℃ for 18 h. The mixture was cooled to room temperature naturally and rinsed with fresh DMF and deionized water three times by centrifugation (8000 rpm, 3 min) to remove the residual reactant and DMF. Finally, the product was dried under vacuum at 60 ℃. In addition, because the material is difficult to dry, it can be coated on a petri dish to increase the specific surface area, and then ground after drying. Finally, The ground sample is placed in a tube furnace, where the temperature is raised to 750 ℃ (5 K/min) and held for 2 hours, and then cooled to room temperature, the Fe@C samples was obtained\u003csup\u003e\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e25\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2 Synthesis process of UIO-66 MOF\u003c/h2\u003e \u003cp\u003eIn a typical preparation, 600 mg (1.88 mmol) of HfCl\u003csub\u003e4\u003c/sub\u003e and 348 mg (2.08 mmol) of BDC were dissolved in 20 mL of DMF. Then sonicated until a homogeneous solution was obtained. The solution was sealed in a 100 mL Teflon-lined stainless-steel autoclave and placed in an oven preheated at 100\u0026deg;C for 24 h. The mixture was cooled to room temperature naturally and rinsed with fresh DMF three times by centrifugation (8000 rpm, 3 min) to remove the residual reactant and DMF. Finally, the UIO-66 was dried under vacuum at 60\u0026deg;C.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3 Synthesis process of UIF MOF\u003c/h2\u003e \u003cp\u003eThe synthesis of UIF MOF followed a modified UiO-66 protocol, wherein Fe@C nanoparticles were introduced as the iron source during crystallization to generate Fe-active sites while maintaining structural integrity.\u003c/p\u003e \u003c/div\u003e"},{"header":"3. Results and discussion","content":"\u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003e3.1 Characterization of the catalysts\u003c/h2\u003e \u003cp\u003eTo characterize the morphology of the synthesized materials, we conducted comprehensive electron microscopy analysis using both scanning (SEM) and transmission (TEM) techniques. Figure\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea shows that the Fe@C MOF exhibits a heterogeneous morphology consisting of irregularly sized nanosheets and nanoparticles. In striking contrast, the UIO-66 MOF (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb) displays highly uniform nanospheres with smooth surfaces. The third-step synthesized UIF material retained the spherical morphology of its UIO-66 precursor but exhibited significantly reduced particle size (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ec). TEM imaging (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ed) confirmed the solid spherical structure of the UIF samples, while the absence of discernible lattice fringes in HRTEM analysis indicates their amorphous nature. Elemental mapping (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eg) confirmed the homogeneous distribution of Fe, Hf, N, C, and O throughout the nanospheres, providing conclusive evidence for the successful incorporation of iron into the UIO framework and the formation of UIF.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eTo analyze the structure, crystal phase, and chemical composition, we performed a series of systematic characterizations. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea, the powder X-ray diffraction (PXRD) pattern of UIO-66 exhibits a characteristic weak diffraction peak at 8\u0026deg;, corresponding to its porous framework structure and consistent with literature reports\u003csup\u003e\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e20\u003c/span\u003e\u003c/sup\u003e. The XRD pattern of the Fe@C sample matches the standard FeO reference (PDF#46-1312), confirming its oxide nature. FTIR spectroscopy (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb) was used to identify organic functional groups, revealing characteristic absorption bands between 3700\u0026thinsp;\u0026minus;\u0026thinsp;475 cm⁻\u0026sup1; for all samples. Distinct peaks were observed at 1590 cm⁻\u0026sup1; and 1420 cm⁻\u0026sup1; (attributed to -COO groups), along with 750 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 480 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (corresponding to Hf-O vibrations)\u003csup\u003e\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e20\u003c/span\u003e\u003c/sup\u003e. Notably, UIF exhibited identical IR spectra before and after irradiation, suggesting preserved metal coordination environments. The irradiated UIO-66 spectrum agreed with previous studies\u003csup\u003e\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e26\u003c/span\u003e,\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e27\u003c/span\u003e\u003c/sup\u003e. XPS Survey Spectrum (Fig. \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e) confirmed UIF's composition (Hf, Fe, C, O), with Hf showing more changes in value states in UIF compared to UIO-66 (Fig. S2), attributed to Hf incorporation and Hf-Fe synergy. Similarly, due to the incorporation of the Hf element, the Fe element exhibited a state where both divalent and trivalent forms coexisted. While PXRD/FTIR showed minimal changes, XPS clearly tracked the valence state evolution from Fe\u003csup\u003e2+\u003c/sup\u003e species in Fe@C to mixed Fe\u003csup\u003e2+\u003c/sup\u003e/Fe\u003csup\u003e3+\u003c/sup\u003e in UIF (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec). High-resolution XPS of the Fe 2p region revealed four deconvoluted peaks (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec and S3): 710.9 eV (Fe Fe 2p₃\u003csub\u003e/\u003c/sub\u003e₂), 724.9 eV (Fe 2p₁\u003csub\u003e/\u003c/sub\u003e₂), and satellite features at 719.3 eV and 732.4 eV. The coexistence of Fe\u003csup\u003e3+\u003c/sup\u003e (713.8 eV, 725.9 eV) and Fe\u003csup\u003e2+\u003c/sup\u003e (710.7 eV, 723.9 eV) was evident, with a 2:1 ratio\u003csup\u003e\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e25\u003c/span\u003e,\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e28\u003c/span\u003e\u003c/sup\u003e. Brunauer-Emmett-Teller (BET) measurements were performed to characterize pore structures. As shown in Fig. S4, UIF samples exhibit significantly increased N₂ adsorption capacity and typical Type IV isotherms. Hysteresis loops occurred at relative pressures (P/P0) of 0.85-1.0, indicating mesopore formation. Barret-Joyner-Halenda (BJH) pore size distribution further confirmed mesoporous characteristics (Fig. S5). The UIF sample possesses BET specific surface area (646.6 m\u0026sup2; g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e), thus providing more active sites for enhanced catalytic performance.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003e3.2 Catalyst performance of different systems\u003c/h2\u003e \u003cp\u003eMethyl orange (MO) solution (50 mg/L) was selected as the model pollutant to evaluate the catalytic degradation performance, consistent with previous studies\u003csup\u003e\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e29\u003c/span\u003e\u003c/sup\u003e. Prior to irradiation (0 kGy), an initial decrease in MO concentration was observed due to catalyst adsorption. Subsequently, the MO concentration exhibited a gradual reduction with increasing irradiation dose, following the reaction kinetics described by Eq. (S1)\u003csup\u003e29\u003c/sup\u003e. Comparative studies revealed the superior performance of UIF catalyst, achieving the highest degradation rate constant (k) among all tested materials (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea). Under 1.2 kGy irradiation with 5 mg UIF catalyst, the degradation efficiency reached 0.9788, corresponding to a 98% removal rate - significantly exceeding the performance of UIO-66 (0.8342) and Fe@C (0.8315) under identical conditions. Notably, UIF enhanced the radiation degradation efficiency from 19.8% (EB alone) to 97.8% (Fig. S6). The enhanced performance stems from two key factors: (1) retention of UIO-66's strong adsorption capacity, and (2) improved radiation degradation through Fe incorporation. The optimized UIF material exhibited a k value of 1.4867 - approximately 8-fold higher than irradiation alone (0.1841). This improvement confirms that Fe introduction creates additional catalytic active sites, while the Fe-Hf synergistic effect further enhances catalytic efficiency.\u003c/p\u003e \u003cp\u003eTo evaluate catalyst stability under irradiation and assess potential secondary contamination from irradiated wastewater, ion leaching concentrations and cycling tests were measured (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eb and S7). At 1.2 kGy irradiation, UIO-66 exhibited minimal leaching, confirming its inherent stability. Remarkably, the Fe-doped UIF material demonstrated even lower iron leaching (0.145 mg/L), indicating that Fe incorporation enhances irradiation stability. Cycling tests demonstrated the material's stability, maintaining 30% MO removal after three consecutive irradiation-centrifugation cycles.\u003c/p\u003e \u003cp\u003eTo evaluate the impact of irradiation dose on catalytic performance, we systematically compared the degradation efficiency of all three materials across incrementally increased doses (1.2\u0026ndash;4.8 kGy). As shown in Fig. S8, UIF consistently outperformed both catalyst-free irradiation and other materials throughout this dose range. Further demonstrating UIF's advantages, we conducted comparative studies at lower irradiation doses (Fig. S9). These results reveal that both UIF and UIO-66 achieve significantly enhanced degradation efficiency under low-dose irradiation conditions when compared to Fe@C or catalyst-free systems.\u003c/p\u003e \u003cp\u003eWe next investigated catalyst concentration effects on MO removal efficiency and rate constants (k) for UIF samples (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ec). Results demonstrate that increasing catalyst concentration significantly enhances degradation performance under fixed conditions, achieving near-complete MO removal (99.6%). Concurrently, we evaluated dose-response relationships across varying catalyst concentrations (Fig. S10).\u003c/p\u003e \u003cp\u003eTo evaluate catalyst performance across wastewater's typical pH range, we systematically tested degradation efficiency under varied pH conditions. Initial measurements revealed the MO solution's native pH of 5.30 (weakly acidic). Using HCl and NaOH solutions, we adjusted the system to pH 2.69 (acidic), 8.09 (weakly alkaline), and 10.62 (strongly alkaline). As demonstrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ed, acidic conditions significantly enhanced MO degradation efficiency. This pH-dependence arises from hydroxyl radical (\u0026middot;OH) consumption through reaction with hydroxide ions (OH\u003csup\u003e\u0026minus;\u003c/sup\u003e) in alkaline media Eq. (S2), thereby inhibiting MO degradation at higher pH values\u003csup\u003e\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e\u003c/sup\u003e. These findings confirm \u0026middot;OH's pivotal role in the catalytic mechanism, with potential supplementary contributions from hydrated electrons\u003csup\u003e31\u003c/sup\u003e. Under 1.2 kGy irradiation at acidic pH, ion leaching measurements (Fig. S11) showed 0.268 mg/L Hf and 0.087 mg/L Fe, both well below wastewater discharge limits. Notably, pH-dependent leaching trends were observed, suggesting pH-mediated effects on both catalyst stability and radiation efficiency.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eAccording to the reported literature, MOF materials have unique advantages in hydrogen production by irradiation decomposition due to their diverse frameworks and topological structures. We evaluated the hydrogen generation performance of our catalysts. Figure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea demonstrates the electron-beam dose dependence of H₂ evolution for all three catalysts. Results confirm that our MOF materials significantly accelerate radiolytic hydrogen production compared to pure water across 1\u0026ndash;30 kGy, with near-linear H₂ yield escalation versus absorbed dose (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eb). The enhancement of irradiation dose contributes to the release of H\u003csub\u003e2\u003c/sub\u003e. This is also consistent with the results reported in the literature, which UiO-66 can be synthesized using various organic linkers and is shown to exhibit a wide variation in water absorption capacity and hydrogen bonding, underlying the fact that the advanced and unique UiO-66 topologies play a vital role\u003csup\u003e\u003cspan additionalcitationids=\"CR33\" citationid=\"CR31\" class=\"CitationRef\"\u003e32\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e34\u003c/span\u003e\u003c/sup\u003e. Notably, at low catalyst concentrations (5 g\u0026middot;L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e), where gamma dose absorption by solids is negligible in radiation equivalence calculations, UIF exhibited 5-fold enhancement over pure water. The maximum radiolytic yield reached G value is 1.17 \u0026times; 10\u003csup\u003e\u0026minus;\u0026thinsp;7\u003c/sup\u003e mol J\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eb), We have reason to think that more efficient and faster H\u003csub\u003e2\u003c/sub\u003e generation rate can be obtained under electron beam irradiation. The change in H\u003csub\u003e2\u003c/sub\u003e concentration (as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ec) shows that an increase in catalyst concentration from 1 g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e to 10 g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003eaccelerates H\u003csub\u003e2\u003c/sub\u003e release. Radiation chemical efficiency was quantified via G-values (H₂ molecules per 100 eV absorbed energy). Using water decomposition Gibbs free energy (237 kJ\u0026middot;mol⁻\u0026sup1;) and Eq. (S3)\u0026sup2;⁰, we calculated the radiation-to-hydrogen (RTH) efficiency. The energy conversion efficiency of rays-to- hydrogen (RTH) in neat water is measured to be ~\u0026thinsp;0.3%, a fairly uncompetitive value. In contrast, this study dramatically improved the RTH efficiency at very low metal concentrations (~\u0026thinsp;5 g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) by using a UIF water interface system, achieving the highest conversion efficiency (~\u0026thinsp;1.11%). Although existing materials such as oxides and zeolites have shown the ability to promote the release of radiolytic H\u003csub\u003e2\u003c/sub\u003e. However, when the concentration is relatively low, or even much higher than the concentration of UIF, the RTH value is lower than that of UIF, as shown in Table S1\u003csup\u003e35,36\u003c/sup\u003e. This establishes MOFs as prime candidates for radiolytic water splitting, distinct from photolytic/electrolytic processes. Reusability studies demonstrated UIF's practical viability. After four irradiation-recovery cycles (cumulative 120 kGy), it retained 35.7% initial G-value efficiency (0.4% RTH; Fig. S12), confirming robust radiation stability.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec9\" class=\"Section2\"\u003e \u003ch2\u003e3.3 Mechanism of degradation and hydrogen production\u003c/h2\u003e \u003cp\u003eTo elucidate the respective contributions of adsorption and catalytic degradation to contaminant removal, we systematically evaluated the adsorption capacities of different catalyst materials. Experiments were conducted using 1.0 g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e catalyst in 50 mg L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e MO solution. The adsorption kinetics were analyzed using both pseudo-first-order and pseudo-second-order models Eq. (S4-S5)\u003csup\u003e\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e20\u003c/span\u003e,\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e37\u003c/span\u003e,\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e38\u003c/span\u003e\u003c/sup\u003e, with the pseudo-second-order model\u003csup\u003e\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e39\u003c/span\u003e\u003c/sup\u003e providing the best fit to the experimental data (see kinetic parameters in Table S2). With the increase of the catalyst content, the adsorption rate increases and the adsorption capacity decreases, almost reaching equilibrium adsorption at 12h. The adsorption capacity qe of UIF was 91.62 mg g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, which was significantly higher than that of UIO-66 (71.44 mg g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) and Fe@C (28.84 mg g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/p\u003e \u003cp\u003eCurrent literature primarily attributes radiolytic degradation mechanisms to hydroxyl radical (\u0026middot;OH) generation via water radiolysis. To elucidate \u0026middot;OH's specific role in MO decomposition, we conducted radical quenching experiments using 1 vol % tert-butanol (a selective \u0026middot;OH scavenger). As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ea, Fe@C exhibited significant suppression of degradation kinetics (13.5% reduction in k-value) upon scavenger addition, confirming \u0026middot;OH's dominant role in its catalytic mechanism. In contrast, UIF and UiO-66 displayed negligible reactivity changes under identical quenching conditions. In addition, the EPR (Electron Paramagnetic Resonance) test of hydroxyl radicals was conducted using DMPO (5, 5-dimethyl-1-pyrroline-N-oxide) as the spin trap agent\u003csup\u003e\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e38\u003c/span\u003e\u003c/sup\u003e. The addition of UIF further enhanced the DMPO/OH signal compared with Fe@C (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ec). These collective findings establish that the bimetallic composition in UIF synergistically promotes \u0026middot;OH production during irradiation.\u003c/p\u003e \u003cp\u003eDecades of research confirm that high-energy radiation generates H₂ primarily through water ionization/excitation pathways involving solvated electrons (e\u003csub\u003esol\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e) and hydrogen atoms H, as described by Eq. (S6-S9)\u003csup\u003e\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e20\u003c/span\u003e\u003c/sup\u003e. To verify e\u003csub\u003esol\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e's dominant contribution to H₂ production in UIF, we employed Cd\u003csup\u003e2+\u003c/sup\u003e as a selective scavenger for solvated electrons\u003csup\u003e\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e40\u003c/span\u003e,\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e41\u003c/span\u003e\u003c/sup\u003e. Control experiments were conducted using Cd\u003csup\u003e2+\u003c/sup\u003e solutions with volume ratios of 0.002, 0.02, 0.2, 0.4 and 0.6 respectively, and the results are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eb. The results show that with the increase of Cd\u003csup\u003e2+\u003c/sup\u003e concentration, the volume of H\u003csub\u003e2\u003c/sub\u003e shows a decreasing trend, which further proves the key role of e\u003csub\u003esol\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e radicals in hydrogen production. Complementary electron paramagnetic resonance (EPR) studies using TEMPO (2,2,6,6-tetramethylpiperidin-1-oxyl) revealed near-complete signal quenching when UIF was present (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ed). This indicates abundant low-energy electron generation during irradiation, leading to TEMPO reduction via electron transfer.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eTo further reveal its catalytic mechanism, we analyzed the changes in the valence states of elements and the possible free radical reactions. The XPS spectra of Fe and Hf before and after EB radiation are shown in Fig. S13. Notable valence shifts occurred in iron species, where both FeFe\u003csup\u003e2+\u003c/sup\u003e and Fe\u003csup\u003e3+\u003c/sup\u003e exhibited substantial transformations. It can be seen that EB radiation provides sufficient Fe\u003csup\u003e2+\u003c/sup\u003e for the generation of \u0026middot;OH. It is reported that the H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e produced by irradiated water can convert Fe\u003csup\u003e2+\u003c/sup\u003e and Fe\u003csup\u003e3+\u003c/sup\u003e into each other to form active substances, as shown in Eq. (S10-11)\u003csup\u003e\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e37\u003c/span\u003e\u003c/sup\u003e. In addition, the Hf element also changes significantly. After irradiation, while the peaks of the oxides of the Hf element decrease, some peaks also disappear accordingly. Therefore, it is reasonable to believe that there may be electron transfer between iron and Hf metals. The synergistic coexistence of Fe and Hf in UIF facilitates: Enhanced coordination in aqueous matrices under irradiation Improved catalytic efficiency for pollutant degradation and mineralization Concurrent clean H₂ energy production. This bifunctional capability positions UIF as a promising technology for environmental remediation with energy co-generation benefits.\u003c/p\u003e \u003c/div\u003e"},{"header":"4. Conclusions","content":"\u003cp\u003eIn summary, we reported MOF-derived Fe-Hf bimetallic catalysts exhibits exceptional radiation-driven catalytic activity for methyl orange (MO) degradation and hydrogen evolution performance. Mechanistic evidence confirms that, by facilitating the transition of iron valence from divalent to mixed (Fe²⁺/Fe³⁺), hafnium doping allows iron to participate in redox cycling that drives free radical generation in water radiolysis. At the same time, Fe-Hf bimetallic catalysts boost the production of hydrated electron during the water radiolysis process. Bimetallic catalysts mediate the concomitant formation of oxidative and reductive free radicals in aqueous radiolysis systems. This capability facilitates energy recovery during organic contaminant remediation while providing a platform to engineer integrated redox reaction architectures.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eCRediT authorship contribution statement\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eDeclaration of Competing Interest\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare no competing financial interest.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eData availability\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eData will be made available on requst.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAppendix A. Supplementary data\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe Supporting Information is available free of charge on the Energy Storage Materials website.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgments\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis work was supported by the National Natural Science Foundation of China (12175188), Nuclear energy development and research projects (HNKF202228(30)), the Fundamental Research Funds for the Central Universities of China (20720210051), XMU Training Program of Innovation and Entrepreneurship for Undergraduates (2021X1173).\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eSeung, J. P. et al. 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J.\u003c/em\u003e\u003cem\u003e,\u003c/em\u003e \u003cstrong\u003e169\u003c/strong\u003e, 258-262 (2011).\u003c/li\u003e\n\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":"npg-asia-materials","isNatureJournal":false,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"am","sideBox":"Learn more about [NPG Asia Materials](http://www.nature.com/am/)","snPcode":"41427","submissionUrl":"https://mts-am.nature.com/cgi-bin/main.plex","title":"NPG Asia Materials","twitterHandle":"@asiamaterials","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature AJ","inReviewEnabled":true,"inReviewRevisionsEnabled":true},"keywords":"Electron beam irradiation, bimetallic catalyst, irradiation degradation, irradiation hydrogen production","lastPublishedDoi":"10.21203/rs.3.rs-6876542/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6876542/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eElectron beam (EB) irradiation technology for organic pollutant degradation primarily exploits oxidizing radicals, while concurrently generated reducing radicals remain underutilized. These reducing species represent not only wasted energy but also impair degradation efficiency through radical neutralization. To overcome this limitation, we developed a synergistic catalyst designed to simultaneously harness both irradiation-driven oxidative and reductive free radicals. Mechanistic studies reveal that hafnium doping facilitates the valence conversion of iron from a purely divalent state (Fe\u0026sup2;⁺) to a mixed Fe\u0026sup2;⁺/Fe\u0026sup3;⁺ state. This mixed-valence iron subsequently mediates free radical generation during water radiolysis through redox cycling between its divalent and trivalent states. Compared to EB irradiation alone, this catalytic system achieves 98% removal of the target pollutant (methyl orange), representing a 5-fold efficiency enhancement. Concurrently, hydrogen production efficiency increases nearly 5-fold. This work establishes a new paradigm for integrated pollutant degradation and energy harvesting.\u003c/p\u003e","manuscriptTitle":"MOF-Derived Bimetallic Catalysts for Simultaneous Irradiation Degradation and Hydrogen Evolution: Synergistic Oxidation-Reduction Processes","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-06-27 11:16:12","doi":"10.21203/rs.3.rs-6876542/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"revise","date":"2025-07-14T10:01:45+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"This content is not available.","date":"2025-07-12T00:47:54+00:00","index":3,"fulltext":"This content is not available."},{"type":"editorInvitedReview","content":"This content is not available.","date":"2025-07-09T11:15:40+00:00","index":1,"fulltext":"This content is not available."},{"type":"editorInvitedReview","content":"This content is not available.","date":"2025-07-02T13:50:39+00:00","index":2,"fulltext":"This content is not available."},{"type":"reviewerAgreed","content":"This content is not available.","date":"2025-06-27T06:25:18+00:00","index":3,"fulltext":"This content is not available."},{"type":"reviewerAgreed","content":"This content is not available.","date":"2025-06-23T08:24:25+00:00","index":2,"fulltext":"This content is not available."},{"type":"reviewerAgreed","content":"This content is not available.","date":"2025-06-23T07:37:16+00:00","index":1,"fulltext":"This content is not available."},{"type":"reviewersInvited","content":"","date":"2025-06-23T07:33:21+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-06-13T11:10:08+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-06-12T05:01:35+00:00","index":"","fulltext":""},{"type":"submitted","content":"NPG Asia Materials","date":"2025-06-12T05:01:34+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"npg-asia-materials","isNatureJournal":false,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"am","sideBox":"Learn more about [NPG Asia Materials](http://www.nature.com/am/)","snPcode":"41427","submissionUrl":"https://mts-am.nature.com/cgi-bin/main.plex","title":"NPG Asia Materials","twitterHandle":"@asiamaterials","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature AJ","inReviewEnabled":true,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"c43f1424-3625-48cc-ad91-ddac8e5d5676","owner":[],"postedDate":"June 27th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"in-revision","subjectAreas":[{"id":50432073,"name":"Physical sciences/Chemistry/Catalysis/Catalyst synthesis"},{"id":50432074,"name":"Physical sciences/Chemistry/Materials chemistry/Metal\u0026#x2013;organic frameworks"}],"tags":[],"updatedAt":"2025-07-14T10:10:41+00:00","versionOfRecord":[],"versionCreatedAt":"2025-06-27 11:16:12","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-6876542","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6876542","identity":"rs-6876542","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}