Journal of Catalysis最新文献

{"title":"Key role of yttrium doping on Cu/CeO2 (111) in water–gas shift reaction: Promotion of cluster dispersity","authors":"Yu-Xuan Zhu ,&nbsp;Yingqi Wang ,&nbsp;Gui-Chang Wang","doi":"10.1016/j.jcat.2025.116405","DOIUrl":"10.1016/j.jcat.2025.116405","url":null,"abstract":"<div><div>Conventional theoretical models of electronic metal-support interaction (EMSI) often assume <strong><em>uniform metal dispersion</em></strong>, leading to conclusions conflicting with experimental observations. It highlights the critical need to incorporate <strong><em>metal dispersion effects</em></strong> in EMSI studies. Here, we investigate how Y³⁺ doping regulates Cu cluster dispersion on CeO₂(1 1 1) for the water–gas shift reaction (WGSR) using density functional theory (DFT), mean-field microkinetic modeling (MF-MKM), and kinetic Monte Carlo (kMC) simulations. Cohesion energy analysis reveals that on undoped ceria, bilayer clusters predominate. However, Y³⁺ (compared to Ce⁴⁺) possesses a smaller radius and lower redox capability, which differentiates loading sites but obstructs EMSI. Excessive doping even restricts the formation of spillover oxygen (O_sp), thereby favoring 3D clusters. The presence of surface spillover oxygen partially compensates for the EMSI weakening. This compensation effect causes the cohesive energy difference between bilayer and O_sp planar-type clusters to become positive, resulting in the advantage of O_sp planar-type clusters at lightly doping level. Kinetic simulations identify O_sp-type planar copper clusters as functional active phases for undoped/lightly doped ceria, while heavily doped systems are regular planar clusters without O_sp. O_sp-type planar clusters exhibit extraordinary catalytic activity due to O_sp-mediated adsorption and reactivity promotion, whereas bilayer clusters manifest low activity. Comprehensive analysis of cluster dispersion and structure–activity relationships discloses non-monotonic WGSR activity dependence on Y-doping: activity of sub-nanometer copper clusters peaks at low doping amount before declining at higher doping levels, aligning with experiments This work highlights the necessity of identifying both dispersion and activity of clusters for specific doping levels. These findings provide critical insights for the design of doped-supported catalysts and establish a theoretical framework for optimizing EMSI in heterogeneous catalysis.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116405"},"PeriodicalIF":6.5,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144924408","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A comprehensive theoretical study on CuOx/Cu(110) catalyzed water–gas shift reaction","authors":"Yu-Bi Huang ,&nbsp;Yingqi Wang ,&nbsp;Gui-Chang Wang","doi":"10.1016/j.jcat.2025.116404","DOIUrl":"10.1016/j.jcat.2025.116404","url":null,"abstract":"<div><div>In recent years, theoretical studies on Cu-based catalysts for the water–gas shift reaction (WGSR) have been conducted extensively. However, the issues concerning the oxidation state of copper atoms under reaction conditions and their roles in catalyzing WGSR remain unresolved. Surface science experiments have demonstrated that clean Cu(110) exhibits higher catalytic activity than clean Cu(111), and a previous study has theoretically indicated that the oxidation can enhance the intrinsic activity of Cu(111). Therefore, determining the surface oxides on Cu(110) and their catalytic activity is fundamental and will provide valuable insights for rational catalyst design. In this paper, ab initio atomistic thermodynamics was performed to reveal the potential phase transitions from clean Cu(110) to Cu₂O (110), including added row-(4 × 1) (AR-41), added row-(2 × 1) (AR-21), as well as added strand-c(6 × 2) (AS-c62) structures. The WGSR mechanisms were systematically investigated on these distinct surfaces by density functional theory (DFT) calculations. Additionally, we identified a volcano-type relationship between the catalytic performance and the oxidation degree of Cu(110), with the mildly oxidized AR-41 structure exhibiting optimal activity, as determined by mean-field microkinetic modeling (MF-MKM) and kinetic Monte Carlo (kMC) simulations. Moreover, the degree of rate control (DRC) analysis revealed that water dissociation is no longer the rate-determining step for oxidized structures compared to clean Cu(110). Instead, the direct oxidation of CO and the production of H₂ may play a more critical role in CuO_x/Cu(110)-catalyzed WGSR. Meanwhile, it was found that the redox and carboxyl mechanisms compete with each other. The carboxyl mechanism predominantly operates at low levels of oxidation, while the redox mechanism takes precedence at high levels of oxidation. Consequently, the appropriate oxidation state will enhance catalytic activity on Cu(110). Additionally, doping with other metal atoms was used as a strategy to improve catalyst performance, and it was found that doping with Pd or Zn may slightly promote the catalytic performance. Furthermore, a comparison between CuO_x/Cu(110) and CuO_x/Cu(111) was conducted, and it was found that they show different catalytic activity due to their unique interfaces of CuO_x and metallic subsurface.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116404"},"PeriodicalIF":6.5,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144928589","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Visible-light-driven aerobic oxidation via a dual ROS-generating manganese(II)-organic framework photocatalyst","authors":"Hui Chen ,&nbsp;Jiahui He ,&nbsp;Zhen Zhou ,&nbsp;Bin Wang ,&nbsp;Xiong-Feng Ma ,&nbsp;Maojun Deng ,&nbsp;Yuanzhen Zhou ,&nbsp;Pascal Van Der Voort","doi":"10.1016/j.jcat.2025.116403","DOIUrl":"10.1016/j.jcat.2025.116403","url":null,"abstract":"<div><div>Developing sustainable and efficient photocatalytic systems for aerobic oxidation remains a pivotal challenge in green chemistry. Herein, we report the rational design and synthesis of a novel manganese(II)-organic framework (An-MnMOF) by integrating anthracene-based photoactive ligands with Mn(II)-oxo clusters. The framework exhibits broad visible-light absorption extending up to 650 nm, efficient charge separation, and dual reactive oxygen species (ROS) generation capabilities. Structural characterization confirms a crystalline 2D lamellar architecture with hierarchical porosity, while mechanistic studies reveal a synergistic interplay between anthracene-mediated light harvesting and Mn(II)-driven redox processes. Under visible-light irradiation, An-MnMOF achieves exceptional catalytic performance in aerobic oxidation reactions, including hydroxylation of arylboronic acids (＞95 % yield) and benzylic C(<em>sp</em>³)-H bond activation (＞85 % yield), outperforming the homogeneous Mn catalyst. The framework’s microporous channels stabilize reactive intermediates, suppressing overoxidation, while its robust chemical and thermal stability enables five consecutive recycling cycles without activity loss. This work establishes a paradigm for noble-metal-free photocatalysis by leveraging MOF-confined dual-function sites for solar-driven organic transformations, advancing sustainable synthesis methodologies.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116403"},"PeriodicalIF":6.5,"publicationDate":"2025-08-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144924405","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ir-catalyzed transfer hydrogenation and N-alkylation of alkynyl/alkenyl arylamines with carbonyls in water","authors":"Jianhua Liao,&nbsp;Huajie Zhu,&nbsp;Shilin Guo,&nbsp;Jinhui Li,&nbsp;Lu Ouyang,&nbsp;Renshi Luo","doi":"10.1016/j.jcat.2025.116402","DOIUrl":"10.1016/j.jcat.2025.116402","url":null,"abstract":"<div><div>Herein, we advance a novel and efficient iridium-catalyzed transfer hydrogenation and <em>N</em>-alkylation of alkynyl/alkenyl arylamines with carbonyls to facilitate the streamlined synthesis of diverse amines. The reaction could be achieved direct hydrogenation and alkylation of alkynyl/alkenyl arylamines with carbonyls using H₂O as reaction media and HCO₂H as hydrogen donor, providing a variety of arylamine derivatives in moderate to excellent yields. Control experiments indicated the <em>N</em>-alkylation of alkynyl/alkenyl arylamines contributed to the reduction of alkynes/alkenes. The practicality of this sustainable process was evidenced by large-scale, catalyst recycling experiments and derivatization of biologically active molecules.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116402"},"PeriodicalIF":6.5,"publicationDate":"2025-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144919085","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unraveling B, N Co-doping synergy in graphitic carbon nitride for efficient CO2 cycloaddition with styrene oxide","authors":"Hafila S. Khairun ,&nbsp;Gazala Parveen ,&nbsp;Ripsa Rani Nayak ,&nbsp;Jogeswar Chhatria ,&nbsp;Sooraj Kunnikuruvan ,&nbsp;Navneet Kumar Gupta","doi":"10.1016/j.jcat.2025.116399","DOIUrl":"10.1016/j.jcat.2025.116399","url":null,"abstract":"<div><div>The cycloaddition of CO₂ and styrene oxide to produce styrene carbonate under solvent-free conditions offers an eco-friendly, atom-efficient, and highly effective approach to CO₂ utilization. This study presents a highly active and selective catalytic system based on boron and nitrogen co-doped graphitic carbon nitride (BN-GCN) for the efficient production of styrene carbonate. Unlike many conventional catalysts, the BN-GCN system operates without needing solvents or metals, functioning as a metal-free heterogeneous catalyst for the cycloaddition of CO₂ with styrene oxide. It outperforms other heteroatom-doped graphitic carbon nitride (X-GCN) catalysts, with the enhanced activity attributed to the synergistic interaction of reactants with B and N sites. XPS analysis reveals that the N moiety and the B atom are critical active sites for cooperative catalysis. The BN-GCN catalyst achieves 75 % conversion and &gt; 90% selectivity for styrene carbonate (SC) formation under mild conditions (353 K, 2 bar CO₂) within 3 h. Comprehensive material characterization, kinetic studies, and reaction data confirm that B and N co-doping facilitates the co-activation of CO₂ and epoxide. Based on density functional theory (DFT) calculations, and experiments, a convenient mechanism has been proposed for this unique method. The B–N bond duality in BN-GCN offers a cost-effective, sustainable, and efficient catalytic pathway for CO₂ utilization.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"452 ","pages":"Article 116399"},"PeriodicalIF":6.5,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144915847","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Construction of visible light-driven ternary S-scheme melamine sponge MS/TpTt/ZIS heterojunction photocatalysts for enhanced photocatalytic pollutant removal and hydrogen evolution","authors":"Qingmei Tang ,&nbsp;Yuqi Wan ,&nbsp;Yuzhuo Wan ,&nbsp;Zhiquan Pan ,&nbsp;Qingrong Cheng","doi":"10.1016/j.jcat.2025.116388","DOIUrl":"10.1016/j.jcat.2025.116388","url":null,"abstract":"<div><div>Charge separation critical for improving photocatalytic performance. But single semiconductor cannot realize efficient charge separation and transport. Little research has been reported on using melamine foam (MS) as a carrier. Herein, we have successfully synthesized a heterojunction MS/TpTt/ZnIn₂S₄-x% (MTZIS-x%) photocatalysis with MS as the carrier by solvothermal method. It was found the degradation rate of MO over MTZIS-3 % could reach almost 100 %, and the biotoxicity tests showed that degraded residual liquid of MO was almost non-biological toxicity. Moreover, the ptotocatalytic H₂ evolution rate of MTZIS-3 % reached to 11523.64 µmol g⁻¹h⁻¹, which was 7.02, 11.91 and 13.19 times than that of ZIS, MS/TpTt and COF-TpTt. And the evolution rate of photoreduction CO₂ to CO was 501.55 µmol g⁻¹ h⁻¹. The excellent photocatalytic property was owing to the S-scheme band structure facilitated the separation of electron-hole efficiently and retained the highly reducing electrons. This work provided a theoretical reference for the construction of efficient new heterojunction photocatalysts using MS as a carrier.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116388"},"PeriodicalIF":6.5,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144919124","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Solventless and low-temperature ring-opening polymerization using deep eutectic solvents of ε-caprolactone and their depolymerization cycles for biodegradable polyesters","authors":"Puracheth Rithchumpon ,&nbsp;Wanich Limwanich ,&nbsp;Kraikrit Utama ,&nbsp;Nathaporn Cheechana ,&nbsp;Natthapol Akkravijitrkul ,&nbsp;Padchanee Sangthong ,&nbsp;Winita Punyodom ,&nbsp;Puttinan Meepowpan","doi":"10.1016/j.jcat.2025.116400","DOIUrl":"10.1016/j.jcat.2025.116400","url":null,"abstract":"<div><div>The catalytic performance of deep eutectic solvents (DESs) between choline chloride (ChCl) and organic acids was investigated for the ring-opening polymerization (ROP) of <em>ε</em>-caprolactone (CL). These organic acids act as hydrogen bond donors (HBDs), while choline chloride serves as the hydrogen bond acceptor (HBA). Among fifteen acids, (–)-camphorsulfonic acid (CSA), diphenyl phosphate (DPP), 2,5-dimethylbenzenesulfonic acid (DSA), and <em>p</em>-toluenesulfonic acid (PTSA) with ChCl at 100:1:1 M ratio could effectively poly(<em>ε</em>-caprolactone) (PCL) with the molecular weight ranging from 8,000 to 10,000 g/mol and a low dispersity (<em>Ð</em>) (1.2–1.5). The ROP kinetics was powerfully investigated differential scanning calorimetry (DSC) technique. PTSA in combination with ChCl exhibited the fastest reaction and the lowest activation energy (<em>E_a</em>). Additionally, the depolymerization processes of PCL back to its CL monomer was studied by thermogravimetric analysis (TGA). Notably, phosphotungstic acid (PTA) demonstrated the highest depolymerization activity achieving a 100 % yield of CL at 160 °C for 1 h under vacuum distillation.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116400"},"PeriodicalIF":6.5,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144919132","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The terphenyl phosphine TRuPhos: a novel and efficient ligand for the palladium-catalyzed arylation of hindered primary alkyl amines with mechanism clarification","authors":"Lixue Zhang ,&nbsp;Guoyu Cheng ,&nbsp;Fabin Zhou ,&nbsp;Xin Yang ,&nbsp;Huicheng Cheng ,&nbsp;Mei Yu ,&nbsp;Dahong Jiang ,&nbsp;Peng Zhou ,&nbsp;He Yang ,&nbsp;Bingxin Yuan ,&nbsp;Wenjun Tang ,&nbsp;Ji-cheng Shi","doi":"10.1016/j.jcat.2025.116391","DOIUrl":"10.1016/j.jcat.2025.116391","url":null,"abstract":"<div><div>Terphenyl phosphines are rising as powerful supporting ligands in the palladium-catalyzed C-N cross-coupling reactions, leading to reduced catalyst loadings and broadened substrate scope. To extend the terphenyl phosphine family, TRuPhos and TSPhos along with their 2-amino-biphenyl-ƞ²-C,N palladium precatalysts have been synthesized and characterized, including one complex by single-crystal diffraction. TRuPhos exhibits unprecedented efficiency in the palladium-catalyzed arylation of many hindered primary alkyl amines. Mechanism studies have clarified that: 1) the transmetalation <strong>path A</strong> involving amine adducts of oxidative addition product does not work by the TRuPhos-supported palladium catalyst in the arylation of hindered primary alkyl amines, but works for that in small bulk amines; 2) the <strong>path C</strong> involving the substitution of halogen atoms on oxidative addition products by <em>t</em>BuO groups seems impossible as well; 3) the reaction occurred between oxidative addition products and sodium amides forming C-N coupling products suggests that <strong>path B</strong> is a possible transmetalation pathway in Pd/TRuPhos-catalyzed arylation of hindered primary alkyl amines.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116391"},"PeriodicalIF":6.5,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144910684","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enhanced hydrogen production performance and stability simultaneously in aqueous-phase reforming of methanol over Pt/V2O3-V8C7 based on strong-weak metal support interactions","authors":"Yuhao Yang ,&nbsp;Jie Ran ,&nbsp;Teng Wang ,&nbsp;Yongning Ma ,&nbsp;Junli Zhu ,&nbsp;Xiaolong Li ,&nbsp;Zhuoya Zhao","doi":"10.1016/j.jcat.2025.116397","DOIUrl":"10.1016/j.jcat.2025.116397","url":null,"abstract":"<div><div>Aqueous phase reforming of methanol (APRM) is an effective method for the storage and transportation of hydrogen (H₂). However, this approach faces challenges due to the limited activity and stability of metal-supported catalysts. In this study, Pt/V₂O₃-V₈C₇ metal-supported catalysts were prepared for APRM and the H₂ production of Pt/V₂O₃-V₈C₇ at 200 °C was 96.52 mmol·g⁻¹·h⁻¹, which is 1.83 times and 1.71 times higher than the H₂ production performance of Pt/V₂O₃ and Pt/V₈C₇, respectively. Moreover, the catalyst demonstrated remarkable stability after 10 in situ cycling tests. Structural characterization revealed that there is a strong metal-support interaction (SMSI) between Pt and V₈C₇, and a weak metal-support interaction (WMSI) between Pt and V₂O₃, which inhibits the sintering of Pt on the metal-supported catalyst. Furthermore, a straightforward experimental method has been developed that enables accurate inference of the catalytic reaction mechanism in APRM without the need for in situ material characterization. The reaction mechanism indicates that the Pt-V₈C₇ interface serves as the active site for the methanol decomposition step, while the surface of V₂O₃ acts as the active site for the water–gas shift reaction step. This strategy of strong–weak MSI offers a novel approach to enhancing both the stability and H₂ production performance in APRM.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"452 ","pages":"Article 116397"},"PeriodicalIF":6.5,"publicationDate":"2025-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144905974","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Carbazolyl-based metal organic framework for photocatalytic antibiotic degradation and H2O2 green generation assisted by silver nanoparticles","authors":"Shan Ding ,&nbsp;Yu-Ting Hui ,&nbsp;Qingfeng Wei ,&nbsp;Guang-Sheng Yang ,&nbsp;Zhe Tang ,&nbsp;Shi-Qi Wang ,&nbsp;Xinning Zhang ,&nbsp;Yi-Jia Wang ,&nbsp;Chunjie Jiang","doi":"10.1016/j.jcat.2025.116401","DOIUrl":"10.1016/j.jcat.2025.116401","url":null,"abstract":"<div><div>Tetracycline, a widely used antibiotic that persists in the environment, is a significant pollutant, making its efficient degradation crucial for ecosystem and human health. Meanwhile, green production of hydrogen peroxide, an important chemical raw material and green oxidant, is significant in various fields. In this study, a novel visible-light-responsive photocatalyst, the ACM-X series material, was successfully synthesized through post-synthetic modification of Cz-MOF-2, with the deposition of Ag nanoparticles on the surface significantly enhancing the photocatalytic performance, enabling efficient degradation of tetracycline (TC) and high-yield production of hydrogen peroxide (H₂O₂) under simulated solar light irradiation. The Ag surface plasmon resonance (SPR) effect played a crucial role in improving charge separation efficiency, as confirmed by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and electrochemical measurements. The ACM-1 catalyst demonstrated exceptional photocatalytic activity, achieving over 95 % TC degradation within 60 min and a H₂O₂ production rate of 50 μmol/h. The free radical scavenging experiments and electron paramagnetic resonance (EPR) technique confirmed that reactive oxygen species (ROS), including superoxide anion radicals (·O₂⁻), hydroxyl radicals (·OH) and singlet oxygen (¹O₂), were identified as key intermediates in the photocatalytic process. Density functional theory (DFT) calculations revealed that Ag modification reduced the band gap of Cz-MOF-2, enhancing light absorption and promoting electron transfer. The 2e⁻ oxygen reduction reaction (ORR) for H₂O₂ production was found to be spontaneous, with Ag acting as an electron and proton transfer mediator. Additionally, the degradation pathway of tetracycline (TC) was elucidated by using a mass spectrometer. The ACM − 1 catalyst exhibited excellent stability and reusability during multiple cycles of use, highlighting its potential in environmental remediation and sustainable chemical synthesis. This work provides a promising strategy for the design of advanced photocatalysts for solar energy conversion and pollutant degradation.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116401"},"PeriodicalIF":6.5,"publicationDate":"2025-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144906336","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}