Journal of Catalysis最新文献_第4页

Unveiling high-performance single-atom alloy catalysts for alkane dehydrogenation through DFT and machine learning synergy 通过DFT和机器学习协同作用揭示烷烃脱氢的高性能单原子合金催化剂

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-05-12 DOI: 10.1016/j.jcat.2025.116213

Haisong Feng , Zhen Ge , Yuan Deng , Pengxin Pu , Shiquan Zhao , Xin Song , Hao Yuan , Yaze Wu , Jing Yang , Yubing Si , Antonio Politano , Xin Zhang , Yong-Wei Zhang

{"title":"Unveiling high-performance single-atom alloy catalysts for alkane dehydrogenation through DFT and machine learning synergy","authors":"Haisong Feng , Zhen Ge , Yuan Deng , Pengxin Pu , Shiquan Zhao , Xin Song , Hao Yuan , Yaze Wu , Jing Yang , Yubing Si , Antonio Politano , Xin Zhang , Yong-Wei Zhang","doi":"10.1016/j.jcat.2025.116213","DOIUrl":"10.1016/j.jcat.2025.116213","url":null,"abstract":"<div><div>The recent surge in shale gas production has renewed interest in efficient alkane dehydrogenation for the synthesis of fuels and high-value chemicals. However, developing cost-effective catalysts that exhibit high catalytic activity while minimizing over-dehydrogenation and carbon deposition remains a significant challenge. Here, we integrate density functional theory (DFT) calculations with machine learning (ML) to design single-atom alloy (SAA) catalysts for efficient alkane dehydrogenation. Using DFT, we calculate 92 C<img>H bond disassociation energy barriers to construct a dataset, which is used to train eight ML algorithms with 12 features. The top-performing Bagging Regression (BAR) model is then employed to predict C<img>H bond activation energy barriers on the surfaces of 53 SAA candidates, enabling rapid screening of methane dehydrogenation activity. Among these, the Ru<sub>1</sub>Cu SAA catalyst exhibits outstanding activity, outperforming pure Pt. Detailed DFT calculations confirm that Ru<sub>1</sub>Cu(111) not only exhibits superior performance in methane dehydrogenation, but also exceptional activity in the dehydrogenation of propane, ethane, and isobutane. Moreover, microkinetic simulations further confirm the high selectivity of the Ru<sub>1</sub>Cu(111) surface toward propylene during propane dehydrogenation. Feature engineering analyses reveal the critical roles of dehydrogenation steps and the surface energy of the single-atom metal in influencing C<img>H bond activation. These findings underscore the effectiveness of the DFT–ML framework for catalyst discovery and highlight Ru<sub>1</sub>Cu SAA as a highly active, selective, and stable catalyst with strong resistance to over-dehydrogenation and carbon deposition, making it a highly promising candidate for alkane dehydrogenation.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116213"},"PeriodicalIF":6.5,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940552","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}

引用次数: 0

Elucidating the role of solvent in C=C bond hydrogenation of maleic acid at metal-solvent interface by AIMD and DFT simulations 用AIMD和DFT模拟阐明了溶剂在金属-溶剂界面马来酸C=C键加氢中的作用

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-05-12 DOI: 10.1016/j.jcat.2025.116212

Aashi D. Parekh , Pallavi Dandekar , Uzma Anjum, Shelaka Gupta

{"title":"Elucidating the role of solvent in C=C bond hydrogenation of maleic acid at metal-solvent interface by AIMD and DFT simulations","authors":"Aashi D. Parekh , Pallavi Dandekar , Uzma Anjum, Shelaka Gupta","doi":"10.1016/j.jcat.2025.116212","DOIUrl":"10.1016/j.jcat.2025.116212","url":null,"abstract":"<div><div><em>Ab-initio</em> Molecular Dynamics (AIMD) and Density Functional Theory (DFT) simulations were used to understand the solvent effects in C=C bond hydrogenation using maleic acid (MAc) to succinic acid (SAc) as a model reaction on Pd (111) surface. In the presence of explicit water molecules, MAc was observed to dissociate to maleate ion (MA). The presence of hydrogen bonding network in water and charge redistribution from the Pd surface to the water molecules stabilized the reactants and intermediates and resulted in low free energy barriers (31.7 and 44.9 kJ/mol) for the first and second step of C=C bond hydrogenation. Interestingly, the C=C bond of MA in presence of water was reduced by the surface H atom rather than the solution-mediated pathway. The surface H atom, however, could be either obtained by direct H<sub>2</sub> dissociation or via H exchange between adsorbed H and nearby water molecules. The free energy barrier for the H exchange between nearby water molecules and surface adsorbed H atom was calculated to be 43.1 kJ/mol. In the absence of hydrogen bonding network in polar aprotic solvent like 1,4-dioxane and vacuum phase, the activation barriers were estimated to be relatively high. In general, the electronic effect of the solvents followed a linear trend, where FMO gap serves as a good descriptor of the reactivity.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116212"},"PeriodicalIF":6.5,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940618","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}

引用次数: 0

Highly dispersed Cu supported on urchin-like TiO2 for efficient hydrodeoxygenation of lignin derivatives 高分散Cu负载在海胆状TiO2上用于木质素衍生物的高效氢脱氧

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-05-12 DOI: 10.1016/j.jcat.2025.116216

Lei Chen , Chenhuan Wang , Ningzhao Shang , Shutao Gao , Chun Wang

引用次数: 0

Ruthenium/N–Heterocyclic carbene-decorated covalent organic framework for N–H insertion cascade nucleophilic cyclization 钌/ n -杂环碳修饰共价有机框架的N-H插入级联亲核环化

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-05-12 DOI: 10.1016/j.jcat.2025.116211

Xiaogang Wang , Fangfang Fan , Mengmeng Hu , Chengfang Qiao , Baoyue Cao , Xue Gong , Michal Szostak

引用次数: 0

Modest modulation on the spin states of Co3O4 nanoframe through vanadium doping for solid-state rechargeable Zn-air/iodide hybrid batteries 钒掺杂对固态可充电锌-空气/碘化物混合电池Co3O4纳米骨架自旋态的适度调制

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-05-12 DOI: 10.1016/j.jcat.2025.116210

Yanli Niu, Wenze Zhang, Mingyang Xu, Xiaozhen Li, Linpo Li

{"title":"Modest modulation on the spin states of Co3O4 nanoframe through vanadium doping for solid-state rechargeable Zn-air/iodide hybrid batteries","authors":"Yanli Niu, Wenze Zhang, Mingyang Xu, Xiaozhen Li, Linpo Li","doi":"10.1016/j.jcat.2025.116210","DOIUrl":"10.1016/j.jcat.2025.116210","url":null,"abstract":"<div><div>The rational construction of bifunctional air cathode electrocatalysts with high intrinsic reversibility and durability is critical for practical applications of rechargeable solid Zn-air batteries (ZABs). Unlike traditional nanomorphology construction methods, this work focus on the enhancement of intrinsic catalytic properties by heteroatom vanadium doping strategy to modulate the spin state of Co<sup>3+</sup> ions active sites at the octahedral sites of spinel Co<sub>3</sub>O<sub>4</sub>. The magnetic measurements and the theoretical calculation consistently reveal that V atom incorporation induce the spin state transition of Co<sup>3+</sup> from low spin state (LS, <span><math><mrow><msubsup><mi>t</mi><mrow><mn>2</mn><mi>g</mi></mrow><mn>6</mn></msubsup><msubsup><mi>e</mi><mrow><mi>g</mi></mrow><mn>0</mn></msubsup></mrow></math></span>) to intermediate spin state (IS, <span><math><mrow><msubsup><mi>t</mi><mrow><mn>2</mn><mi>g</mi></mrow><mn>5</mn></msubsup><msubsup><mi>e</mi><mrow><mi>g</mi></mrow><mn>1</mn></msubsup></mrow></math></span>), and reduces the energy gap between the Co 3d and O 2p band centers, which balance the adsorption/desorption of oxygen intermediates and further enhance the oxygen reaction kinetics. Consequently, the optimized V-Co<sub>3</sub>O<sub>4</sub> demonstrated a small potential gap value of 0.74 V between the ORR half-wave potential and the OER potential at 10 mA m<sup>−2</sup>. More importantly, the introduction of KI in solid-state electrolyte provides a more thermodynamically favorable pathway. Thereby, the assembled ZAB displays excellent long-term durability (180 h), offering a promising power source for the next-generation electronics. This work advances a feasible design concept to tune catalytic activity for ZABs by optimizing the spin states and developing novel solid-state electrolytes.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116210"},"PeriodicalIF":6.5,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940615","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}

引用次数: 0

Constructing well-distributed cerium oxide nanoparticles on alumina-carbon nanosheet for boosting the synthesis of imine from benzyl alcohol and aniline 在氧化铝-碳纳米片上构建分布均匀的氧化铈纳米颗粒，促进苯甲醇和苯胺合成亚胺

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-05-12 DOI: 10.1016/j.jcat.2025.116208

Yan Hao , Zheng Gao , Linlin Du , Yifan Wang , Moxin Miao , Yang Zhang , Qiang Sun , Qinghu Tang

{"title":"Constructing well-distributed cerium oxide nanoparticles on alumina-carbon nanosheet for boosting the synthesis of imine from benzyl alcohol and aniline","authors":"Yan Hao , Zheng Gao , Linlin Du , Yifan Wang , Moxin Miao , Yang Zhang , Qiang Sun , Qinghu Tang","doi":"10.1016/j.jcat.2025.116208","DOIUrl":"10.1016/j.jcat.2025.116208","url":null,"abstract":"<div><div>Considering the unique redox property and the excellent oxygen storage-diffusion ability of CeO<sub>2</sub> nanoparticles as well as the advantages of large external surface area and accelerated mass transfer due to the open structure of two-dimensional nanosheets, well-distributed CeO<sub>2</sub> nanoparticles supported on alumina-carbon nanosheet catalysts, which were prepared by a facile impregnation and subsequent pyrolysis procedure, were investigated for the synthesis of imine from benzyl alcohol and aniline by using air as the sole oxidant. The physical and chemical properties of the synthesized Ce/ALC catalysts were characterized by various techniques. It was found that an Al–Ce–O solid solution could be formed between supported Ce and Al within ALC during the pyrolysis procedure. The formation of Al–Ce–O solid solution is beneficial for generating more defective sites, promoting to adsorb and activate oxygen. Therefore, the activity of Ce/ALC catalyst for oxidative coupling of benzyl alcohol and aniline was enhanced with the addition of alumina. An appropriate Al/Ce ratio could obtain a large amount of surface Ce<sup>3+</sup> ions, more readily available oxygen species and balanced acid-base sites, which were very crucial for achieving a high imine yield. The Ce/ALC-2 catalyst with Al/Ce ratio of ∼7 exhibited the highest catalytic activity. After 8 h of reaction at 80 °C, the benzyl alcohol conversion reached 99 % with an imine yield of 99 %, and the productivity of imine was 2.48 mmol g<sub>cat.</sub> <sup>−1</sup>h<sup>−1</sup>. The coordinatively unsaturated Ce<sup>3+</sup>–V<sub>ö</sub> defects were suggested as the active sites for the oxidative coupling of benzyl alcohol and aniline. In addition, this catalyst also exhibited good stability and recyclability, which might provide an alternative strategy for the oxidative coupling reaction.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116208"},"PeriodicalIF":6.5,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940616","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}

引用次数: 0

Large-scale, continuous preparation of MnO2 for highly efficient oxidative coupling of amines to imines under mild conditions 在温和条件下，大规模连续制备MnO2以实现胺与亚胺的高效氧化偶联

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-05-10 DOI: 10.1016/j.jcat.2025.116209

Jia-qi Bai , Huangfei Liu , Mei Ma, Zhangkai Qian, Durui Liu, Mengdie Cai, Jingshuai Chen, Lisheng Guo, Yuxue Wei, Fang Chen, Song Sun

{"title":"Large-scale, continuous preparation of MnO2 for highly efficient oxidative coupling of amines to imines under mild conditions","authors":"Jia-qi Bai , Huangfei Liu , Mei Ma, Zhangkai Qian, Durui Liu, Mengdie Cai, Jingshuai Chen, Lisheng Guo, Yuxue Wei, Fang Chen, Song Sun","doi":"10.1016/j.jcat.2025.116209","DOIUrl":"10.1016/j.jcat.2025.116209","url":null,"abstract":"<div><div>Aerobic oxidation self-coupling of amines is an important method to prepare imines, however, the reported catalyst suffered from expensive price, complex preparation method and harsh reaction condition. Herein, large-scale, continuous preparation of MnO<sub>2</sub> was achieved by cheap microfluidic method and applied in the oxidative coupling of amines to imines. The δ-MnO<sub>2</sub> showed 98.0 % yield with initial TOF of 4.17 h<sup>−1</sup> under 343 K and 0.1 MPa O<sub>2</sub>, which was the maximum among the reported non-noble metallic based catalysts under mild reaction conditions. Moreover, the δ-MnO<sub>2</sub> can be reused at least 7 times and exhibited wide substrate applicability. Furthermore, the various characterizations showed that the superior catalytic performance can be ascribed to the high concentration of surface Mn<sup>3+</sup>, rich oxygen vacancies and more acidic and basic sites. Additionally, the reaction path and mechanism were proposed based on the kinetics and <em>in-situ</em> DRIFTS. This work provided a feasible approach to prepare large-scale MnO<sub>2</sub> for highly efficient oxidative coupling of amines to imines under mild conditions with low cost.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116209"},"PeriodicalIF":6.5,"publicationDate":"2025-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143932584","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}

引用次数: 0

HOF-to-MOF transformation strategy for Porphyrin-based MOF photocatalysts 卟啉基MOF光催化剂的HOF-to-MOF转化策略

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-05-09 DOI: 10.1016/j.jcat.2025.116207

Mengting Wu , Zhipeng Xie , Jiaxu Qi , Jie Hu , Lele Wang , Weikang Wang , Qinqin Liu , Yazhou Zhou , Jimmy C. Yu

{"title":"HOF-to-MOF transformation strategy for Porphyrin-based MOF photocatalysts","authors":"Mengting Wu , Zhipeng Xie , Jiaxu Qi , Jie Hu , Lele Wang , Weikang Wang , Qinqin Liu , Yazhou Zhou , Jimmy C. Yu","doi":"10.1016/j.jcat.2025.116207","DOIUrl":"10.1016/j.jcat.2025.116207","url":null,"abstract":"<div><div>Photocatalysis is a sustainable and eco-friendly technology for solar energy conversion. However, the development of advanced photocatalysts remains challenging due to slow exciton dynamics and limited active site accessibility. Herein, we present a novel transformation strategy for synthesizing metal–organic frameworks (MOFs) from hydrogen-bonded organic frameworks (HOFs). This transformation is driven by the in-situ conversion of hydrogen bonds to coordination bonds. A series of 4,4′,4″,4‴-(porphyrin-5,10,15,20-tetrayl) tetra benzoic acid (TCPP)-based MOFs, denoted as H<sub>III</sub>-MT (M = Cu, Zn, Fe, Ce, and Mg), were successfully synthesized from TCPP HOF (H<sub>III</sub>). The HOF offers a flexible framework that guides the precise assembly of porphyrin ligands and metal centers, making it possible to develop a highly ordered molecular arrangement with abundant metal active sites. The resulting H<sub>III</sub>-CuT exhibits remarkable photocatalytic performance and achieves 88 % carbamazepine degradation under solar light. This efficiency surpasses template-free CuT, H<sub>III</sub>, and aggregated TCPP by 2.4, 3.6, and 8 times, respectively. The enhanced performance is due to prolonged electron lifetimes and improved substrate adsorption. This work provides a new pathway for designing high-performance MOF photocatalysts with controlled orientation and tailored structure, opening great opportunities environmental remediation and sustainable energy applications.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116207"},"PeriodicalIF":6.5,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143931117","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}

引用次数: 0

Promoting activation of N2 and H2O via dual active sites synergistically for efficient photocatalytic ammonia synthesis 通过双活性位点协同促进N2和H2O的活化，实现高效光催化合成氨

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-05-09 DOI: 10.1016/j.jcat.2025.116197

Hao Du , Huimin Li , Zufan Yang , Shengjie Xia , Jing Chen , Yue Meng , Litong Bian , Geng Yang , Guanhua Zhang

{"title":"Promoting activation of N2 and H2O via dual active sites synergistically for efficient photocatalytic ammonia synthesis","authors":"Hao Du , Huimin Li , Zufan Yang , Shengjie Xia , Jing Chen , Yue Meng , Litong Bian , Geng Yang , Guanhua Zhang","doi":"10.1016/j.jcat.2025.116197","DOIUrl":"10.1016/j.jcat.2025.116197","url":null,"abstract":"<div><div>Photocatalytic nitrogen fixation is a green synthetic process for the direct conversion of N<sub>2</sub> and H<sub>2</sub>O to ammonia using solar energy. However, the scarcity of N<sub>2</sub> and H<sub>2</sub>O active sites is a limiting factor in the kinetics of nitrogen fixation reactions. The construction of spatially synergistic dual active sites is a feasible strategy to overcome this challenge. Herein, Fe-doped CdS (FCS) photocatalysts containing S vacancy have been prepared by a simple one-step solvothermal method. The results show that S vacancy in FCS preferentially adsorb H<sub>2</sub>O molecules and activate them to active hydrogen (H*) for nitrogen reduction. Fe sites tend to adsorb N<sub>2</sub> molecules and promote the d− band center of CdS to move to Fermi level (E<sub>f</sub>), which significantly improves the activation ability of N<sub>2</sub> molecules. The unique dual active sites greatly reduce Gibbs free energy of N<sub>2</sub> and H<sub>2</sub>O activation and improve surface reaction kinetics of nitrogen reduction reaction. NH<sub>4</sub><sup>+</sup> production rate of FCS reached 13.39 μmol · h<sup>−1</sup> without sacrificial reagent, which was 13.2 times higher than that of CdS. This study proves the significance of synergy between active sites for improving reaction efficiency and provides inspiration for the construction of dual active systems in photocatalytic nitrogen reduction.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116197"},"PeriodicalIF":6.5,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143931116","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}

引用次数: 0

Radical-mediated Cα-Cβ cleavage by ZnIn2S4-based heterojunction materials in photo-electro-catalysis znin2s4基异质结材料在光电催化中自由基介导的Cα-Cβ裂解

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-05-08 DOI: 10.1016/j.jcat.2025.116189

Jifang Zhang , Chengcheng Suo, Xinchi Hao, Xingyu Zhu, Yiheng Zhuang, Cunyuan Hu, Wei Li, Sha Luo, Bing Tian, Chunhui Ma, Shouxin Liu

{"title":"Radical-mediated Cα-Cβ cleavage by ZnIn2S4-based heterojunction materials in photo-electro-catalysis","authors":"Jifang Zhang , Chengcheng Suo, Xinchi Hao, Xingyu Zhu, Yiheng Zhuang, Cunyuan Hu, Wei Li, Sha Luo, Bing Tian, Chunhui Ma, Shouxin Liu","doi":"10.1016/j.jcat.2025.116189","DOIUrl":"10.1016/j.jcat.2025.116189","url":null,"abstract":"<div><div>The selective cleavage of lignin specific linkages for production of high-value chemicals remains a significant challenge due to inherent inertness and complex structure. In this study, we developed a Photo-Electro-Catalysis (PEC) strategy utilizing radicals, which achieved high catalytic efficiency for lignin depolymerization at room temperature (from 10 °C to 35 °C). A heterojunction material composed of 2D ZnIn<sub>2</sub>S<sub>4</sub> nanosheets and carbon nanoparticles was synthesized to facilitate efficient electron transfer and radical generation. The quantum yield (2.1858) exceeding 1 suggested a radical chain mechanism in the PEC process. Mechanistic studies revealed that oxygen radical combine with C-centered radicals to form a C<sub>β</sub>-OOH peroxide intermediate, leading to C<img>C bond cleavage. Notably, chlorine radicals (•Cl) were introduced for the first time in lignin PEC depolymerization, initiating C<sub>β</sub>-H functionalization, cyclization and ring-opening reactions. This approach achieved 100 % C<sub>α</sub>-C<sub>β</sub> cleavage and over 90 % mass conversion of native G-units lignin. The highest product yields were 233.34 mg g<sup>−1</sup> (benzaldehyde), 66.03 mg g<sup>−1</sup> (acetophenone), and 54.98 mg g<sup>−1</sup> (phenol) from the β-O-4 dimer. This study provides novel insights into radical mechanisms and catalytic strategies for lignin depolymerization into high-value chemicals.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116189"},"PeriodicalIF":6.5,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143927183","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}

引用次数: 0