Journal of Catalysis最新文献

{"title":"Ni-catalyzed ring-opening hydrocyanation of methylenecyclopropanes toward cyano-substituted quaternary carbon centers","authors":"Jianxi Chen,&nbsp;Zhaohang Jiang,&nbsp;Ting Wang,&nbsp;Mingdong Jiao,&nbsp;Xianjie Fang","doi":"10.1016/j.jcat.2025.116361","DOIUrl":"10.1016/j.jcat.2025.116361","url":null,"abstract":"<div><div>Transition-metal-catalyzed hydrofunctionalization of methylenecyclopropanes represents a useful transformation, typically yielding 1,2-hydrofunctionalization products as the major outcome. In this work, we report an unprecedented, highly selective nickel-catalyzed hydrocyanation of methylenecyclopropanes that affords 1,4-hydrofunctionalization products, forming acyclic cyano-substituted quaternary carbon centers. Mechanistic studies suggest that this reaction proceeds via a <em>β</em>-carbon elimination process involving a diene intermediate. DFT calculations further revealed that the regioselectivity for quaternary carbon center formation was controlled by a delicate interplay of steric and noncovalent interactions during the C–CN reductive elimination step.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116361"},"PeriodicalIF":6.5,"publicationDate":"2025-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144802937","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":"Structure-oriented optimization of hierarchical porous conjugated polymers for enhanced PET-RAFT polymerization","authors":"Qing Jiang, Yunye Huang, Zhen Lu, Yuanhao Lin, Xiafeng Liao, Danni Tang, Linxi Hou, Longqiang Xiao","doi":"10.1016/j.jcat.2025.116366","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116366","url":null,"abstract":"Hierarchically porous materials are highly valued for their large surface areas and tunable pore architectures, making them promising heterogeneous catalysts for photoinduced electron transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization. However, the specific influence of pore structure on catalytic performance remains poorly understood. In this study, hierarchically porous conjugated organic polymers (COPs) were synthesized using a silica hard-template method and employed as photocatalysts for PET-RAFT polymerization. Under white LED light irradiation, the effects of template size and concentration on pore structure and photocatalytic performance were systematically investigated. Notably, a silica template with a concentration of 60 mg/mL and a particle size of 300 nm produced a COP with an average pore size of 6.91 nm, which exhibited the best photocatalytic performance. The polymerization rate under these conditions was 2.5 times higher than that of the control. The synergy among micropores, mesopores, and macropores enhanced photocatalytic efficiency by increasing surface area, promoting mass transfer, and improving charge carrier mobility. Spectroscopic and electrochemical analyses further revealed that the optimized pore structure significantly enhances charge carrier dynamics by facilitating charge separation and migration. This structural modulation effectively reduces charge recombination, thereby improving the photocatalytic efficiency in PET-RAFT polymerization. These findings provide valuable insights into the rational design of porous photocatalysts for advanced PET-RAFT systems.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"70 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144797550","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":"Quasi-homogeneous catalytic platform of efficient enantioselective dual photocatalysis: Brush-supported Ir complexes/chiral phosphoric acids for the economic synthesis of optically active molecules","authors":"Yongyue Luo,&nbsp;Wenyan Tian,&nbsp;Yang Zhou,&nbsp;Xuebing Ma","doi":"10.1016/j.jcat.2025.116373","DOIUrl":"10.1016/j.jcat.2025.116373","url":null,"abstract":"<div><div>Current heterogeneous enantioselective photocatalysis of dual catalysts faces the key limiting factors including multi-step immobilization of catalysts, insufficient electron/energy transfer and limited mass transfer of reactants. In this paper, the direct immobilization of dual catalysts without molecular modification, including three catalyst combinations of Ir complexes and chiral phosphoric acids (CPAs), into SiO₂-grafted linear poly(4-vinylbenzyl chloride) (PVBC) brushes is developed via one-pot Friedel-Crafts alkylation. The PVBC brushes-supported dual catalysts possess improved optical properties including light-harvesting, optical bandgap energy, emission lifetime, and quantum yield in comparison to pore-anchored dual catalysts. Meanwhile, owing to the open-ended structure and good dispersibility of PVBC brushes in organic solvents, the energy/electron transfer and mass transfer of reactants to catalytic sites are improved due to quasi-homogeneous catalysis, which enables the anchored dual catalysts to achieve comparable catalytic performances to homogeneous counterparts in enantioselective photocatalysis. Overall, the quasi-homogeneous enantioselective photocatalysis of dual catalysts provides an effective platform for the low-cost synthesis of chiral molecules in green manner.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116373"},"PeriodicalIF":6.5,"publicationDate":"2025-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144802934","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":"Organocatalytic hydroboration of imines, nitriles, and amides using choline-based ionic liquids","authors":"Barbara Krupa ,&nbsp;Mateusz Nowicki ,&nbsp;Jakub Szyling ,&nbsp;Jędrzej Walkowiak","doi":"10.1016/j.jcat.2025.116362","DOIUrl":"10.1016/j.jcat.2025.116362","url":null,"abstract":"<div><div>This study reports the application of choline-based ionic liquids as organocatalysts in the hydroboration of imines, nitriles, and amides. The best results characterized by mild reaction conditions and low catalyst loading, were obtained for choline acetate, which showed high functional groups tolerance. Moreover, the one-pot hydroboration sequence and coupling reactions enabled the synthesis of amides, imines, and primary, secondary, and tertiary amines from nitriles with high yields. In these studies, the recyclability of the catalyst was proved by carrying out repetitive batch experiments. The NMR studies and DFT calculations revealed that the choline and acetate borohydrides are catalytically active species in this process.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116362"},"PeriodicalIF":6.5,"publicationDate":"2025-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144797551","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":"cis-Diphosphine ethene ligand-Ni complexes catalyzed cyanation of aryl and heteroaryl chlorides","authors":"Zhenqiang Ma ,&nbsp;Yalong Li ,&nbsp;Xulu Lv ,&nbsp;Zhibin Li ,&nbsp;Xixi Song ,&nbsp;Fengqian Zhao ,&nbsp;Junliang Wu","doi":"10.1016/j.jcat.2025.116360","DOIUrl":"10.1016/j.jcat.2025.116360","url":null,"abstract":"<div><div>The development of ligands is an important driver for transition metal-catalyzed coupling reactions, which can activate more inert bonds or achieve milder conditions. Here, a novel <em>cis</em>-diphosphine ethene ligand-Ni complex was employed for the cyanation of aryl chlorides as well as heteroaryl chlorides. Various functional groups and heterocyclic skeletons were compatible in the catalytic system, and near-equivalent yields were obtained in several examples. In addition, three pharmaceutical molecules were synthesized to demonstrate the potential application of this catalytic system.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116360"},"PeriodicalIF":6.5,"publicationDate":"2025-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144792671","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":"Unveiling the influence of electrolyte pH on the structural evolution of cobalt oxide pre-catalyst in oxygen evolution reaction","authors":"Xuyao Duo ,&nbsp;Zhonghui Hu ,&nbsp;Hengkang Pan ,&nbsp;Bingxu Chen ,&nbsp;Fengchen Zhou ,&nbsp;Panpan Liu ,&nbsp;Yifan Zhang ,&nbsp;Wen Luo ,&nbsp;Zailai Xie ,&nbsp;Runhai Ouyang ,&nbsp;Xing Huang ,&nbsp;Jia Yu ,&nbsp;Yuanqing Wang","doi":"10.1016/j.jcat.2025.116355","DOIUrl":"10.1016/j.jcat.2025.116355","url":null,"abstract":"<div><div>The pH effects play a critical role in electro-catalysis, yet their influence on the structural evolution of electrocatalysts during the oxygen evolution reaction (OER) remains underexplored. In this study, we combined in-situ Raman and UV–Vis spectroscopy with density functional theory (DFT) calculations to track the structural evolution of electrodeposited amorphous cobalt (oxy)hydroxide under different pH conditions. Our findings reveal distinct responses of the synthesized catalyst to varying electrolyte pH levels. The formation of relatively ordered β-CoOOH structure from amorphous cobalt (oxy)hydroxide under alkaline conditions may serve as the active phase, while the less active amorphous cobalt (oxy)hydroxide remained stable under neutral conditions. This study emphasizes the pivotal role of electrolyte pH in driving surface reconstruction of metal oxides, even in the absence of applied electrode potential.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116355"},"PeriodicalIF":6.5,"publicationDate":"2025-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144792857","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":"Ligand-regulated Schiff base complexes for efficient electrocatalytic carbon dioxide reduction","authors":"Siying Wang ,&nbsp;Shuaiqi Wang ,&nbsp;Qiangwei Li ,&nbsp;Leqing Deng ,&nbsp;Lidong Wang","doi":"10.1016/j.jcat.2025.116356","DOIUrl":"10.1016/j.jcat.2025.116356","url":null,"abstract":"<div><div>The electrocatalytic CO₂ reduction (ECR) driven by renewable energy to value-added chemicals represents a promising route for realizing carbon neutrality. Coordination-isolated metal complex-based molecular catalysts are booming in the field of ECR because of their impressive catalytic activity. However, it is extremely challenging to precisely modify the ECR performance of complex-based molecular catalysts. Given the adjustable organic ligand structures, herein, we investigate the ECR performance of cobalt-based molecular catalysts by regulating their ligand structures. It is found that the introduction of conjugated phenyl and electron-donating methyl groups in the Schiff base ligand endows the CoSOP3C complex catalyst with a significantly promoted electroreduction performances of CO₂ to CO and a remarkably suppressed water decomposition activity. As a result, CoSOP3C presents an impressively high Faradaic efficiency (FE) of 91.2 % for CO at −0.66 V versus reversible hydrogen electrode (<em>vs.</em> RHE) and current of 22.1 ± 2 mA/cm². Mechanistic studies reveal that Co (I) intermediate in the Co-based molecular catalysts is the active center for CO₂ electroreduction and the reduced CoSOP3C possesses the most stable Co (I) intermediate. The possible catalytic mechanism of Co-Schiff complex for electrochemical CO₂ reduction is also proposed. The present study may shed some light on further exploration of high-performance metal complex-based molecular electrocatalysts for the emerging ECR.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116356"},"PeriodicalIF":6.5,"publicationDate":"2025-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144792672","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":"Oxygen vacancy enhanced WO3-photocatalyzed aerobic dehydrogenation of C1 and C2 alcohols to construct N-heterocycles","authors":"Kai Xu ,&nbsp;Xueping Zhang ,&nbsp;Mei Hong ,&nbsp;Ai Chang ,&nbsp;Yamei Lin ,&nbsp;Guo-Ping Lu","doi":"10.1016/j.jcat.2025.116364","DOIUrl":"10.1016/j.jcat.2025.116364","url":null,"abstract":"<div><div>The green synthesis of <em>N</em>-heterocycles from renewable methanol and ethanol is a significant research direction in the fields of pharmaceuticals, chemistry and material. Addressing issues such as low catalyst efficiency and reliance on additives in traditional methods, this study has designed an oxygen vacancy-regulated WO₃ photocatalyst for efficient aerobic dehydrogenation and cyclization of methanol and ethanol to construct <em>N</em>-heterocyclic frameworks such as quinazolines, quinazolinones, benzimidazoles, and pyridines. This approach has the following advantages: mild conditions (room temperature), the use of 1 atm O₂ as a green oxidant, free of additive and precious metal catalyst, broad substrate scope (75 examples), cheap and recyclable catalyst (9 runs, $0.18/g), thereby make it high potentials for application in drug synthesis. Mechanistic studies revealed that alcohol dehydrogenation is the rate-determining step, driven by the synergistic catalysis of photogenerated holes (h⁺) and singlet oxygen (¹O₂). Promotion mechanism of oxygen vacancies is also illustrated: (1) Enhancing alcohol adsorption; (2) improving light absorption to generate more h⁺ and ¹O₂. To the best of our knowledge, this represents the first example of oxygen vacancy-modulated semiconductor photocatalysis for <em>N</em>-heterocycle synthesis using methanol and ethanol as C1 and C2 sources.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116364"},"PeriodicalIF":6.5,"publicationDate":"2025-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144792684","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":"Facilitated charge transfer of Mo–S bridge in non-noble plasmonic Z-scheme heterojunction for bifunctional photocatalytic hydrogen evolution and antibacterial","authors":"Shuming Li, Yupeng Guo, Peng She, Heng Rao, Xuejing Li, Ping She, Jun-Sheng Qin","doi":"10.1016/j.jcat.2025.116365","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116365","url":null,"abstract":"The development of efficient materials for sustainable energy conversion and antibacterial has drawn increasing attention. Precious metal nanoparticles have aroused great interest in photocatalysis due to their local surface plasmon resonance (LSPR) effect, but the high cost limits their practical application. In this study, a non-noble plasmonic MoO_3−x was adopted to combine with ZnIn₂S₄ (ZIS) to construct M@ZIS Z-scheme heterojunction for bifunctional photocatalysis. The LSPR effect of MoO_3−x can broaden the light absorption range, while the introduction of Mo–S chemical bonds enhances the photogenerated charge separation of the heterojunction. The optimized M@ZIS achieved a photocatalytic hydrogen evolution (PHE) rate of 11.10 mmol g⁻¹ h⁻¹ and achieved 100 % photocatalytic sterilization efficiency for <em>Escherichia coli</em> within 30 min. This study provides a novel strategy for the design and development of efficient bifunctional photocatalysts for energy and environmental issues.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"32 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144792860","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":"Unveiling the role of Cu-amine complexes in optimizing interfacial charge transfer dynamics between MoO2/CdZnS photocatalyst and amine substrate","authors":"Shaohui Zhang, Yupei Zhu, Yibin Chen, Xiaoyi Hu, Deshun Wang, Xiong-Feng Ma, Lele Wang, Jing Li, Huaxiang Lin, Jinlin Long, Zhaohui Li, Rusheng Yuan","doi":"10.1016/j.jcat.2025.116347","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116347","url":null,"abstract":"Engineering interfacial charge transfer between the excited heterogeneous photocatalysts and molecular substrates is an essential step in photocatalytic transformation of solar energy to chemical bonds. However, lack of accessing channel that equates bond linkage in function (at the molecular level) to bridging rigid catalysts and soft molecules makes the charge transfer inefficient at the border crossing. Herein, by merging a solid catalyst (MoO₂/Cd_0.9Zn_0.1S)-initiated photocatalytic process and a metal-complex-mediated photoredox process, a programming charge transfer in tandem was reached with distinct kinetics, and thus propelled efficient generation of long-lived interfacial electrons in photoredox reactions. In principle, the introduced Cu²⁺ metal center as the medium enables the efficient bridging of the amine substrate and oxidation sites and reduction sites of MoO₂/Cd_0.9Zn_0.1S (MS) photocatalyst via in-situ coordination and weak interaction. Such formed Cu-amine complexes serve as an electron shuttle delivering the electron from amine to the valence band of Cd_0.9Zn_0.1S (CZS) via LMCT process, thus accelerating the oxidation of amine. Moreover, the Mo–S bond at the interface of the MS Schottky junction significantly enhances electron transfer from the conduction band of CZS to MoO₂, thereby boosting H₂ generation. As a result, the optimized photocatalyst afforded high H₂ and N-benzylideneaniline production in photocatalytic H₂ generation from amine and synchronously C–N coupling, which is significantly higher than CZS (78.6 and 18.0 times) and 5 % MS (17.2 and 2.3 times) respectively. The design of interfacial electron transfer mode will deepen our understanding of surface science and heterogeneous photocatalysis in solar-driven redox reactions.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"69 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144787196","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}