ACS Catalysis 最新文献_第4页

Rhodium-Catalyzed Atroposelective C–H Alkylation of 1-Aryl Isoquinoline Derivatives with Cyclopropanols 铑催化的 1-芳基异喹啉衍生物与环丙醇的无选择性 C-H 烷基化反应

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-02-20 DOI: 10.1021/acscatal.5c00111

Wen-Wen Zhang, Quannan Wang, Chao Zheng, Shu-Li You

引用次数: 0

Manganese-Catalyzed Electrochemical Oxidation of Tryptophan-Containing Peptides and Indole Derivatives by O2

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-02-20 DOI: 10.1021/acscatal.4c05576

Min Xu, Qiaomin He, Xiaojiang Li, Ying Huang, Yiyi Weng

{"title":"Manganese-Catalyzed Electrochemical Oxidation of Tryptophan-Containing Peptides and Indole Derivatives by O2","authors":"Min Xu, Qiaomin He, Xiaojiang Li, Ying Huang, Yiyi Weng","doi":"10.1021/acscatal.4c05576","DOIUrl":"https://doi.org/10.1021/acscatal.4c05576","url":null,"abstract":"Tryptophan oxidation products derived from the dioxygenation and monooxygenation of tryptophan derivatives exhibit a wide range of biological activities. Nature has evolved finely tuned biosynthetic pathways to oxidize tryptophan derivatives using molecular oxygen (O2) as a co-substrate via enzymatic epoxidation steps. Nevertheless, the strategies involving these metalloenzymes are constrained by substrate specificity and the structural complexity of the enzymes. Driven by the practical demands for chemical conversions, there exists a longstanding quest for bioinspired catalysts guided by biomimetic catalytic principles in chemical transformations. In this regard, we herein present a single-step manganese-catalyzed aerobic electrochemical oxygenation of tryptophan-containing peptides (including peptide drugs) guided by the biomimetic catalytic principles to access the 3-hydroxy-oxindole- or 3-hydroxy-tetrazolo[1,5-a]indole-containing peptides and derivatives with broad functional group tolerances and high site selectivity under buffer conditions. Mechanistic investigations support that Mn-peroxo species are involved in the oxidation and the electricity contributes to the electron-transfer steps in the catalytic loop.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"64 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451525","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

Structure Sensitivity of an Atomic Co-Promoted In2O3 Catalyst toward CO2 Hydrogenation to Methanol

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-02-20 DOI: 10.1021/acscatal.5c00504

Shanshan Dang, Xiaoya Ding, Jinying Li, Junchao Chang, Zhenzhou Zhang, Peng Gao, Weifeng Tu, Yifan Han

{"title":"Structure Sensitivity of an Atomic Co-Promoted In2O3 Catalyst toward CO2 Hydrogenation to Methanol","authors":"Shanshan Dang, Xiaoya Ding, Jinying Li, Junchao Chang, Zhenzhou Zhang, Peng Gao, Weifeng Tu, Yifan Han","doi":"10.1021/acscatal.5c00504","DOIUrl":"https://doi.org/10.1021/acscatal.5c00504","url":null,"abstract":"Deciphering the relationship between the active site structure and the CO2 hydrogenation to methanol mechanism over In2O3-supported high-dispersed metal catalysts faces great challenges. Herein, by using atomically dispersed Co@In2O3 with the main exposed facet as a model catalyst, Co@In2O3 (111) and Co@In2O3 (012) are prepared to investigate the structure sensitivity toward CO2 hydrogenation. Co@In2O3 (012) exhibits higher methanol selectivity (78.0%) with a prominent durability within a 100 h time-on-stream test at 280 °C and 9000 mL g–1 h–1, while Co@In2O3 (111) exhibits a mediocre selectivity of methanol (64.7%) but relatively higher CO2 conversion. Experiments and theoretical simulations substantiate that the hydrogenation of CO2 to methanol follows the formate pathway over both catalysts. The oxygen vacancy sites on the Co@In2O3 (012) surface can more effectively stabilize the intermediates of the CO2 hydrogenation reaction and exhibit a lower reaction energy barrier of the rate-determining step about the conversion of HCOO* to H2COO*, achieving a higher methanol selectivity. This study might be of great aid in providing comprehensive insight into the structure–activity relationship of Co@In2O3 catalysts and the design of robust catalysts for highly selective hydrogenation of CO2 to methanol.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"2 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462320","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

Unraveling the Common Nature of O and S Doping in Improving Electrochemical O2 Reduction Reaction Performance of FeN4C 揭示掺杂 O 和 S 在改善 FeN4C 电化学氧气还原反应性能中的共性

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-02-20 DOI: 10.1021/acscatal.4c06491

Yuan Yuan, Jiapeng Ma, Baotao Kang, Jin Yong Lee

{"title":"Unraveling the Common Nature of O and S Doping in Improving Electrochemical O2 Reduction Reaction Performance of FeN4C","authors":"Yuan Yuan, Jiapeng Ma, Baotao Kang, Jin Yong Lee","doi":"10.1021/acscatal.4c06491","DOIUrl":"https://doi.org/10.1021/acscatal.4c06491","url":null,"abstract":"Heteroatom-doped Fe-N-C catalysts have emerged as promising alternatives to noble metals for the oxygen reduction reaction (ORR) due to their lower cost. However, the underlying mechanisms responsible for their enhanced performance, particularly electrochemical stability, remain a subject of debate. This study leverages density functional theory calculations coupled with a constant potential and implicit solvent model to investigate the electrochemical stabilities and activities of pyridinic (PD-) and pyrrolic FeN4C (PL-FeN4C) catalysts. Our findings reveal that the hydrogenation susceptibility of coordinating nitrogen atoms is a critical determinant of electrochemical stability within FeN4C catalysts. Moreover, we demonstrate that oxygen and sulfur doping exerts similar effects on enhancing the overall ORR performance of PD-FeN4C catalysts: (1) by reducing the p-band center of the coordinating nitrogen, thereby improving their resistance to hydrogenation, and (2) by increasing the valence electrons of iron, leading to stronger adsorption of reaction intermediates and consequently enhanced ORR activity. Finally, our predictions suggest that O/S-doped PL-FeN4C catalysts could achieve significantly improved electrochemical stability and superior ORR performance in both acidic and alkaline environments. These insights contribute to a deeper understanding of microenvironment engineering in single-atom catalysts (SACs) and offer valuable guidelines for the development of unprecedented M-N-C catalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"20 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462158","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

Single Atom Embedding Enhanced Macroscopic Polarization in Carbon Nitride Nanosheets for pH-Universal Piezo-Photocatalytic Nitrate Reduction over a Wide Concentration Range

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-02-20 DOI: 10.1021/acscatal.4c06247

Jinzhou Liu, Lujie Jin, Zhongqin Dai, Yujin Ji, Jin Qian, Yan Lu, Jiong Wang, Bo Shen, Youyong Li, Rong Xu, Guanyu Liu, Jiwei Zhai

{"title":"Single Atom Embedding Enhanced Macroscopic Polarization in Carbon Nitride Nanosheets for pH-Universal Piezo-Photocatalytic Nitrate Reduction over a Wide Concentration Range","authors":"Jinzhou Liu, Lujie Jin, Zhongqin Dai, Yujin Ji, Jin Qian, Yan Lu, Jiong Wang, Bo Shen, Youyong Li, Rong Xu, Guanyu Liu, Jiwei Zhai","doi":"10.1021/acscatal.4c06247","DOIUrl":"https://doi.org/10.1021/acscatal.4c06247","url":null,"abstract":"Piezo-photocatalytic nitrate reduction reaction (NO3–RR) is an ammonia synthesis approach as a promising alternative to the conventional energy-intensive Haber–Bosch process. Herein, we designed carbon nitride nanosheet supported Cu single atom (C3N4/Cu) catalysts with tunable electronic structures via coordination environment engineering. The embedding of single atoms into carbon nitride leads to enhanced piezoelectricity, which originates from the induced non-centrosymmetric cavities in nanosheets. The resulting macroscopic polarization facilitates the transport of photogenerated charge carriers together with suppressed charge recombination endowed by rich nitrogen vacancies in C3N4/Cu. Furthermore, it favors the dissociation of water to provide sufficient active hydrogen for the hydrogenation of NO3– with reduced energy barriers during the NO3–RR. Consequently, C3N4/Cu attains an ammonia yield rate of up to 25.2 mg h–1 gcat–1 without a sacrificial reagent. Moreover impressively, it maintains yield rates above 5 mg h–1 gcat–1 at pH values of 1–14 and over a wide range of NO3– concentrations from 0.01 to 2 mol L–1, indicative of its catalytic versatility for actual wastewater treatment.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"2 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462304","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

Ruthenium-Catalyzed γ-Selective Intermolecular Amidation of Nonactivated Distal Methylene C–H Bonds of Terminal Alkenes via Olefin Chain-Walking Isomerization

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-02-20 DOI: 10.1021/acscatal.4c06639

Yiu-Wai Yeung, Sing-Fung Hung, Chi-Ming Au, Marco Chan, Chun-Ming Chan, Wing-Yiu Yu

{"title":"Ruthenium-Catalyzed γ-Selective Intermolecular Amidation of Nonactivated Distal Methylene C–H Bonds of Terminal Alkenes via Olefin Chain-Walking Isomerization","authors":"Yiu-Wai Yeung, Sing-Fung Hung, Chi-Ming Au, Marco Chan, Chun-Ming Chan, Wing-Yiu Yu","doi":"10.1021/acscatal.4c06639","DOIUrl":"https://doi.org/10.1021/acscatal.4c06639","url":null,"abstract":"Here we report the development of the [(p-cymene)Ru(II)]-catalyzed γ-selective intermolecular amidation of nonactivated distal methylene C–H bonds of terminal alkenes using sulfonyl azides and dioxazolones as the nitrogen sources. Initiated by the π-allyl Ru(II) complexes formation, the ruthenium complexes undergo spontaneous chain-walking isomerization via proton-assisted 1,3-allyl migration along the hydrocarbon chain. For alkenes containing a distal aryl substituent, the chain-walking isomerization afforded the aryl-conjugated alkenes as the most dominant isomerized products. With sulfonyl azides as the nitrogen source and the [(p-cymene)Ru] catalyst, the aryl-conjugated alkenes were further converted to the corresponding allyl tosylamides with >20:1 γ-selectivity. Unlike those cases with sulfonyl azide as the nitrene source, the analogous amidation with dioxazolones afforded the corresponding allylcarboximides in ca. 5:1 γ-selectivity. The nature of the chain-walking alkene isomerization and the origin of the γ-selectivity have been delineated.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"50 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462305","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

Dual Copper/Photoredox Catalysis for Radical-Mediated Arylation and Alkylation of Sulfenamides

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-02-20 DOI: 10.1021/acscatal.5c00082

Mingjun Zhang, Yuhao Tan, Hehe Yang, Xiaoyang Fu, Yuxiu Liu, Ziwen Wang, Qingmin Wang

引用次数: 0

Reversible Spillover Wakens Reactivity of Dormant Modular Hydrochlorination Catalysts

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-02-20 DOI: 10.1021/acscatal.4c06661

Xinping Duan, Yuxin Zhao, Hung-Lung Chou, Jiachang Zuo, Ruixin Wang, Weizhou Jiao, Huihuang Fang, Yanping Zheng, Haiqiang Lin, Linmin Ye, Youzhu Yuan

{"title":"Reversible Spillover Wakens Reactivity of Dormant Modular Hydrochlorination Catalysts","authors":"Xinping Duan, Yuxin Zhao, Hung-Lung Chou, Jiachang Zuo, Ruixin Wang, Weizhou Jiao, Huihuang Fang, Yanping Zheng, Haiqiang Lin, Linmin Ye, Youzhu Yuan","doi":"10.1021/acscatal.4c06661","DOIUrl":"https://doi.org/10.1021/acscatal.4c06661","url":null,"abstract":"Metals atomically anchored on oxides have actively realized ultimate atom efficiency. However, a “molecular cork” effect causes the intrinsically reactive sites to remain dormant in various important catalytic processes. Here, we report a strategy to waken dormant atomic Au on cobalt-doped CeO2 islands (Au/CoCeO2) that are typically recognized as barely active in acetylene hydrochlorination by precisely controlling reversible C2H2 spillover facilitated by porous carbon materials, igniting its reactivity of Au-oxo sites and enhanced stability. In this vein, the C2H2 coverage on the nitrogen-doped carbon (NC) surface reversibly spills over onto HCl-corked metal sites, uncorking the strongly bound HCl. The Au/CoCeO2 + NC system displays a 2 orders of magnitude higher activity than modular Au/CoCeO2 and obtains an enhanced catalytic activity and durability than the state-of-the-art catalyst, Au/NC. This contribution unveils a distinct Eley–Rideal-like mechanism that exists on the Au/CoCeO2 + NC system, exchanging the conventional Langmuir–Hinshelwood pathway dominated over Au/NC. Collectively, our findings reinforce the importance of taming the reaction pathways for advancing catalyst design.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"130 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451528","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

Organic Molecular Cage-Mediated pH-Responsive Reversible Protein Self-Assembly with Multi-Enhanced Enzymatic Performance

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-02-20 DOI: 10.1021/acscatal.5c00240

Zhongxu Guo, Weixi Kong, Liya Zhou, Ying He, Li Ma, Guanhua Liu, Yunting Liu, Yanjun Jiang

{"title":"Organic Molecular Cage-Mediated pH-Responsive Reversible Protein Self-Assembly with Multi-Enhanced Enzymatic Performance","authors":"Zhongxu Guo, Weixi Kong, Liya Zhou, Ying He, Li Ma, Guanhua Liu, Yunting Liu, Yanjun Jiang","doi":"10.1021/acscatal.5c00240","DOIUrl":"https://doi.org/10.1021/acscatal.5c00240","url":null,"abstract":"Despite the various advantages and versatile applications of protein self-assemblies, their use as immobilized enzymes in biocatalysis, especially for organic synthesis, has rarely been reported. Here, we achieved the pH-responsive reversible self-assembly of an industrially important amine dehydrogenase (AmDH) with the assistance of porous organic molecular cages (OMCs). The thus-formed AmDH–OMC self-assemblies as heterogeneous biocatalysts demonstrated the following advantages that are highly challenging to conventional immobilization strategies: (1) multiperformance enhancements, including stability, activity, kinetics, and catalytic efficiency; (2) high recoverability and recyclability of both the enzyme and the OMCs; and (3) mechanistic elucidation of the AmDH–OMC intermolecular interaction at the molecular level by molecular dynamics simulations. This strategy also enabled the in situ preparation and application of multienzyme and enzyme–metal coimmobilized biocatalysts for the enantioselective synthesis of chiral amines in batch and flow systems, demonstrating its high synthetic utility.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"81 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451527","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

Organocatalytic Atroposelective Hydroselenation of Alkynes To Access Axially Chiral Vinyl Selenides

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-02-20 DOI: 10.1021/acscatal.4c07281

Yi-Xin Wang, Jing-Run Wang, Chen Cui, Zhen Wang, Yu Lu, Xiao-Hui Yang

引用次数: 0