Chem Catalysis最新文献_第3页

Radical-mediated regiodivergent C(sp3)–H functionalization of N-substituted indolines via enzymatic carbene transfer 通过酶促碳烯转移对 N-取代吲哚啉进行自由基介导的 C(sp3)-H 功能化

IF 9.4

Chem Catalysis Pub Date : 2024-11-21 DOI: 10.1016/j.checat.2024.101133

Bo M. Couture, Ru Cui, Jia-Min Chu, Zhuofan Shen, Sagar D. Khare, Yong Zhang, Rudi Fasan

{"title":"Radical-mediated regiodivergent C(sp3)–H functionalization of N-substituted indolines via enzymatic carbene transfer","authors":"Bo M. Couture, Ru Cui, Jia-Min Chu, Zhuofan Shen, Sagar D. Khare, Yong Zhang, Rudi Fasan","doi":"10.1016/j.checat.2024.101133","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101133","url":null,"abstract":"Indolines are ubiquitous structural motifs occurring in pharmaceuticals and natural products. Here, we report a strategy for regio- and stereoselective C(sp3)–H functionalization of N-substituted indolines via carbene transfer chemistry mediated by engineered CYP119-based catalysts. These systems offer high enantioselectivity and high catalytic efficiency, as well as regiodivergent selectivity, furnishing an efficient and convenient route for diversification of these important scaffolds via direct C(sp3)–H functionalization. Selective functionalization of exocyclic C(sp3)–H bond in N-methyl indolines was also achieved, and a biocatalytic cascade combining enzyme-mediated α- and β-C(sp3)–H functionalization yielded a polycyclic indoline-containing motif found in drugs. Mechanistic and computational studies support a radical-mediated C–H functionalization pathway and provide insights into protein-mediated regiodivergent selectivity. Altogether, this work offers a direct and tunable strategy to access functionalized indolines as key building blocks for medicinal chemistry and natural product synthesis and provides first insights into the mechanism of P450-catalyzed C(sp3)–H carbene insertion.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"23 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142679038","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Spatial effects define CO2 electrolysis systems 界定二氧化碳电解系统的空间效应

IF 9.4

Chem Catalysis Pub Date : 2024-11-21 DOI: 10.1016/j.checat.2024.101185

Siddhartha Subramanian, Hugo-Pieter Iglesias van Montfort, Thomas Burdyny

{"title":"Spatial effects define CO2 electrolysis systems","authors":"Siddhartha Subramanian, Hugo-Pieter Iglesias van Montfort, Thomas Burdyny","doi":"10.1016/j.checat.2024.101185","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101185","url":null,"abstract":"CO2 electrolyzers show promise as a cleaner alternative to produce value-added chemicals. In the last decade, research has shifted from classifying CO2 reduction activity and selectivity as a catalytic property (zero-dimensional [0D]) to one that includes the complex interactions of gas, liquid, and solid species between the cathode and anode (1D). To scale CO2 electrolyzers, however, 2D and 3D spatial variations in product selectivity, activity, and stability arise due to the design of reactor components, as well as concentration variations of the reactants, intermediates, and products. Conventional “black-box” measurement protocols are then insufficient to characterize CO2 electrolyzers. Here, we discuss the critical multi-dimensional phenomena occurring inside these electrochemical systems, which impact the observed performance. Recent literature is used to demonstrate how a spatial perspective is essential for proper data interpretation, designing effective catalysts, and prolonging CO2 electrolyzer lifetimes. Researchers should then define CO2 electrolysis systems in multiple dimensions (2D and 3D).","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"8 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142679029","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Strong activity-based volcano-type relationship for dry reforming of methane through modulating Ni-CeO2 interaction over Ni/CeO2-SiO2 catalysts 通过调节 Ni/CeO2-SiO2 催化剂上 Ni-CeO2 的相互作用实现甲烷干转化的强活性火山型关系

IF 9.4

Chem Catalysis Pub Date : 2024-11-21 DOI: 10.1016/j.checat.2024.101189

Yufeng Li, Zhenwei Li, Nan Wang, Yajun Zha, Ke Zheng, Yuebing Xu, Bing Liu, Xiaohao Liu

{"title":"Strong activity-based volcano-type relationship for dry reforming of methane through modulating Ni-CeO2 interaction over Ni/CeO2-SiO2 catalysts","authors":"Yufeng Li, Zhenwei Li, Nan Wang, Yajun Zha, Ke Zheng, Yuebing Xu, Bing Liu, Xiaohao Liu","doi":"10.1016/j.checat.2024.101189","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101189","url":null,"abstract":"The dry reforming of methane (DRM) reaction holds significance for efficient conversion of CH4 and CO2 into syngas for the subsequent production of premium fuels and high-value chemicals. However, catalyst deactivation is easily caused by carbon deposition over Ni-based catalysts. Here, we investigated the effects of ultrasmall CeO2 nano-islands on the DRM reaction and found a strong volcano-type relationship between CeO2 content and reaction activity over Ni/CeO2-SiO2 catalysts. A suitable CeO2 amount can only slightly suppress CH4 dissociation but largely promote carbon species elimination. More importantly, the presence of these CeO2 nano-islands positively affected the types and location of coke species by “carbon-phobic effect” and thus alleviated coverage of Ni active sites. As a result, a higher TOFCH4 was obtained by an increase of about 82% and a continuous 2,000-h run almost without any side reaction, and deactivation was achieved along with CO2 and CH4 conversions at about 96% and 92%, respectively.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"74 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142679030","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Close-loop chemical recycling unlocked via waste polyolefins-ethylene co-metathesis 通过废弃聚烯烃与乙烯的共甲氧基化反应实现闭环化学循环利用

IF 9.4

Chem Catalysis Pub Date : 2024-11-21 DOI: 10.1016/j.checat.2024.101194

Pavel A. Kots

引用次数: 0

Deoxygenative alcohol–nucleophile coupling via carbocations 通过碳化作用实现脱氧醇-核亲和剂偶联

IF 9.4

Chem Catalysis Pub Date : 2024-11-18 DOI: 10.1016/j.checat.2024.101187

Léa Thai-Savard, Jason R. Zbieg, Jack A. Terrett

引用次数: 0

Visible light-driven excited-state copper-BINAP catalysis for accessing diverse chemical reactions 利用可见光驱动激发态铜-BINAP 催化技术实现多样化化学反应

IF 9.4

Chem Catalysis Pub Date : 2024-11-15 DOI: 10.1016/j.checat.2024.101184

Upasana Mukherjee, Jagrut A. Shah, Ming-Yu Ngai

引用次数: 0

Metal cation exchange with zeolitic acid sites modulates hydrocarbon pool propagation during CO2 hydrogenation 金属阳离子与沸石酸位点的交换调节二氧化碳加氢过程中碳氢化合物池的扩散

IF 9.4

Chem Catalysis Pub Date : 2024-11-13 DOI: 10.1016/j.checat.2024.101183

Fatima Mahnaz, Balaji C. Dharmalingam, Jasan Robey Mangalindan, Jenna Vito, Jithin John Varghese, Manish Shetty

{"title":"Metal cation exchange with zeolitic acid sites modulates hydrocarbon pool propagation during CO2 hydrogenation","authors":"Fatima Mahnaz, Balaji C. Dharmalingam, Jasan Robey Mangalindan, Jenna Vito, Jithin John Varghese, Manish Shetty","doi":"10.1016/j.checat.2024.101183","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101183","url":null,"abstract":"We demonstrate that the exchange of zeolitic Brønsted acid sites (BASs) with cations from metal oxides plays a pivotal role in the propagation of hydrocarbon pools (HCPs) during CO2 hydrogenation. We probed the likelihood of In2O3, ZnZrOx, and Cr2O3 migration and their cation exchange with BASs of a silicoaluminophosphate, SAPO-34, by integrating them at nanoscale proximity (∼1,400 nm). Analysis with NH3 temperature-programmed desorption and transmission Fourier transform infrared spectroscopy showed ion exchange of BASs with Inδ+ and Znδ+ but not for Crδ+. We measured the C3/C2 hydrocarbon ratio (indicating relative propagation of olefin to aromatic cycles) and paraffin-to-olefin ratio, which revealed that Inδ+ species inhibited HCPs inside the channels of SAPO-34, while Znδ+ species enhanced hydrogen transfer and secondary hydrogenation. Combining reactivity data with occluded hydrocarbon analysis and 13C solid-state nuclear magnetic resonance spectroscopy, we show that ion-exchanged species affect HCP propagation. Overall, our work provides insights for the rational integration of bifunctional catalysts.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"3 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601710","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Symmetry-breaking CoN3S1 centers enable inert chloride ion adsorption for facilitating self-driven overall seawater splitting 打破对称的 CoN3S1 中心可实现惰性氯离子吸附，从而促进自驱动的整体海水分离

IF 9.4

Chem Catalysis Pub Date : 2024-11-12 DOI: 10.1016/j.checat.2024.101169

Canhui Zhang, Xu Liu, Cheng Zhen, Hanxu Yao, Liangliang Xu, Haibing Ye, Yue Wang, Xingkun Wang, M. Danny Gu, Minghua Huang, Heqing Jiang

{"title":"Symmetry-breaking CoN3S1 centers enable inert chloride ion adsorption for facilitating self-driven overall seawater splitting","authors":"Canhui Zhang, Xu Liu, Cheng Zhen, Hanxu Yao, Liangliang Xu, Haibing Ye, Yue Wang, Xingkun Wang, M. Danny Gu, Minghua Huang, Heqing Jiang","doi":"10.1016/j.checat.2024.101169","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101169","url":null,"abstract":"A self-driven seawater splitting system could efficiently produce hydrogen from abundant seawater. However, high Cl− concentrations in seawater lead to catalyst corrosion and deactivation, impairing performance in the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). Here, we adopted single-atom Co-N-C-based catalysts, in which the electronic structure around the central Co site can be controlled and adjusted at an atomic level. Experimentally, the target N and S co-doped hollow carbon sphere (Co-N/S-HCS) catalyst, featuring asymmetric Co-N3S1 sites, shows excellent ORR/OER/HER performance. By employing density functional theory and molecular dynamics simulations of real-time simulations, we reveal that the S doped in the asymmetric Co-N3S1 model leads to a customized electronic structure around the central Co site, enabling weakened adsorption of the corrosive Cl− and excellent ORR/OER/HER activities. Moreover, the seawater-based Zn-air batteries (S-ZABs) assembled by the Co-N/S-HCS deliver a cycling performance exceeding 650 h, and the overall seawater splitting system can run continuously for 1,100 h.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"71 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142599720","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Illuminating selectivity descriptors for the methanol-to-propylene process over Ca-modified and unmodified zeolite ZSM-5 甲醇制丙烯工艺在钙改性和未改性沸石 ZSM-5 上的光照选择性描述符

IF 9.4

Chem Catalysis Pub Date : 2024-11-12 DOI: 10.1016/j.checat.2024.101168

Abhay Dokania, Xuan Gong, Edy Abou-Hamad, Alla Dikhtiarenko, Tuiana Shoinkhorova, Yiru Ye, Javier Patarroyo, Nimer Wehbe, Abhishek Dutta Chowdhury, Jorge Gascon

{"title":"Illuminating selectivity descriptors for the methanol-to-propylene process over Ca-modified and unmodified zeolite ZSM-5","authors":"Abhay Dokania, Xuan Gong, Edy Abou-Hamad, Alla Dikhtiarenko, Tuiana Shoinkhorova, Yiru Ye, Javier Patarroyo, Nimer Wehbe, Abhishek Dutta Chowdhury, Jorge Gascon","doi":"10.1016/j.checat.2024.101168","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101168","url":null,"abstract":"There is a growing demand for propylene calls for effective carbon reduction methods. The methanol-to-propylene (MTP) process stands out as a promising solution for meeting global propylene demand sustainably. In this study, we identify the mechanistic factors responsible for enhanced reactivity, superior propylene selectivity, and durable catalyst lifespan in the MTP process catalyzed by both unmodified siliceous and Ca-modified ZSM-5 zeolites. By employing advanced characterization techniques like in situ UV-visible and solid-state NMR spectroscopy, along with well-designed control experiments, we highlight the importance of the alkene cycle within the zigzag channel of zeolite ZSM-5 for superior propylene selectivity. Furthermore, our work identifies oxymethylene species as a key intermediate that enhances the lifetime of the alkene cycle and governs MTP catalysis. We also explore the synergistic interaction between Lewis-Brønsted acids and their impact on hydrocarbon pool species to deepen our understanding of zeolite catalysis.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"19 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142599687","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Shifting hydrogenation pathway via electronic activation for efficient nitrate electroreduction to ammonia in sewages 通过电子活化改变氢化途径，在污水中将硝酸盐高效电还原为氨气

IF 9.4

Chem Catalysis Pub Date : 2024-11-12 DOI: 10.1016/j.checat.2024.101182

Wenye Zhong, Xuepeng Xiang, Peiyan Chen, Jiayu Su, Zhiheng Gong, Xueming Liu, Shijun Zhao, Nian Zhang, Chunhua Feng, Zhibin Zhang, Yan Chen, Zhang Lin

{"title":"Shifting hydrogenation pathway via electronic activation for efficient nitrate electroreduction to ammonia in sewages","authors":"Wenye Zhong, Xuepeng Xiang, Peiyan Chen, Jiayu Su, Zhiheng Gong, Xueming Liu, Shijun Zhao, Nian Zhang, Chunhua Feng, Zhibin Zhang, Yan Chen, Zhang Lin","doi":"10.1016/j.checat.2024.101182","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101182","url":null,"abstract":"Electrochemical hydrogenation reactions have attracted worldwide attention as a sustainable alternative to thermo-catalytic hydrogenations. Nevertheless, the Faradaic efficiency, in many cases, is limited by the competing side reaction of hydrogen evolution. In this work, we demonstrate that the hydrogenation pathway can be effectively modulated by electronic activation near the interface. In a heterostructure consisting of a Cu foam matrix and Co3O4 decoration layer (Co@Cu), the surface Co is effectively activated by electrons transferring from underneath Cu, leading to strongly promoted reactant adsorption and weakened Co-H bonding. Consequently, the hydrogenation pathway on the Co site shifts from H-H coupling to nitrate reduction, resulting in an outstanding nitrate reduction reaction (NO3−RR) Faradaic efficiency of 97.67%. A hybrid reactor combining electroreduction and membrane separation is further constructed to realize an NH3 recovery rate as high as 857.1 g-N m−2 d−1 from actual sewage. The results can be generalized for other electrochemical hydrogenation reactions for energy and environment applications.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"33 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142599718","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0