ACS Chemical Biology最新文献_第10页

Modulating CO2 Electroreduction Activity on Mo2C and Promoting C2 Product by Grain Boundary Engineering: Insights from First-Principles Calculations 通过晶界工程调节 Mo2C 上的二氧化碳电还原活性并促进 C2 产物：第一原理计算的启示

IF 11.3 2区生物学

ACS Chemical Biology Pub Date : 2024-10-23 DOI: 10.1021/acscatal.4c0320210.1021/acscatal.4c03202

Yuxing Lin, Fangqi Yu, Lei Li, Yameng Li, Rao Huang and Yuhua Wen*,

{"title":"Modulating CO2 Electroreduction Activity on Mo2C and Promoting C2 Product by Grain Boundary Engineering: Insights from First-Principles Calculations","authors":"Yuxing Lin, Fangqi Yu, Lei Li, Yameng Li, Rao Huang and Yuhua Wen*, ","doi":"10.1021/acscatal.4c0320210.1021/acscatal.4c03202","DOIUrl":"https://doi.org/10.1021/acscatal.4c03202https://doi.org/10.1021/acscatal.4c03202","url":null,"abstract":"Recently, two-dimensional transition-metal carbides and/or nitrides (MXenes) have attracted extensive interest owing to their promising applications in electrochemistry, especially in electrocatalysis for the CO2 reduction reaction (CO2RR). However, there still exist challenges in developing MXene electrocatalysts with high activity and selectivity. Grain boundaries (GBs) could potentially provide active sites for chemical reactions, and their existence may be helpful for improving various electrocatalytic performances of MXenes. In this work, we constructed nine types of GBs in the Mo2C monolayer and employed density functional theory (DFT) calculations to systematically investigate their effects on the conversion efficiency of CO2 and the diversity of CO2RR products. Our study reveals that the presence of different valence states of Mo atoms at the GBs breaks the symmetry of CO2 adsorption on Mo2C, which promotes the activation of CO2 and diversifies the CO2RR products. Especially, these GBs exhibited remarkably low limiting potentials for C1 products, e.g., −0.29 V for CH4 on 5|7c GB, −0.31 V for CH3OH on 4|8 GB, and −0.55 V for HCOOH on 4|4a GB. Furthermore, the reduced potential barriers at the GBs, such as 0.26 eV for 5|7b GB and 0.13 eV for 8|8b GB, facilitate the C–C coupling and promote the formation of C2 products. These findings demonstrate that the introduction of GBs can enhance both the electrocatalytic activity of Mo2C for the CO2RR and the diversity of CO2RR products, therefore paving the way for designing and advancing high-efficiency MXene electrocatalysts through GB engineering.","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16423–16433 16423–16433"},"PeriodicalIF":11.3,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142571149","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Reaction Mechanisms and Applications of Single Atom Catalysts for Thermal-Catalytic Carbon Dioxide Hydrogenation Toward Oxygenates 单原子催化剂在热催化二氧化碳加氢制氧过程中的反应机理与应用

IF 11.3 2区生物学

ACS Chemical Biology Pub Date : 2024-10-23 DOI: 10.1021/acscatal.4c0606510.1021/acscatal.4c06065

Fei Wang, Yicheng Liu, Mengke Peng, Mengyao Yang, Yuanyuan Chen, Juan Du* and Aibing Chen*,

{"title":"Reaction Mechanisms and Applications of Single Atom Catalysts for Thermal-Catalytic Carbon Dioxide Hydrogenation Toward Oxygenates","authors":"Fei Wang, Yicheng Liu, Mengke Peng, Mengyao Yang, Yuanyuan Chen, Juan Du* and Aibing Chen*, ","doi":"10.1021/acscatal.4c0606510.1021/acscatal.4c06065","DOIUrl":"https://doi.org/10.1021/acscatal.4c06065https://doi.org/10.1021/acscatal.4c06065","url":null,"abstract":"Thermo-catalytic CO2 hydrogenation to high-value oxygenates has been regarded as one of the most powerful strategies that can potentially alleviate excessive CO2 emissions. However, due to the high chemical stability of CO2 and the variability of hydrogenation pathways, it is still challenging to achieve highly active and selective CO2 hydrogenation. Single atom catalysts (SACs) with ultrahigh metal utilization efficiency and extraordinary electronic features have displayed growing importance for thermo-catalytic CO2 hydrogenation with multiple strategies developed to improve performances. Here, we review breakthroughs in developing SACs for efficient CO2 hydrogenation toward common oxygenates (CO, HCOOH, CH3OH, and CH3CH2OH) in the following order: first, an analysis of reaction mechanisms and thermodynamics challenges of CO2 hydrogenation reactions; second, a summary of metal SAs designed by dividing them into the two categories of the single- and dual-sites; third, discussion of support effects with a focus on approaches to regulating strong metal–support interaction (MSI). Summarily, current challenges and future perspectives to develop higher-performance SACs in CO2 hydrogenation are presented. We expect that this review can bring more design inspiration to trigger innovation in catalytic CO2 evolution materials and eventually benefit the achievement of the carbon-neutrality goal.","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16434–16458 16434–16458"},"PeriodicalIF":11.3,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142571207","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Variable Mechanisms for Cobalt-Catalyzed Alkyne Dimerization Pinpointed by Quasi-Classical Trajectory Simulations 准经典轨迹模拟指出钴催化炔烃二聚化的可变机制

IF 11.3 2区生物学

ACS Chemical Biology Pub Date : 2024-10-23 DOI: 10.1021/acscatal.4c0374910.1021/acscatal.4c03749

Haohua Chen, Zhile Dang, Xiantong Sha, Yu Wang, Zhiguo Zhang, Yixin Luo* and Yu Lan*,

{"title":"Variable Mechanisms for Cobalt-Catalyzed Alkyne Dimerization Pinpointed by Quasi-Classical Trajectory Simulations","authors":"Haohua Chen, Zhile Dang, Xiantong Sha, Yu Wang, Zhiguo Zhang, Yixin Luo* and Yu Lan*, ","doi":"10.1021/acscatal.4c0374910.1021/acscatal.4c03749","DOIUrl":"https://doi.org/10.1021/acscatal.4c03749https://doi.org/10.1021/acscatal.4c03749","url":null,"abstract":"Transition metal-catalyzed alkyne dimerization represents a powerful method for the construction of enynes. However, the ambiguous hydrogen transfer mechanism during the dimerization has resulted in controlling the regio-, stereo-, and, where applicable, chemoselectivity remaining a long-standing challenge. Herein, a combination of DFT calculations and quasi-classical MD simulations was used to interrogate the dynamic motion of hydrogen in cobalt-catalyzed alkyne dimerization. The collective results inspired us to propose, for the first time, a substrate-dependent differential hydride transfer model involving either concerted oxidative hydrogen transfer or stepwise oxidative addition, followed by alkyne insertion. The practicability and universality of this oxidative hydride transfer mechanism were further validated by the theoretical studies of experimentally observed selective cross- and homo-dimerization. Charge distribution analyses depicted that the differentiation between those two hydride transfer mechanisms originates from the α-silicon effect, which can stabilize the neighboring negative charge of the alkyne. Furthermore, a comprehensive DFT study of the substituent effects of alkynes reveals that the electron-withdrawing group will accelerate the oxidative hydride transfer process, which can open up avenues for mechanistic-oriented selective dimerization.","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16469–16478 16469–16478"},"PeriodicalIF":11.3,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142560485","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Role of High-Valence Metal Dissolution in Oxygen Evolution Kinetics of the Advanced FeNiOx Catalysts 高价金属溶解在高级氧化铁镍催化剂氧进化动力学中的作用

IF 11.3 2区生物学

ACS Chemical Biology Pub Date : 2024-10-22 DOI: 10.1021/acscatal.4c0445410.1021/acscatal.4c04454

Jun Ke, Jiaxi Zhang*, Longhai Zhang, Shunyi He, Chengzhi Zhong, Li Du, Huiyu Song, Xiaoming Fang*, Zhengguo Zhang and Zhiming Cui*,

{"title":"Role of High-Valence Metal Dissolution in Oxygen Evolution Kinetics of the Advanced FeNiOx Catalysts","authors":"Jun Ke, Jiaxi Zhang*, Longhai Zhang, Shunyi He, Chengzhi Zhong, Li Du, Huiyu Song, Xiaoming Fang*, Zhengguo Zhang and Zhiming Cui*, ","doi":"10.1021/acscatal.4c0445410.1021/acscatal.4c04454","DOIUrl":"https://doi.org/10.1021/acscatal.4c04454https://doi.org/10.1021/acscatal.4c04454","url":null,"abstract":"The incorporation of high-valence metals into FeNi-based oxides has been widely accepted as an efficient approach for facilitating the alkaline oxygen evolution reaction (OER), but the corresponding structure–property relationship remains unclear due to the lack of identification of the real structure. In this study, we reveal the surface evolution processes of M-doped FeNi oxides (M is Mo, V, and W) and elucidate the role of M dissolution in enhancing oxygen evolution kinetics. Taking Mo as an example, the high-valence metal Mo was doped into FeNiOx and its leaching behavior was observed during OER. By combining in situ Raman analysis, electrochemical measurement, and first-principles calculation, it was unveiled that the electro-dissolution of Mo, in the form of MoO42–, led to preferential removal of lattice oxygen, thereby facilitating the adsorption step of OH and triggering the lattice oxygen-mediated mechanism for promoting OER. Consequently, the optimized FeNiMoOx displayed an overpotential of only 235 mV to reach 10 mA/cm2 and a 30-fold enhancement in specific activity compared with that of FeNiOx at 1.53 V. Our findings provide a different perspective on the intricate association between dissolution of high-valence metal and alkaline OER performance, elucidating the key role of the dissolution-induced structure change on promoting the OER mechanism.","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16363–16373 16363–16373"},"PeriodicalIF":11.3,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142570990","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Merging Consecutive PET Processes within a Metal–Organic Cage for Abiotic–Biotic Combined Photocatalytic Biomass Reforming 在金属有机笼内合并连续 PET 过程，实现非生物-生物联合光催化生物质转化

IF 11.3 2区生物学

ACS Chemical Biology Pub Date : 2024-10-22 DOI: 10.1021/acscatal.4c0601810.1021/acscatal.4c06018

Zhefan Li, Junkai Cai*, Lingxiao Wang and Chunying Duan*,

{"title":"Merging Consecutive PET Processes within a Metal–Organic Cage for Abiotic–Biotic Combined Photocatalytic Biomass Reforming","authors":"Zhefan Li, Junkai Cai*, Lingxiao Wang and Chunying Duan*, ","doi":"10.1021/acscatal.4c0601810.1021/acscatal.4c06018","DOIUrl":"https://doi.org/10.1021/acscatal.4c06018https://doi.org/10.1021/acscatal.4c06018","url":null,"abstract":"Combining abiotic photocatalytic modules with enzymatic conversion to reform biomass represents a compelling way for sustainable energy schemes but faces marked challenges on the electron and proton transport corresponding to the cofactor regeneration and shuttling between biotic and abiotic partners. Herein, we report a consecutive photoinduced electron-transfer approach to reform biomass into fuels and active H-source for nitroarene reduction by grafting a cage-dye-NADH (nicotinamide adenine dinucleotide) clathrate with glucose dehydrogenase (GDH). Under light irradiation, the cage-dye-NADH clathrate acts as a photoactive relay to conduct two photoinduced 1e– electron-transfer reactions consecutively with a 2e– oxidation of NADH to NAD+, guaranteeing an orderly path related to cofactor regeneration. When the clathrate is positioned inside the pocket of GDH to join a biotic NAD+-mediated synthesis, the metal–organic artificial enzyme facilitates fast cofactor generation and shuttling between the artificial clathrate and the native enzyme within one working module. The grafting enzyme combines artificial photocatalysis and enzymatic dehydrogenation to endow an efficient conversion of biomass feedstocks into green H-source, innovating a unique paradigm for the sustainable energy scheme that combines energy of two photons in one turnover cycle. The superiority of the grafting enzyme allows the direct hydrogenation and reduction of fine chemicals and enables tandem nitroarene reduction with a turnover number reaching 15,000, providing a distinguished avenue for biomass utilization and solar energy conversion.","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16374–16382 16374–16382"},"PeriodicalIF":11.3,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142560513","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Engineering Chemical and Catalytic Activity of Metal Surface Sites by Controlling Strain and Ligand Effects in Nonmodel Nanoparticle Catalysts 通过控制非模型纳米粒子催化剂中的应变和配体效应，实现金属表面位点的化学和催化活性工程化

IF 11.3 2区生物学

ACS Chemical Biology Pub Date : 2024-10-22 DOI: 10.1021/acscatal.4c0385710.1021/acscatal.4c03857

Bill Yan, and , Suljo Linic*,

{"title":"Engineering Chemical and Catalytic Activity of Metal Surface Sites by Controlling Strain and Ligand Effects in Nonmodel Nanoparticle Catalysts","authors":"Bill Yan,  and , Suljo Linic*, ","doi":"10.1021/acscatal.4c0385710.1021/acscatal.4c03857","DOIUrl":"https://doi.org/10.1021/acscatal.4c03857https://doi.org/10.1021/acscatal.4c03857","url":null,"abstract":"Binding energy of reactants on heterogeneous catalyst surface sites is a well-established catalytic activity descriptor for many chemical reactions. However, systematically manipulating the binding energies by engineering the catalytic surface sites has proven challenging. Herein, we propose a nanoparticle catalyst structure that contains an alloy core composed of miscible metal atoms, surrounded by layers of a different material, and covered by a layer of catalytically active metal. The alloy core controls the lattice strain of the nanoparticle and therefore the distance between the surface atoms, while the subsurface layer atoms induce a ligand effect on the surface atoms. We show that this class of materials allows us to systematically control the adsorbate binding energies with high precision. We illustrate our findings by developing nonmodel nanoparticle catalysts that employ an AuCu alloy with controlled composition as the core, Au as the surrounding layers, and Pt as the active surface metal. Electrochemical CO stripping measurements suggest that the CO binding energy on the surface Pt sites can be systematically tuned by varying the composition of the alloy core. Our analysis suggests that the change in the CO binding energy of Pt is the result of the combined ligand effect from the Au layers and strain effect from the AuCu core. The presented catalyst structure allows for precise modulation of the strain and ligand effect for tuning the local chemical environment of any catalytic materials, which may aid the development of next-generation catalysts.","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16383–16391 16383–16391"},"PeriodicalIF":11.3,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142560445","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Recruitment to the Proteasome Is Necessary but Not Sufficient for Chemically Induced, Ubiquitin-Independent Degradation of Native Proteins 招募到蛋白酶体对于化学诱导的、依赖于泛素的原生蛋白降解是必要的，但并不充分

IF 3.5 2区生物学

ACS Chemical Biology Pub Date : 2024-10-22 DOI: 10.1021/acschembio.4c0042210.1021/acschembio.4c00422

Madeline Balzarini, Joel Tong, Weijun Gui, Isuru M. Jayalath, Bin-Bin Schell and Thomas Kodadek*,

{"title":"Recruitment to the Proteasome Is Necessary but Not Sufficient for Chemically Induced, Ubiquitin-Independent Degradation of Native Proteins","authors":"Madeline Balzarini, Joel Tong, Weijun Gui, Isuru M. Jayalath, Bin-Bin Schell and Thomas Kodadek*, ","doi":"10.1021/acschembio.4c0042210.1021/acschembio.4c00422","DOIUrl":"https://doi.org/10.1021/acschembio.4c00422https://doi.org/10.1021/acschembio.4c00422","url":null,"abstract":"Targeted protein degradation (TPD) is a promising strategy for drug development. Most degraders function by forcing the association of the target protein (TP) with an E3 Ubiquitin (Ub) ligase, which, in favorable cases, results in the polyubiquitylation of the TP and its subsequent degradation by the 26S proteasome. An alternative strategy would be to create chemical dimerizers that bypass the requirement for polyubiquitylation by recruiting the target protein directly to the proteasome. Direct-to-proteasome degraders (DPDs) may exhibit different characteristics than ubiquitin-dependent degraders, but few studies of this type of TPD have been published, largely due to the dearth of suitable proteasome ligands. To facilitate studies of DPDs, we report here a mammalian cell line in which the HaloTag protein is fused to the proteasome via Rpn13, one of the ubiquitin receptors. In these cells, a chloroalkane serves as a covalent proteasome ligand surrogate. We show that chimeric molecules comprised of a chloroalkane linked to a ligand for the BET family of proteins or the Cdk2/7/9 family of kinases result in ubiquitin-independent degradation of some of these target proteins. We use this system, the first that allows facile degradation of native proteins in a ubiquitin-independent fashion, to probe two issues: the effect of varying the length of the linker connecting the chloroalkane and the target ligand and the selectivity of degradation within the protein families engaged by the target ligand.","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"19 11","pages":"2323–2335 2323–2335"},"PeriodicalIF":3.5,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142640998","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Cu-Albumin Artificial Enzymes with Peroxidase and Oxidase Activity for Stereoselective Oxidations 具有过氧化物酶和氧化酶活性的铜-白蛋白人工酶，用于立体选择性氧化反应

IF 11.3 2区生物学

ACS Chemical Biology Pub Date : 2024-10-22 DOI: 10.1021/acscatal.4c0573210.1021/acscatal.4c05732

Maham Liaqat, Emma McDonald, Robert Jervine Valdez Ortega, Aaron Lopes, Flavia Codreanu, Hannah Carlisle, Challa V. Kumar, Xudong Yao, James F. Rusling and Jie He*,

引用次数: 0

Proteolytic Performance Is Dependent on Binding Efficiency, Processivity, and Turnover: Single Protease Insights 蛋白水解性能取决于结合效率、加工性和周转率：单一蛋白酶的启示

IF 11.3 2区生物学

ACS Chemical Biology Pub Date : 2024-10-22 DOI: 10.1021/acscatal.4c0418210.1021/acscatal.4c04182

Emily Winther Sørensen, Freya Björk Reinhold, Andreas Faber, Steen Bender, Jacob Kæstel-Hansen, Jeannette de Sparra Lundin, Errika Voutyritsa, Per Hedegaard, Sune M. Christensen and Nikos S. Hatzakis*,

{"title":"Proteolytic Performance Is Dependent on Binding Efficiency, Processivity, and Turnover: Single Protease Insights","authors":"Emily Winther Sørensen, Freya Björk Reinhold, Andreas Faber, Steen Bender, Jacob Kæstel-Hansen, Jeannette de Sparra Lundin, Errika Voutyritsa, Per Hedegaard, Sune M. Christensen and Nikos S. Hatzakis*, ","doi":"10.1021/acscatal.4c0418210.1021/acscatal.4c04182","DOIUrl":"https://doi.org/10.1021/acscatal.4c04182https://doi.org/10.1021/acscatal.4c04182","url":null,"abstract":"Proteases are essential enzymes for a plethora of biological processes and biotechnological applications, e.g., within the dairy, pharmaceutical, and detergent industries. Decoding the molecular-level mechanisms that drive protease performance is the key to designing improved biosolutions. However, the direct dynamic assessment of the fundamental partial reactions of substrate binding and activity has proven to be a challenge with conventional ensemble approaches. We developed a single-molecule (SM) assay for the direct and parallel recording of the stochastic binding interaction of Savinase, a serine-type protease broadly employed in biotechnology, with casein, while synchronously monitoring proteolytic degradation of the substrate. This assay allowed us to elucidate how the overall activity of Savinase and its variants depends on binding efficiency, turnover, and activity per binding event. We identified three distinct binding states, with mutations primarily affecting the long-lived state, indicating that it contributes to the overall activity and suggesting a level of processivity in Savinase. These insights, inaccessible through conventional methods, provide valuable perspectives for engineering proteases with improved hydrolytic performance.","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16335–16343 16335–16343"},"PeriodicalIF":11.3,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142560441","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Direct Detection of Key Intermediates during the Product Release in Rhenium Bipyridine-Catalyzed CO2 Reduction Reaction 在联吡啶铼催化的二氧化碳还原反应中直接检测产物释放过程中的关键中间产物

IF 11.3 2区生物学

ACS Chemical Biology Pub Date : 2024-10-22 DOI: 10.1021/acscatal.4c0604410.1021/acscatal.4c06044

Samir Chattopadhyay, Mun Hon Cheah, Reiner Lomoth and Leif Hammarström*,

{"title":"Direct Detection of Key Intermediates during the Product Release in Rhenium Bipyridine-Catalyzed CO2 Reduction Reaction","authors":"Samir Chattopadhyay, Mun Hon Cheah, Reiner Lomoth and Leif Hammarström*, ","doi":"10.1021/acscatal.4c0604410.1021/acscatal.4c06044","DOIUrl":"https://doi.org/10.1021/acscatal.4c06044https://doi.org/10.1021/acscatal.4c06044","url":null,"abstract":"Rhenium bipyridine tricarbonyl complexes, fac-[Re(bpy)(CO)3X]n+, are highly effective in selectively converting CO2 to CO under electrochemical and photochemical conditions. Despite numerous mechanistic studies aimed at understanding its CO2 reduction reaction (CO2RR) pathway, the intermediates further into the catalytic cycle have escaped detection, and the steps leading to product release remained elusive. In this study, employing stopped-flow mixing coupled with time-resolved infrared spectroscopy, we observed, for the first time, the reduced Re-tetracarbonyl species, [Re(bpy)(CO)4]0, with a half-life of approximately 55 ms in acetonitrile solvent. This intermediate is proposed to be common in both electrochemical and photochemical CO2RR. Furthermore, we directly observed the release of the product (CO) from this intermediate. Additionally, we detected the accumulation of [Re(bpy)(CO)3(CH3CN)]+ as a byproduct following product release, a significant side reaction under conditions with a limited supply of reducing equivalents mirroring photochemical conditions. The process could be unambiguously attributed to an electron transfer-catalyzed ligand substitution reaction involving [Re(bpy)(CO)4]0 by simultaneous real-time detection of all involved species. We believe that this side reaction significantly impacts the CO2RR efficiency of this class of catalysts under photochemical conditions or during electrocatalysis at mild overpotentials.","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16324–16334 16324–16334"},"PeriodicalIF":11.3,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscatal.4c06044","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142560442","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0