ACS Catalysis 最新文献

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Synergy of Oxygen Vacancies and Confinement Effect in CO2 Reforming of Toluene over Hydrotalcite-Derived Hollow-Sphere NiCo@Al2O3 Catalysts 水滑石衍生空心球NiCo@Al2O3催化剂上甲苯CO2重整中氧空位的协同作用和约束效应
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2025-05-28 DOI: 10.1021/acscatal.5c02360
Yongqi Kuang, Nadeemuddin Sk, Jing Dai, Sonali Das, Shuzhuang Sun, Shibo Xi, Lina Liu
{"title":"Synergy of Oxygen Vacancies and Confinement Effect in CO2 Reforming of Toluene over Hydrotalcite-Derived Hollow-Sphere NiCo@Al2O3 Catalysts","authors":"Yongqi Kuang, Nadeemuddin Sk, Jing Dai, Sonali Das, Shuzhuang Sun, Shibo Xi, Lina Liu","doi":"10.1021/acscatal.5c02360","DOIUrl":"https://doi.org/10.1021/acscatal.5c02360","url":null,"abstract":"CO<sub>2</sub> reforming of tar is a promising pathway for the simultaneous conversion of undesirable tars and CO<sub>2</sub> generated from biomass gasification, which is critical for syngas upgrading and utilization. However, catalyst deactivation caused by coking is a severe issue for supported catalysts in this application. In this study, hydrotalcite-derived NiCo alloys supported by Al<sub>2</sub>O<sub>3</sub> nanosheet self-assembled hollow spheres were constructed by a template-sacrificial coprecipitation method. The hollow-sphere CS@NiCo(CP) catalyst exhibited superior activity and stability compared to NiCo(CP), NiCo(HT), and CS/NiCo(HT) catalysts synthesized by conventional coprecipitation, conventional hydrothermal, and template-sacrificial hydrothermal methods. The confinement effect of the hollow structure and porous shells enriched the local concentrations of CO<sub>2</sub> relative to toluene adjacent to the catalytic sites, owing to the high diffusion resistance of toluene through the shell. Furthermore, the abundant oxygen defects and stronger basic sites in the CS@NiCo(CP) catalyst further facilitated the adsorption and activation of CO<sub>2</sub> and provided higher quantities of active oxygen species for the gasification and elimination of surface carbon intermediates produced by toluene cleavage. <i>In situ</i> diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments suggest that abundant oxygen defects in the catalyst accelerated the critical steps of the ring-opening and oxidation of toluene.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"25 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144153980","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
Mechanistic Insights into the Intercorrelation between the Hydrogen Evolution Reaction and Nitrate Reduction to Ammonia: A Review 析氢反应与硝酸还原制氨相互关系的机理研究进展
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2025-05-28 DOI: 10.1021/acscatal.5c00591
Tuo Zhang, Kaige Shi, Baodui Wang, Xiangyang Hou
{"title":"Mechanistic Insights into the Intercorrelation between the Hydrogen Evolution Reaction and Nitrate Reduction to Ammonia: A Review","authors":"Tuo Zhang, Kaige Shi, Baodui Wang, Xiangyang Hou","doi":"10.1021/acscatal.5c00591","DOIUrl":"https://doi.org/10.1021/acscatal.5c00591","url":null,"abstract":"The industrial synthesis of ammonia is characterized by harsh conditions, high energy consumption, and significant environmental pollution. In contrast, electrocatalytic nitrate reduction under ambient conditions presents a potential green and sustainable alternative to the energy-intensive industrial process. Hydrogen evolution reaction (HER), one of the most fundamental reactions in nature, is closely linked to the reaction mechanism of electrocatalytic nitrate reduction to ammonia (NRA), particularly in electrocatalysis, as both processes rely on proton transfer and electron exchange. The reactive hydrogen intermediates in HER often interact with the hydrogenation process in NRA, making it crucial to understand their interplay for the development of efficient electrocatalysts. By tuning the properties of electrocatalysts, water splitting can be elevated or suppressed to a point that enhances the selectivity of NRA, thereby optimizing ammonia production yields. However, there has been little systematic review of the mechanistic relationship between HER and NRA. This perspective provides a comprehensive overview of theoretical and experimental advances in HER and NRA processes, with a particular emphasis on their mechanistic relevance.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"183 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144153977","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
Remote Stereocontrol in the C6-Functionalization of Indoles via Synergistic Ion-Pair Catalysis 协同离子对催化作用下吲哚c6功能化的远程立体控制
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2025-05-28 DOI: 10.1021/acscatal.5c00780
Zhi-Qiang Zhu, Han-Peng Pan, Liang Long, Ze-Yu Su, Ai-Jun Ma, Jin-Bao Peng, Hao Gao, Guo-Dong Chen, Yong-Heng Wang, Xiang-Zhi Zhang
{"title":"Remote Stereocontrol in the C6-Functionalization of Indoles via Synergistic Ion-Pair Catalysis","authors":"Zhi-Qiang Zhu, Han-Peng Pan, Liang Long, Ze-Yu Su, Ai-Jun Ma, Jin-Bao Peng, Hao Gao, Guo-Dong Chen, Yong-Heng Wang, Xiang-Zhi Zhang","doi":"10.1021/acscatal.5c00780","DOIUrl":"https://doi.org/10.1021/acscatal.5c00780","url":null,"abstract":"Remote stereocontrol is a long-standing challenge in synthetic chemistry due to the diminishing influence of a catalyst’s chiral environment over extended distances. This limitation is particularly pronounced in the enantioselective C6-functionalization of indoles, a transformation of significant interest in pharmaceutical research and natural product synthesis. We herein present a visible-light-induced direct asymmetric C6-functionalization of indoles achieved through synergistic dual catalysis employing a chiral phosphoric acid and magnesium sulfate, which achieves precise remote stereocontrol. The reaction proceeds via an alkyne-carbonyl metathesis/1,6-addition cascade involving arylalkynes, benzoquinones, and indoles. This strategy facilitates the de novo synthesis of diverse enantioenriched indoles with acyclic all-carbon quaternary chiral centers at the C6 position, delivering high yields and enantioselectivities from simple and readily available starting materials. Moreover, the resulting products can be easily transformed into a range of structurally diverse molecules with all-carbon quaternary chiral centers, which are otherwise difficult to synthesize with a high enantiomeric purity. Several products also exhibit promising anticancer activities, highlighting their potential pharmaceutical relevance. Computational and experimental investigations reveal that magnesium sulfate significantly promotes the formation of the reaction precursor (binding free energy: −68.5 kcal/mol), demonstrating its strong capacity to bind reactant components even at low concentrations, which would markedly enhance the reaction productivity, as long as the reaction barrier is feasible. Moreover, magnesium sulfate promotes parallel π–π stacking interactions between the aromatic ring of the <i>para</i>-quinone methide intermediate and the indole ring, thereby enhancing both reactivity and enantioselectivity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"18 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144153978","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
Iron-Carbene-Mediated Catalytic Activation of Conventional Thioglycosides for Stereoselective 1,2-cis-Furanosylations 铁-碳烯介导的传统巯基苷立体选择性1,2-顺式呋喃基化催化活化
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2025-05-28 DOI: 10.1021/acscatal.5c02301
Surya Pratap Singh, Umesh Chaudhary, Chance W. Lander, Adrienne Daroczi, Yihan Shao, Indrajeet Sharma
{"title":"Iron-Carbene-Mediated Catalytic Activation of Conventional Thioglycosides for Stereoselective 1,2-cis-Furanosylations","authors":"Surya Pratap Singh, Umesh Chaudhary, Chance W. Lander, Adrienne Daroczi, Yihan Shao, Indrajeet Sharma","doi":"10.1021/acscatal.5c02301","DOIUrl":"https://doi.org/10.1021/acscatal.5c02301","url":null,"abstract":"The catalytic activation of glycosyl donors using earth-abundant metals, particularly iron (Fe), remains a significant challenge in achieving 1,2-<i>cis</i> glycosylations. Accessing the most catalytically activated donors requires multiple steps and a carefully designed process including the most stable and commonly used thioglycoside donors. Conventional thioglycosides, which are readily accessible, often necessitate stoichiometric amounts of activators or harsh reaction conditions for activation, making it quite challenging to achieve stereoselective glycosylation, especially 1,2-<i>cis</i> selectivity. In this work, we developed an iron-carbene-mediated catalytic activation method for conventional thioglycosides. This one-pot approach exhibits high chemoselectivity, favoring <i>S</i>-insertion into the carbene over the insertion into the O–H, resulting in a sulfur ylide, a suitable leaving group. Upon elimination, the resulting sulfonium ion generates an oxocarbenium ion, which, through C2–O–iron coordination, directs incoming glycosyl acceptors from the <i>cis</i>-face, ensuring high 1,2-<i>cis</i> stereoselectivity. The induction of high 1,2-<i>cis</i> selectivity through an iron-chelation mechanism is further supported by density functional theory (DFT) studies. This methodology demonstrates broad applicability, accommodating various glycosyl donors such as <span>d</span>-ribose, <span>d</span>-arabinose, and <span>l</span>-arabinose, along with a wide range of glycosyl acceptors. We successfully applied this strategy to synthesize the challenging 1,2-<i>cis</i> ribotetrafuranoside, further underscoring its synthetic utility.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"14 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144153979","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
Deciphering CO2 and H2 Activation on ZnZrOx Solid-Solution Catalyst: Atomic-Level Insights into Methanol Synthesis 破译ZnZrOx固溶催化剂上CO2和H2的活化:甲醇合成的原子水平见解
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2025-05-27 DOI: 10.1021/acscatal.5c01398
Tongyao Wang, Chizhou Tang, Linhai He, Lanqi Ning, Meiling Guo, Xuebin Liu, Lixin Liang, Rongtan Li, Yi Ji, Kuizhi Chen, Jijie Wang, Qiang Fu, Pan Gao, Guangjin Hou
{"title":"Deciphering CO2 and H2 Activation on ZnZrOx Solid-Solution Catalyst: Atomic-Level Insights into Methanol Synthesis","authors":"Tongyao Wang, Chizhou Tang, Linhai He, Lanqi Ning, Meiling Guo, Xuebin Liu, Lixin Liang, Rongtan Li, Yi Ji, Kuizhi Chen, Jijie Wang, Qiang Fu, Pan Gao, Guangjin Hou","doi":"10.1021/acscatal.5c01398","DOIUrl":"https://doi.org/10.1021/acscatal.5c01398","url":null,"abstract":"The application of ZnO–ZrO<sub>2</sub>-based oxide catalysts in the CO<sub>2</sub>-to-methanol hydrogenation reaction has garnered significant attention; yet, insights into the active site configurations and reaction mechanism remain elusive. In this study, by employing advanced solid-state NMR techniques, we comprehensively investigated the surface active sites and the activation of CO<sub>2</sub> and H<sub>2</sub> molecules on the ZnZrO<sub><i>x</i></sub> solid-solution catalyst, complemented by comparative investigations on supported ZnO/ZrO<sub>2</sub> catalysts. We revealed the intricate surface structure of the ZnZrO<sub><i>x</i></sub> solid-solution catalyst at the atomic level, highlighting the presence of a disordered surface ZnO phase and the Zn–OH–Zr interface, as identified by <sup>17</sup>O MAS NMR. Notably, the ZnZrO<sub><i>x</i></sub> solid-solution and supported ZnO/tetragonal-ZrO<sub>2</sub> catalysts exhibit strikingly similar surface features, correlating with their comparable catalytic performances. A key breakthrough is the direct identification of active bidentate carbonate species formed through the CO<sub>2</sub> interaction with surface oxygen vacancies, specifically at the Zn–[Ov]–Zr interface. Using trimethylphosphine as a probe molecule, the relationship between oxygen vacancies and methanol production was confirmed by <sup>31</sup>P NMR. More importantly, NMR analysis provides the direct evidence on the formation of surface zinc hydride (Zn–H) over both ZnZrO<sub><i>x</i></sub> solid-solution and supported ZnO/ZrO<sub>2</sub> catalysts during H<sub>2</sub> activation. These Zn–H species, in close proximity to oxygen vacancies, are shown to readily activate CO<sub>2</sub> even at room temperature, leading to the formation of a surface formate intermediate and thereby facilitating methanol production. This study offers fundamental atomic-level insights into the critical surface active sites and reaction mechanism underlying CO<sub>2</sub> hydrogenation on the ZnO–ZrO<sub>2</sub>-based catalysts, and also paves the way for the rational design of more efficient catalysts for methanol production.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"48 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144145439","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
Polarized Ni0-Niδ+ Catalysts Enable Asymmetric C–C Coupling for Long-Chain Hydrocarbons in Electrochemical CO2 Reduction 极化Ni0-Niδ+催化剂使长链烃在电化学CO2还原过程中实现不对称C-C偶联
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2025-05-27 DOI: 10.1021/acscatal.4c07353
Haowen Ding, Wenwei Cai, Xinzhe Yang, Yu Zhang, Shunning Li, Feng Pan, Shisheng Zheng
{"title":"Polarized Ni0-Niδ+ Catalysts Enable Asymmetric C–C Coupling for Long-Chain Hydrocarbons in Electrochemical CO2 Reduction","authors":"Haowen Ding, Wenwei Cai, Xinzhe Yang, Yu Zhang, Shunning Li, Feng Pan, Shisheng Zheng","doi":"10.1021/acscatal.4c07353","DOIUrl":"https://doi.org/10.1021/acscatal.4c07353","url":null,"abstract":"The efficient electrochemical CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) to long-chain hydrocarbons (C<sub>3+</sub>) still remains a formidable task even on the widely investigated copper-based catalysts. Recently, nickel-based catalysts have garnered wide attention for their promising ability to generate C<sub>3+</sub> products. The design of Ni<sup>0</sup>-Ni<sup>δ+</sup> domains, analogous to the renowned Cu<sup>0</sup>-Cu<sup>δ+</sup> strategy, stands out as a hallmark approach, achieving substantial yields of C<sub>3</sub>–C<sub>6</sub> compounds. However, theoretical understanding remains significantly limited. Here, we employ full-solvent ab initio molecular dynamics simulations with a slow-growth approach to investigate Ni<sup>0</sup>-Ni<sup>δ+</sup>-mediated C–C coupling at partially polarized nickel. In this system, the nonpolarized region is constantly covered by the generated *CO, while the polarized domain─through strategic modulation of Ni’s d-band center─mitigates the poisoning effects of *CO<sub>2</sub> and *CO, thereby enhancing their activation. This facilitates C–C coupling primarily between *COOH and *CH<i><sub>x</sub></i>(x = 1, 2), with significantly lower kinetic barriers compared to conventional *CO-involved pathways, laying the foundation for sustained carbon chain growth. Extending this concept to other metals (<i>M</i> = Fe, Rh, Pd, Co and Ru) with similar adsorption characteristics akin to Ni further underscores the potential of M<sup>0</sup>-M<sup>δ+</sup> domains for CO<sub>2</sub> electroreduction. Our study elucidates the microscopic mechanisms by which polarization strategies promote the formation of long-chain products, providing an original perspective for designing CO<sub>2</sub> electroreduction catalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"44 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144145438","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
A Machine Learning-Driven, Probability-Based Approach to Enzyme Catalysis 一种机器学习驱动、基于概率的酶催化方法
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2025-05-27 DOI: 10.1021/acscatal.5c02431
Sudip Das, Umberto Raucci, Enrico Trizio, Peilin Kang, Rui P.P. Neves, Maria J. Ramos, Michele Parrinello
{"title":"A Machine Learning-Driven, Probability-Based Approach to Enzyme Catalysis","authors":"Sudip Das, Umberto Raucci, Enrico Trizio, Peilin Kang, Rui P.P. Neves, Maria J. Ramos, Michele Parrinello","doi":"10.1021/acscatal.5c02431","DOIUrl":"https://doi.org/10.1021/acscatal.5c02431","url":null,"abstract":"The workings of enzymes depend crucially on transition state structures, which encode critical chemical information necessary to control their efficiency and selectivity. However, capturing these configurations and describing them on a statistical basis remains a significant challenge due to their transient nature. Here, we leverage a novel enhanced sampling scheme based on a machine-learned committor function to provide a probabilistic characterization of transition states in enzymatic reactions. Applied to the glycolysis reaction of maltopentaose catalyzed by human pancreatic α-amylase, this approach successfully reveals the critical role of water molecules in shaping the catalytic landscape, dictating whether the reaction follows a water-assisted or water-mediated mechanism, and providing atomistic insight on how specific hydrogen bonding interactions within the catalytic pocket can influence the stability of transition states. Our findings highlight the potential of this machine-learning-based enhanced sampling scheme to study rare events in complex biochemical systems, offering a powerful tool for unveiling mechanistic details that are often elusive with traditional simulation approaches and paving the way for accelerating the rational design of novel enzymes through more accurate dynamics-activity correlations targeting the transition state ensemble.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"18 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144145440","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
Cyclic Voltammetry–Synchronized Operando HERFD-XANES and RIXS Analyses of Adsorbed Structures and Bonding States of Active Oxygen Species on Pt Nanoparticle Electrocatalysts in PEFC 循环伏安-同步Operando HERFD-XANES和RIXS分析PEFC中Pt纳米颗粒电催化剂上活性氧的吸附结构和键合状态
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2025-05-27 DOI: 10.1021/acscatal.5c01160
Hiroko Ariga-Miwa, Takehiko Sasaki, Tomohiro Sakata, Kotaro Higashi, Takefumi Yoshida, Oki Sekizawa, Takuma Kaneko, Tomoya Uruga, Yasuhiro Iwasawa
{"title":"Cyclic Voltammetry–Synchronized Operando HERFD-XANES and RIXS Analyses of Adsorbed Structures and Bonding States of Active Oxygen Species on Pt Nanoparticle Electrocatalysts in PEFC","authors":"Hiroko Ariga-Miwa, Takehiko Sasaki, Tomohiro Sakata, Kotaro Higashi, Takefumi Yoshida, Oki Sekizawa, Takuma Kaneko, Tomoya Uruga, Yasuhiro Iwasawa","doi":"10.1021/acscatal.5c01160","DOIUrl":"https://doi.org/10.1021/acscatal.5c01160","url":null,"abstract":"This study presents an operando analysis of Pt nanoparticle (NP) electrocatalysts in a polymer electrolyte fuel cell (PEFC) under cyclic voltammetry (CV), utilizing a multimodal system combining high-energy resolution fluorescence detected X-ray absorption near-edge structure (HERFD-XANES), resonant inelastic X-ray scattering (RIXS), X-ray diffraction (XRD), and quick X-ray absorption fine structure (QXAFS) techniques. The developed multi-analysis provides insight into the voltage-dependent adsorption structures and bonding states of active oxygen species on Pt NPs. CV-synchronized HERFD-XANES spectra reveal the evolution of Pt electronic states, highlighting shifts in bonding characteristics associated with changes in the applied voltage. In the anodic scan, oxygen species adsorb on Pt NPs at specific voltages, inducing structural changes that can be detected via XRD and QXAFS analysis. Density functional theory (DFT) calculations combined with finite difference method near-edge structure (FDMNES) simulations predict the stability and binding configurations of adsorbed oxygen species, emphasizing the role of edge sites of Pt NPs in the oxygen reduction reaction (ORR) activity. Additionally, the study evaluates degradation effects through accelerated durability tests (ADT), showing how Pt NP coarsening impacts adsorption dynamics and the electronic structure under ADT cycling. The CV processes were visualized by operando HERFD-XANES and RIXS spectroscopies. The findings demonstrate the potential of CV-synchronized HERFD-XANES and RIXS to provide atomistic insights into catalytic mechanisms on Pt NPs, supporting the optimization of Pt-based electrocatalysts for improved performance and durability in PEFC applications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"33 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144154051","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
Enabling Efficient Synthesis of Dihydrostilbenoid via Palladium-Catalyzed Redox-Neutral Deacylative Arylation 钯催化氧化还原中性脱酰芳基化高效合成二氢二苯乙烯
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2025-05-27 DOI: 10.1021/acscatal.5c02437
Yafei Wan, Tengfei Kang, Zhehui Xu, Weikang Xiong, Gang Li, Jianyang Dong, Dong Xue
{"title":"Enabling Efficient Synthesis of Dihydrostilbenoid via Palladium-Catalyzed Redox-Neutral Deacylative Arylation","authors":"Yafei Wan, Tengfei Kang, Zhehui Xu, Weikang Xiong, Gang Li, Jianyang Dong, Dong Xue","doi":"10.1021/acscatal.5c02437","DOIUrl":"https://doi.org/10.1021/acscatal.5c02437","url":null,"abstract":"Carbon–Carbon (C–C) bonds constitute the fundamental framework of organic molecules, and their cleavage and reorganization play pivotal roles in both biological systems and industrial processes. Herein, we present a palladium-catalyzed deacylative arylation of diverse methyl ketones under light-free and redox-neutral conditions, offering an efficient approach to constructing C(sp<sup>2</sup>)–C(sp<sup>3</sup>) bonds. This radical cross-coupling protocol features a broad substrate scope and good functional group compatibility, facilitating the late-stage modification of drug molecules and the synthesis of bioactive natural dihydrostilbenoids. The process leverages a redox-neutral mechanism, wherein the palladium complex serves as an oxidant and the ketone-derived prearomatic intermediates (PAIs) act as a reductant. Mechanistic investigations validate our hypothesis regarding the dual roles of the palladium complex in this transformation.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"34 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144145528","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
Regulating High Electron Spin State in Co3S4 for Enhanced Water Splitting 调节Co3S4中的高电子自旋态以增强水的分裂
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2025-05-27 DOI: 10.1021/acscatal.4c07849
Youyu Long, Shuwen Zhao, Lilian Wang, Hao Deng, Tao Sun, Jingwen Jiang, Tingting Liu, Shaodong Sun, Anran Chen, Hua Zhang
{"title":"Regulating High Electron Spin State in Co3S4 for Enhanced Water Splitting","authors":"Youyu Long, Shuwen Zhao, Lilian Wang, Hao Deng, Tao Sun, Jingwen Jiang, Tingting Liu, Shaodong Sun, Anran Chen, Hua Zhang","doi":"10.1021/acscatal.4c07849","DOIUrl":"https://doi.org/10.1021/acscatal.4c07849","url":null,"abstract":"Implementing the hydrogen economy requires reducing the energy costs of electrocatalytic water splitting, thus making it crucial to design low-cost and high-efficiency electrocatalysts to minimize the needed overpotential for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Here, we propose a non-noble metal bifunctional electrocatalyst (HS Co<sub>3</sub>S<sub>4</sub>) with a high-spin state by adjusting the coordination structure of spinel sulfide (Co<sub>3</sub>S<sub>4</sub>). An analysis based on crystal field theory, molecular orbital theory, and density functional theory revealed that the unpaired electrons in the low-coordination Co in HS Co<sub>3</sub>S<sub>4</sub> occupied the high-energy e<sub>g</sub>* orbitals, resulting in a high-spin state. This unpaired electron in a high-spin state accelerates the transfer of electrons from the catalyst to the reaction intermediate, reducing the activation energy required for the electrocatalytic reaction and facilitating the HER and OER. The developed HS Co<sub>3</sub>S<sub>4</sub> catalyst requires overpotentials of 70 and 222 mV to drive a current density of 10 mA cm<sup>–2</sup> for HER and OER, respectively. An anion exchange membrane water electrolyzer with this catalyst requires only 1.78 V to achieve an industrial-level current density of 1 A cm<sup>–2</sup>, and it can operate stably for 1000 h. This work provides a promising strategy to regulate the electron spin state of low-cost catalysts for large-scale hydrogen production.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"153 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144154050","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
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