ACS Catalysis 最新文献_第3页

Synergistic Cobaloxime Catalysis for Photo-Dehydrogenative Transformations 协同钴肟催化光脱氢转化

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-05-29 DOI: 10.1021/acscatal.5c00343

Aindrila Mandal, Matthew Lim, Lili Zhang, Kuo-Wei Huang, Shashikant U. Dighe

引用次数: 0

Anomalous Enhancement of the Electrocatalytic Hydrogen Evolution Reaction in AuPt Nanoclusters AuPt纳米团簇中电催化析氢反应的异常增强

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-05-29 DOI: 10.1021/acscatal.4c07859

Jiahui Kang, Jan Kloppenburg, Jiali Sheng, Zhenyu Xu, Kristoffer Meinander, Hua Jiang, Zhong-Peng Lv, Esko I. Kauppinen, Qiang Zhang, Xi Chen, Milla Vikberg, Olli Ikkala, Miguel A. Caro, Bo Peng

{"title":"Anomalous Enhancement of the Electrocatalytic Hydrogen Evolution Reaction in AuPt Nanoclusters","authors":"Jiahui Kang, Jan Kloppenburg, Jiali Sheng, Zhenyu Xu, Kristoffer Meinander, Hua Jiang, Zhong-Peng Lv, Esko I. Kauppinen, Qiang Zhang, Xi Chen, Milla Vikberg, Olli Ikkala, Miguel A. Caro, Bo Peng","doi":"10.1021/acscatal.4c07859","DOIUrl":"https://doi.org/10.1021/acscatal.4c07859","url":null,"abstract":"Energy- and resource-efficient electrocatalytic water splitting is of paramount importance to enable hydrogen production. The best bulk catalyst for the hydrogen evolution reaction (HER), platinum, is one of the scarcest elements on Earth. The use of nanoclusters significantly reduces the amount of raw material required for HER, while nanoalloying further enhances performance by modulating hydrogen adsorption. However, the interplay between the atomic structure and HER performance in alloyed nanoclusters remains unclear. In this study, we report an anomalous HER enhancement at low and intermediate Au contents in monodisperse AuPt nanoclusters immobilized on carbon nanotubes. This enhancement is driven by the segregation of Au atoms toward the nanocluster surface and a synergistic effect, whereby the ability of surface Pt atoms to bind hydrogen is increased in the presence of adjacent Au atoms. This enhancement is noteworthy and “anomalous”, given that the overall hydrogen adsorption activity significantly decreases for pure Au nanoclusters compared to pure Pt nanoclusters. We rationalize these observations by combining extensive experimental characterization data with detailed atomistic simulations based on purpose-built machine learning interatomic potential and Markov-chain Monte Carlo simulations with variable chemical potential. The agreement between simulation and experiment allows us to develop a mechanistic understanding of the atomic-scale processes underlying the enhanced HER activity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"3 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165350","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

Peroxidation Activation of Ethane with Hydrogen and Oxygen by Au-Based MWW Zeolite Acidic Catalyst 金基MWW沸石酸性催化剂对乙烷氢氧过氧化活化的研究

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-05-29 DOI: 10.1021/acscatal.5c01446

Kui Xu, Yao Xiao, Sijia Liu, Guiying Wu, Bingbing Luo, Jingru Jin, Xianfeng Yi, Aoqiang Peng, Jianhong Gong, Anmin Zheng, Fang Jin

{"title":"Peroxidation Activation of Ethane with Hydrogen and Oxygen by Au-Based MWW Zeolite Acidic Catalyst","authors":"Kui Xu, Yao Xiao, Sijia Liu, Guiying Wu, Bingbing Luo, Jingru Jin, Xianfeng Yi, Aoqiang Peng, Jianhong Gong, Anmin Zheng, Fang Jin","doi":"10.1021/acscatal.5c01446","DOIUrl":"https://doi.org/10.1021/acscatal.5c01446","url":null,"abstract":"The oxidative activation of ethane to produce ethene and oxygenates has attracted wide interest. An alternative reaction process for peroxidation activation of ethane in the presence of H2 and O2 at mild temperatures is performed by Au-based MWW zeolite acidic catalysts to produce acetic acid and ethene without the COx generation. A nanometal oxide encapsulated Au nanoparticle catalyst was synthesized by homogeneously distributing Au nanoparticles on the atom-planting introduced TiOx or SnOx in the hydroxyl group of MWW zeolite. The Au cluster size, the catalyst Brønsted, and Lewis acidity determine the stability of in situ generated H2O2 and control acetic acid and ethene selectivity. We propose a heterogeneous catalytic mechanism in which the Au cluster can promote ethane activation through α-H cracking of the C–H bond; this activated ethane then interacts with hydroperoxyl radicals (HOO*) on the Au cluster surface or the hydroxyl radicals (OH*) from decomposition of the in situ generated H2O2, and ethylhydrogen peroxide and ethanol are formed as key reaction intermediates for acetic acid. The Au surface OH* can promote β-H scission of ethane dehydrogenation for ethene. The Brønsted acid and Au–Ti in aluminosilicate MWW zeolite can activate ethane at 623 K and stabilize hydroperoxyl radicals with an acetic acid productivity of 4.04 mol gAu–1 h–1 and 87.08% selectivity. At 823 K, Au–Sn in deborosilicate MWW zeolite promotes ethane dehydrogenation to ethene with a productivity of 4.33 mol gAu–1 h–1 and 98.5% selectivity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"5 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165386","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

Streamlined Carbonylation of Csp3–H Bonds: Divergent Synthesis of Diverse Carbonyl Compounds Csp3-H键的流线型羰基化：不同羰基化合物的发散合成

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-05-29 DOI: 10.1021/acscatal.5c02925

Le-Cheng Wang, Hefei Yang, Qiangwei Li, Xiao-Feng Wu

{"title":"Streamlined Carbonylation of Csp3–H Bonds: Divergent Synthesis of Diverse Carbonyl Compounds","authors":"Le-Cheng Wang, Hefei Yang, Qiangwei Li, Xiao-Feng Wu","doi":"10.1021/acscatal.5c02925","DOIUrl":"https://doi.org/10.1021/acscatal.5c02925","url":null,"abstract":"Transition metal-catalyzed carbonylation reactions present a promising strategy for synthesizing valuable carbonyl-containing compounds. However, a significant limitation is the need for stepwise optimization of reaction conditions for different carbonyl types due to the inherent reactivity differences among coupling partners. In this context, we introduce a general photochemical strategy that facilitates the efficient synthesis of a diverse range of carbonyl compounds. This approach minimizes the need for extensive optimization by maintaining consistent reaction conditions, effectively addressing the challenges posed by varying reactivity and providing a versatile tool for organic synthesis. Moreover, this mild and practical method establishes a distinctive approach for obtaining valuable carbonyl compounds from abundant and low-cost starting materials while showcasing its flexibility with various coupling partners. By leveraging readily available aliphatic C–H bonds, this protocol offers a complementary approach to traditional Csp3–H carbonylation, positioning it as a crucial asset in the research toolkit for carbonyl synthesis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"3 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144176705","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

Stability of Single Atom Alloys Catalyst: A Theoretical and Experimental Perspective 单原子合金催化剂的稳定性：理论和实验的观点

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-05-29 DOI: 10.1021/acscatal.5c01586

Tianwei He, Ran Shi, Tong Zhou, Alain Rafael Puente Santiago, Qingju Liu

{"title":"Stability of Single Atom Alloys Catalyst: A Theoretical and Experimental Perspective","authors":"Tianwei He, Ran Shi, Tong Zhou, Alain Rafael Puente Santiago, Qingju Liu","doi":"10.1021/acscatal.5c01586","DOIUrl":"https://doi.org/10.1021/acscatal.5c01586","url":null,"abstract":"Single-atom alloys (SAAs) catalysts, consisting of reactive metal atoms embedded within a less reactive metal host, have garnered significant attention due to their excellent catalytic activity, selectivity, and high atomic efficiency. However, at elevated temperatures, the migration and aggregation of single atoms can lead to catalyst deactivation. In operational environments, especially in the presence of oxidizing agents or reaction intermediates, surface reconstruction may further undermine the stability. The interaction between the doped metal atoms and the host metal surface is crucial for stabilizing single atoms and preventing aggregation. Despite substantial progress in this field, the factors influencing the stability of SAAs remain poorly understood. This review provides a timely and comprehensive overview of the key factors affecting the stability of SAAs, addressing both intrinsic structural stability and catalytic performance. Strategies to enhance SAAs stability, such as surface modification and optimization of the reaction conditions, are discussed in detail. Additionally, the roles of advanced characterization techniques and theoretical simulations in understanding SAAs stability and reaction mechanisms are explored. The review also highlights the challenges of scaling up SAAs for industrial applications and outlines future research directions for developing more stable and efficient SAAs. Overall, this work emphasizes the critical importance of stability for the practical application of SAAs catalysts from both theoretical and experimental perspectives.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"48 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144176709","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

Beyond Equilibrated Structures: Sequential Lattice Oxygen Evolution Shapes Mars–van Krevelen Catalytic Oxidation on β-MnO2(110) 超越平衡结构：顺序晶格析氧形成β-MnO2的Mars-van Krevelen催化氧化（110）

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-05-29 DOI: 10.1021/acscatal.5c00169

Yuan Fang, Bohua Wang, Zhangyun Liu, Zheng Chen, Mingfeng Li, Xin Xu

{"title":"Beyond Equilibrated Structures: Sequential Lattice Oxygen Evolution Shapes Mars–van Krevelen Catalytic Oxidation on β-MnO2(110)","authors":"Yuan Fang, Bohua Wang, Zhangyun Liu, Zheng Chen, Mingfeng Li, Xin Xu","doi":"10.1021/acscatal.5c00169","DOIUrl":"https://doi.org/10.1021/acscatal.5c00169","url":null,"abstract":"Catalytic oxidation on a large number of reducible transition metal oxides can be described by the Mars–van Krevelen (MvK) mechanism, wherein the redox behavior of lattice oxygen (Olat) plays a central role. As a result, the formation energy (Evac) of the oxygen vacancy (OV), typically derived from a stoichiometric or thermodynamically equilibrated surface, is widely used as a descriptor of the catalytic activity. However, this approach overlooks the dynamic evolution of the surface due to the continuous consumption of Olat during the reaction. In this work, using CO oxidation on β-MnO2(110) as a probe, we combine density functional theory and kinetic Monte Carlo simulations to demonstrate the importance of sequential consumption and regeneration of Olat in dictating catalytic performance. We find that Evac is not static but varies with OV concentration, altering the equilibrium between Olat reduction and regeneration. As the accumulation of OV shifts the reaction mechanism from being reduction-dominated to regeneration-dominated, the steady-state surface composition deviates significantly from the prediction based on the thermodynamic equilibrium model. Only by accounting for the dynamic variation of Olat can the simulated apparent activation energies and reaction orders be closely reconciled with experimental observations. This work challenges the traditional reliance on the initial Evac and offers a more accurate portrayal of catalytic oxidation within the MvK mechanism, which provides useful guidance for predicting and optimizing catalytic activity toward real-world applications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"57 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165381","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

Asymmetric Remote Leaving Group-Promoted Propargylic Substitution 不对称远离离去基促进丙炔取代

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-05-29 DOI: 10.1021/acscatal.5c01798

Yuan-Xiang Yang, Yi-Fan Wang, Guo-Qiang Lin, Zhi-Tao He

引用次数: 0

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":"CO2 reforming of tar is a promising pathway for the simultaneous conversion of undesirable tars and CO2 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 Al2O3 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 CO2 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 CO2 and provided higher quantities of active oxygen species for the gasification and elimination of surface carbon intermediates produced by toluene cleavage. In situ 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 para-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