ACS Catalysis 最新文献

Synthesis of (Z)-Allylsilanes by Cu-Catalyzed Regioselective Protosilylation of Allenes via a Single-Electron Process

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-01-25 DOI: 10.1021/acscatal.4c07488

Min Kim, Seongha Kim, Yurim Lee, Yunmi Lee, Sangwon Seo, Byunghyuck Jung

{"title":"Synthesis of (Z)-Allylsilanes by Cu-Catalyzed Regioselective Protosilylation of Allenes via a Single-Electron Process","authors":"Min Kim, Seongha Kim, Yurim Lee, Yunmi Lee, Sangwon Seo, Byunghyuck Jung","doi":"10.1021/acscatal.4c07488","DOIUrl":"https://doi.org/10.1021/acscatal.4c07488","url":null,"abstract":"Hydrosilylation of allenes has gained prominence as an economically viable method for preparing vinylsilanes or allylsilanes. However, development of transition metal (TM)-catalyzed hydrosilylation remains challenging owing to the difficulty in controlling the regioselectivity and stereoselectivity. Specifically, access to (Z)-allylsilanes via first-row TM-catalyzed hydrosilylation is limited by the lack of mechanistic diversity, indicating the need for unprecedented approaches to achieve this valuable yet underexplored chemical space. We herein present the Cu-catalyzed protosilylation of allenes in either organic solvent or water, which affords (Z)-allylsilanes in high yields, with up to >98:2 regioselectivity and (Z)-selectivity. In contrast to conventional TM-catalyzed hydrosilylation or Cu-catalyzed protosilylation, our process involves a single-electron pathway for inserting Cu–SiMe2Ph into the allene. Radical trap experiments and systematic computational studies support the proposed mechanism. Our method is gram-scalable, and the synthetic utility is demonstrated by the preparation of deuterium-incorporated (Z)-allylsilanes through reactions in D2O.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"2 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143031062","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

Harnessing Hydrogen Spillover by Lattice Strain for Enhanced Photocatalytic Hydrogen Evolution of ZnIn2S4

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-01-25 DOI: 10.1021/acscatal.4c07308

Fan Gao, Wen-Gang Cui, Xinqiang Wang, Zhenglong Li, Yongchang Chen, Zichao Shen, Ke Wang, Yong Gao, Jian Miao, Yaxiong Yang, Jian Chen, Shaohua Shen, Hongge Pan

{"title":"Harnessing Hydrogen Spillover by Lattice Strain for Enhanced Photocatalytic Hydrogen Evolution of ZnIn2S4","authors":"Fan Gao, Wen-Gang Cui, Xinqiang Wang, Zhenglong Li, Yongchang Chen, Zichao Shen, Ke Wang, Yong Gao, Jian Miao, Yaxiong Yang, Jian Chen, Shaohua Shen, Hongge Pan","doi":"10.1021/acscatal.4c07308","DOIUrl":"https://doi.org/10.1021/acscatal.4c07308","url":null,"abstract":"Hydrogen spillover has been believed to play an essential role in the reaction path in photocatalysis, yet its rational regulation remains a considerable challenge for the design of highly efficient photocatalysts. Herein, hydrogen spillover can be well regulated at ZnIn2S4 with surface decorated by cubic α-MoC1–x quantum dots (QDs) with different lattice strain (ZIS/QDs). With the increasing lattice strain of α-MoC1–x, the composite shows first increased and then decreased photocatalytic hydrogen evolution (PHE). Spectroscopic characterizations and calculation analysis indicate that PHE performance of ZIS/QDs is highly corelated with hydrogen spillover rather than charge transfer process. Further systematic investigations suggest that compressive lattice strain uplifts the Fermi level of α-MoC1–x and optimizes the interfacial spillover barrier between α-MoC1–x and ZnIn2S4, achieving well-manipulated hydrogen spillover and enhanced PHE performance. This work demonstrates a general design from the perspective of lattice strain to harness hydrogen spillover effect in heterogeneous interface for hydrogen generation.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"139 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143031061","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

Disentangling Plasmonic Enhancement of Electronic and Thermal Effects in Catalysis Using In Operando X-ray Diffraction

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-01-25 DOI: 10.1021/acscatal.4c06841

Rebeca Miyar, Ieng Wai Un, Shani Har Lavan, Yonatan Dubi, Joshua H. Baraban, Yonatan Sivan, Brian A. Rosen

{"title":"Disentangling Plasmonic Enhancement of Electronic and Thermal Effects in Catalysis Using In Operando X-ray Diffraction","authors":"Rebeca Miyar, Ieng Wai Un, Shani Har Lavan, Yonatan Dubi, Joshua H. Baraban, Yonatan Sivan, Brian A. Rosen","doi":"10.1021/acscatal.4c06841","DOIUrl":"https://doi.org/10.1021/acscatal.4c06841","url":null,"abstract":"Photocatalysis by illumination of plasmonic catalytic nanostructures may offer energetically efficient and highly selective alternatives to state-of-the-art thermocatalysis, which typically requires significant energy input for a high temperature operation. While many demonstrations of plasmonic photocatalysis exist, disagreement remains regarding the mechanism(s). Originally, nonthermal (so-called “hot”) carriers appeared responsible for the catalysis, but recently heating emerged as a likely primary mechanism. Distinguishing between these two mechanisms is difficult since it requires accurate knowledge of the catalyst temperature. Here, we report in operando X-ray diffraction under illumination to unambiguously determine the average temperature of the catalyst during CO oxidation by measuring lattice parameters of both the catalytic nanoparticles and their oxide support. By simultaneously measuring the reaction rate, we find that “hot” carriers play no role in this reaction with this catalyst. Our experimental design provides a generally applicable method for the determination of the catalytic mechanism and paves the way for future chemical studies of catalytic plasmonic nanostructures.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"41 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143031060","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

Rational Design of Core–Shell Structured Pd@MIL-100(Fe) for Efficient Visible Light-Initiated Syntheses of Secondary Amines from Nitro Aromatics and Benzyl Alcohols

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-01-24 DOI: 10.1021/acscatal.4c06074

Liangliang Hu, Hurunqing Liu, Zhaohui Li

{"title":"Rational Design of Core–Shell Structured Pd@MIL-100(Fe) for Efficient Visible Light-Initiated Syntheses of Secondary Amines from Nitro Aromatics and Benzyl Alcohols","authors":"Liangliang Hu, Hurunqing Liu, Zhaohui Li","doi":"10.1021/acscatal.4c06074","DOIUrl":"https://doi.org/10.1021/acscatal.4c06074","url":null,"abstract":"A rational design of MNPs@MOFs (MNPs = metal nanoparticles, MOFs = metal–organic frameworks) nanocomposites is important for their application as multifunctional catalysts for light-initiated one-pot tandem/cascade reactions. Herein, the Pd@MIL-100(Fe) nanocomposite with a core–shell structure, in which Pd colloids of ca. 3 nm are encapsulated inside the matrix of MIL-100(Fe), was constructed successfully via self-assembly of MIL-100(Fe) in preformed PVP-capped Pd colloids (PVP = polyvinylpyrrolidone) at room temperature. Via a successful combination of MOF-based photocatalysis with Pd-based hydrogenation, Pdrpvp@MIL-100(Fe), with PVP partially removed, exhibited superior performance for the reaction between nitro aromatics and benzyl alcohols to produce secondary amines. Comparison of activity over Pdrpvp@MIL-100(Fe) with that of the other two types of MNPs/MIL-100(Fe) nanocomposites suggests that its superior activity can be attributed to the presence of well-stabilized stable Pd nanoparticles (NPs) for hydrogenation and the unoccupied cavities in MOFs to promote the mass diffusion, especially in the case of larger substrates, as well as an efficient charge transfer from the MOF to Pd NPs for their cooperation. This study indicates that a rational strategy in the construction of metal NPs/MOFs nanocomposites is important for their application as multifunctional catalysts for light-initiated one-pot tandem/cascade reactions.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"52 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143027046","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

Identification of Intermetallic CoSb as a Cost-Effective and High-Performance Catalyst for Acetylene Semihydrogenation

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-01-24 DOI: 10.1021/acscatal.4c06028

Xiaohu Ge, Jinquan Ming, Yundao Jing, Nina Fei, Lingling Guo, Yueqiang Cao, Hao Jiang, Jing Zhang, Gang Qian, Xinggui Zhou, Xuezhi Duan

{"title":"Identification of Intermetallic CoSb as a Cost-Effective and High-Performance Catalyst for Acetylene Semihydrogenation","authors":"Xiaohu Ge, Jinquan Ming, Yundao Jing, Nina Fei, Lingling Guo, Yueqiang Cao, Hao Jiang, Jing Zhang, Gang Qian, Xinggui Zhou, Xuezhi Duan","doi":"10.1021/acscatal.4c06028","DOIUrl":"https://doi.org/10.1021/acscatal.4c06028","url":null,"abstract":"Designing high-efficiency and cost-effective catalysts for acetylene semihydrogenation holds significance for the production of polymer-grade ethylene in the chemical industry but remains difficult. In this study, we demonstrate an efficient synthesis of the CoSb intermetallic catalyst achieved through the in situ capture of molten Sb by Co, aiming to identify the Co-based catalysts for acetylene semihydrogenation. Combined investigations using X-ray diffraction, aberration-corrected high-resolution scanning transmission electron microscopy, and X-ray absorption spectroscopy demonstrate the presence of the pure CoSb intermetallic phase in the synthesized CoSb catalyst. The CoSb intermetallic catalyst, with a well-defined atomic arrangement and fine-regulated electronic properties, delivers 94.0% ethylene selectivity at ∼100% acetylene conversion. Temperature-programmed experiments and in situ spectroscopic studies, combined with theoretical calculations, unravel that the good hydrogenation performance arises from the moderate σ-binding of acetylene and easy desorption of ethylene on the fine-tuned Co active sites by Sb. These insights would be valuable for the creation of high-efficiency catalysts for acetylene semihydrogenation and potentially for other alkynes as well.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"34 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143027045","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

Data Science-Driven Discovery of Optimal Conditions and a Condition-Selection Model for the Chan–Lam Coupling of Primary Sulfonamides

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-01-24 DOI: 10.1021/acscatal.4c07972

Shivaani S. Gandhi, Giselle Z. Brown, Santeri Aikonen, Jordan S. Compton, Paulo Neves, Jesus I. Martinez Alvarado, Iulia I. Strambeanu, Kristi A. Leonard, Abigail G. Doyle

{"title":"Data Science-Driven Discovery of Optimal Conditions and a Condition-Selection Model for the Chan–Lam Coupling of Primary Sulfonamides","authors":"Shivaani S. Gandhi, Giselle Z. Brown, Santeri Aikonen, Jordan S. Compton, Paulo Neves, Jesus I. Martinez Alvarado, Iulia I. Strambeanu, Kristi A. Leonard, Abigail G. Doyle","doi":"10.1021/acscatal.4c07972","DOIUrl":"https://doi.org/10.1021/acscatal.4c07972","url":null,"abstract":"Secondary N-arylsulfonamides are common in pharmaceutical compounds owing to their valuable physicochemical properties. Direct N-arylation of primary sulfonamides presents a modular approach to this scaffold but remains a challenging disconnection for transition metal-catalyzed cross coupling broadly, including the Chan–Lam (CL) coupling of nucleophiles with (hetero)aryl boronic acids. Although the CL coupling reaction typically operates under mild conditions, it is also highly substrate-dependent and prone to overarylation, limiting its generality and predictivity. To address these gaps, we employed data science tools in tandem with high-throughput experimentation to study and model the CL N-arylation of primary sulfonamides. To minimize bias in training set design, we applied unsupervised learning to systematically select a diverse set of primary sulfonamides for high-throughput data collection and modeling, resulting in a novel data set of 3,904 reactions. This workflow enabled us to identify broadly applicable, highly selective conditions for the CL coupling of aliphatic and (hetero)aromatic primary sulfonamides with complex organoboron coupling partners. We also generated a regression model that successfully identifies not only high-yielding conditions for the CL coupling of various sulfonamides but also sulfonamide features that dictate reaction outcome.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"74 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143027047","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

CO2 Hydrogenation to Methanol on CoIn2/In2O3: The Role of the Alloy/Oxide Interface in Driving Catalytic Activity and Selectivity

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-01-24 DOI: 10.1021/acscatal.4c06851

Biao Gao, Bin Yang, Kazuto Hatakeyama, Yifu Wang, Longtai Li, Shintaro Ida, Tatsumi Ishihara, Limin Guo

{"title":"CO2 Hydrogenation to Methanol on CoIn2/In2O3: The Role of the Alloy/Oxide Interface in Driving Catalytic Activity and Selectivity","authors":"Biao Gao, Bin Yang, Kazuto Hatakeyama, Yifu Wang, Longtai Li, Shintaro Ida, Tatsumi Ishihara, Limin Guo","doi":"10.1021/acscatal.4c06851","DOIUrl":"https://doi.org/10.1021/acscatal.4c06851","url":null,"abstract":"CO2 catalytic hydrogenation to methanol is promising for CO2 utilization. In2O3-based catalysts are attracting much attention because of their high methanol selectivity. However, a low CO2 conversion rate limits the overall methanol yield. Herein, we developed the interface of the CoIn2 alloy and In2O3 oxide as a CoIn2/In2O3 catalyst and successfully achieved high performance for the hydrogenation of CO2 to methanol. Experimental and theoretical results indicated that the alloy/oxide interface is stable during the reaction atmosphere; the high performance arising from the electronic interaction between CoIn2 and In2O3, which improves the electron density at the CoIn2 interface, facilitates H2 dissociation, CO2 adsorption, and the hydrogenation of formate intermediates to methanol, which justifies the sustained high methanol selectivity and production rate. The optimized catalyst showed a methanol selectivity up to 74% and a high methanol space-time yield up to 0.69 gMeOHgcat–1h–1 at 5.0 MPa, H2/CO2 = 3:1, 300 °C and 36,000 mLgcat–1h–1.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"1 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143031066","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

Practical Synthesis of Chiral Ferrocenenylphosphino-Gold(I) Catalysts and NEST Analysis of the Enantioinduction

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-01-24 DOI: 10.1021/acscatal.4c07495

Pablo Mora, Imma Escofet, Maria Besora, Federica Cester Bonati, Antonio M. Echavarren

引用次数: 0

Enantioselective Synthesis of Axially Chiral Alkylidenecycloalkanes via Copper-Catalyzed Functionalization of Acyl Allenols

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-01-24 DOI: 10.1021/acscatal.4c06387

Baihui Gong, Qingbin Lu, Ruikang Sun, Zelin Li, Yihan Chen, Aijun Lin, Hequan Yao, Shang Gao

引用次数: 0

Molybdenum Single-Atom Solid-Acid Catalyst for the Hydrogen Evolution Reaction in the Alkaline Electrolyte

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-01-24 DOI: 10.1021/acscatal.4c05602

Guang Yang, Chunyu Zhang, Zhigang Chen, Juan Wang, Guoliang Gao, Zhiyun Li, Rong Huang, Yi Cui

{"title":"Molybdenum Single-Atom Solid-Acid Catalyst for the Hydrogen Evolution Reaction in the Alkaline Electrolyte","authors":"Guang Yang, Chunyu Zhang, Zhigang Chen, Juan Wang, Guoliang Gao, Zhiyun Li, Rong Huang, Yi Cui","doi":"10.1021/acscatal.4c05602","DOIUrl":"https://doi.org/10.1021/acscatal.4c05602","url":null,"abstract":"Tailoring the gradient-pH catalytic environment around single-atom centers is rather meaningful in water electrolysis. Herein, we report a two-step strategy including hydrothermal and electrochemical optimization to synthesize PO43– and AlOx– simultaneously coordinated Mo single-atom catalysts on carbon-coated Ni foam. The abundant bridging oxygen atoms between Mo and P/Al atoms result in appealing adsorption and activation of water reactant, as well as an energy-favorable hydrogen desorption behavior due to their solid-acid nature. Consequently, the well-designed Mo–P–Al@NF @NF single-atom solid-acid catalyst system exhibits a comparable hydrogen evolution reaction activity in 1.0 M KOH electrolyte with current response beginning at nearly zero overpotential, delivering a typical current density of 10 mA/cm2 only requiring overpotential of 48 mV. Moreover, it also shows comparable stability with negligible activity degradation after continuous hydrogen production over 100 h. Our work may provide a guideline for the development of single-atom solid-acid catalysts toward highly efficient water electrolysis and beyond.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"76 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143027015","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