ACS Catalysis 最新文献

Suzuki–Miyaura Cross-Couplings of Alkylboranes: Transmetalation Studies and Synthesis of Model Organopalladium Pretransmetalation Species 烷基硼烷的铃木-宫浦交叉耦合：反金属化研究和有机钯预反金属化物种模型的合成

IF 12.9 1区化学

ACS Catalysis Pub Date : 2024-10-12 DOI: 10.1021/acscatal.4c05053

Angus Olding, Curtis C. Ho, Nigel T. Lucas, Brian F. Yates, Allan J. Canty, Alex C. Bissember

{"title":"Suzuki–Miyaura Cross-Couplings of Alkylboranes: Transmetalation Studies and Synthesis of Model Organopalladium Pretransmetalation Species","authors":"Angus Olding, Curtis C. Ho, Nigel T. Lucas, Brian F. Yates, Allan J. Canty, Alex C. Bissember","doi":"10.1021/acscatal.4c05053","DOIUrl":"https://doi.org/10.1021/acscatal.4c05053","url":null,"abstract":"This report investigates the transmetalation of B-alkyl-9-borabicyclo[3.3.1]nonane (B-alkyl-9-BBN) coupling partners in Csp2–Csp3 Suzuki–Miyaura (SM) reactions. Kinetically stable, model organopalladium(II) SM pretransmetalation intermediates were synthesized, which enabled comprehensive X-ray crystallographic and NMR spectroscopic characterization of these elusive species at last. Computational studies of kinetically relevant systems were consistent with transmetalation proceeding with retention of configuration with respect to the carbon atom via a frontside SE2 (coordination) mechanism. This is proposed to involve a four-membered transition state with electron transfer into the vacant palladium dx2–y2 orbital. Furthermore, integrated theoretical and experimental results indicated that in the presence of hydroxide in THF/water mixtures, catalytic turnover is kinetically favored via anionic transmetalation path A, which involves the initial reaction of [Pd(Ph)(PPh3)2Br] with [B-alkyl-9-BBN(OH)]−, over neutral path B, which requires initial formation of [Pd(Ph)(PPh3)2OH] then reaction with B-alkyl-9-BBN. It is notable that in path A, the conversion of [Pd(Ph)(PPh3)2Br] to the phenylpalladium(II) boronate pretransmetalation species only appears to be feasible if phosphine ligand exchange with [B-alkyl-9-BBN(OH)]− precedes the loss of bromide. It is likely that these nuances derive, at least partly, from the very high Lewis acidity and steric bulk of the boron center within B-alkyl-9-BBN and its derivatives.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142415615","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

Molecular Understanding of Heterogeneous Hydroformylation on Rh1/CeO2: Morphology Effects 对 Rh1/CeO2 上异质加氢甲酰化的分子理解：形态学效应

IF 12.9 1区化学

ACS Catalysis Pub Date : 2024-10-12 DOI: 10.1021/acscatal.4c04921

Boyang Liu, Yifan Sun, Muhan Li, Zhangxinyu Fan, Xiao Chen, Xiaocheng Lan, Qin Zhong, Tiefeng Wang

引用次数: 0

Engineering the Atomic Configurations of Surface-Active Sites for Retuning the Photoreduction CO2 Selectivity 改造表面活性位点的原子构型，重新调整光氧化 CO2 选择性

IF 12.9 1区化学

ACS Catalysis Pub Date : 2024-10-11 DOI: 10.1021/acscatal.4c03304

Min Shen, Yan Ye, Mingyue Wang, Xiaocong Liang, Hao Tang, Yulan Wang, Chuchu Zhou, Shilan Zhang, Sikang Xue, Can Yang, Wandong Xing, Zhiyang Yu

引用次数: 0

Efficient Dehydration of 1-Phenylethanol to Styrene by Copper(II) and Zinc(II) Fused-Bisoxazolidine Catalysts 铜（II）和锌（II）熔融双噁唑烷催化剂将 1-苯乙醇高效脱水成苯乙烯的过程

IF 12.9 1区化学

ACS Catalysis Pub Date : 2024-10-11 DOI: 10.1021/acscatal.4c04572

Aurodeep Panda, Caroline R. Wood, William W. Brennessel, William D. Jones

引用次数: 0

Tuning the Reconstruction of Metal–Organic Frameworks during the Oxygen Evolution Reaction 在氧进化反应中调整金属有机框架的重构

IF 12.9 1区化学

ACS Catalysis Pub Date : 2024-10-11 DOI: 10.1021/acscatal.4c03618

Xiaoxin Ma, Lena Schröck, Guanhui Gao, Qing Ai, Maider Zarrabeitia, Caiwu Liang, Mian Zahid Hussain, Rachit Khare, Kun-Ting Song, Daniel J. Zheng, Max Koch, Ifan E. L. Stephens, Shujin Hou, Yang Shao-Horn, Julien Warnan, Aliaksandr S. Bandarenka, Roland A. Fischer

{"title":"Tuning the Reconstruction of Metal–Organic Frameworks during the Oxygen Evolution Reaction","authors":"Xiaoxin Ma, Lena Schröck, Guanhui Gao, Qing Ai, Maider Zarrabeitia, Caiwu Liang, Mian Zahid Hussain, Rachit Khare, Kun-Ting Song, Daniel J. Zheng, Max Koch, Ifan E. L. Stephens, Shujin Hou, Yang Shao-Horn, Julien Warnan, Aliaksandr S. Bandarenka, Roland A. Fischer","doi":"10.1021/acscatal.4c03618","DOIUrl":"https://doi.org/10.1021/acscatal.4c03618","url":null,"abstract":"Recently, there has been growing interest in the conversion of metal–organic frameworks (MOFs) into metal-hydroxide catalysts for alkaline oxygen evolution reactions (OERs). While studies have shown that the initial OER performance of MOF-derived intermediates surpasses that of traditional metal-hydroxide catalysts, ongoing debates persist regarding these catalysts' durability and electrochemical stability. Moreover, the inevitable reorganization (aging) of MOF-derived catalysts from disordered to ordered phases, particularly those primarily composed of nickel oxyhydroxides, remains a topic of discussion. To address these issues, we propose a straightforward approach to mitigating MOF reconstruction and modulating aging in harsh alkaline environments by introducing additional organic carboxylate linkers into electrolytes. Specifically, we focus on two examples: Ni-BPDC-MOFs and NiFe-BPDC-MOFs, of formula [M2(OH)2BPDC] (M: Ni and Fe; BPDC = 4,4′-biphenyldicarboxylate). Experimental results indicate that alkaline electrolytes containing additional BPDC linkers exhibit enhanced OER activity and a prolonged electrochemical lifespan. Complemented by in situ Raman spectroscopy, our findings suggest that manipulating the coordination equilibrium of the organic linker involved in Ni-MOF formation (linker assembly) and reconstruction (linker leaching) leads to the formation of more disordered nickel oxyhydroxide phases as the active catalyst material, which shows enhanced OER performance.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142405531","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

Pt1Bi Single-Atom Alloy for a Coupled Photocatalytic CO2 Reduction and Aryl Olefin Oxidation System 用于光催化二氧化碳还原和芳基烯烃氧化耦合系统的 Pt1Bi 单原子合金

IF 12.9 1区化学

ACS Catalysis Pub Date : 2024-10-11 DOI: 10.1021/acscatal.4c02868

Peng Bai, Yicheng Zhao, Yongdan Li

{"title":"Pt1Bi Single-Atom Alloy for a Coupled Photocatalytic CO2 Reduction and Aryl Olefin Oxidation System","authors":"Peng Bai, Yicheng Zhao, Yongdan Li","doi":"10.1021/acscatal.4c02868","DOIUrl":"https://doi.org/10.1021/acscatal.4c02868","url":null,"abstract":"Solar-driven CO2 reduction provides a promising strategy to produce fuels and value-added chemicals, while the efficiency and economy of the system are often limited by the coupled oxidation half-reaction. Here, we develop a synergistic system coupling photocatalytic CO2 reduction to CO and aryl olefin oxidation to aryl ketone with a high-efficiency and improved atom economy over a TiOx-supported Pt1Bi single-atom alloy photocatalyst. Combined experimental and computational studies elucidate the spontaneous electron transfer from Bi to Pt in the dark, which is enhanced under light radiation. Density functional theory calculations reveal that the oxidation process of aryl olefin favors the protonation of CO2 and the dissociation of COOH* to CO*, and Bi facilitates CO2 protonation and CO desorption on the Pt site. The generation rate of CO reaches 391 μmol g–1 h–1 with an electron selectivity of 91.4% using alpha-methylstyrene as the substrate, and the yield of the acetophenone product is 449 μmol g–1 h–1 with a 95.5% selectivity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142405633","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}

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Advances in Direct Fluoroalkylation of Organic Substrates with Partially Fluorinated Alkyl Motivs 有机底物与部分氟化烷基基团直接氟烷基化的研究进展

IF 12.9 1区化学

ACS Catalysis Pub Date : 2024-10-11 DOI: 10.1021/acscatal.4c04986

Sebastian Barata-Vallejo, Sergio M. Bonesi, Al Postigo

{"title":"Advances in Direct Fluoroalkylation of Organic Substrates with Partially Fluorinated Alkyl Motivs","authors":"Sebastian Barata-Vallejo, Sergio M. Bonesi, Al Postigo","doi":"10.1021/acscatal.4c04986","DOIUrl":"https://doi.org/10.1021/acscatal.4c04986","url":null,"abstract":"Partially fluorinated alkyl groups other than methyl are increasingly playing crucial roles in the development of fluorinated drugs with diverse biological activities, thus creating an innovative chemical space within organofluorine chemistry. For studies of structure–activity relationships, late-stage modification with such groups or substituents into substrates that bear biological activity is essential. This perspective will study catalytic protocols for the direct introduction of partially fluorinated alkyl groups such monofluoroalkylated (−CHFR, –CH2CH2F), difluoroalkylated (−CF2Me, –CH2CF2H), trifluoroalkylated (−CHR(CF3), –CH2CF3, –CH2CH2CF3, –CH(Me)CF3, –C(Me)2CF3), and pentafluoropropylated (−CH2C2F5) onto (hetero)aromatic compounds, double bonds, isonitriles, alkyl halides, and N, O, and S atoms.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142405532","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

Chelation and Stabilization of Dynamic Single- Atom Cu in Metal–Organic Frameworks for Selective Hydrogenation Reactions 金属有机框架中动态单原子铜的螯合与稳定，用于选择性氢化反应

IF 12.9 1区化学

ACS Catalysis Pub Date : 2024-10-10 DOI: 10.1021/acscatal.4c05097

Yushan Wu, Yawen Tong, Yao Luo, Junchen Xu, Xiang-Kui Gu, Mingyue Ding

{"title":"Chelation and Stabilization of Dynamic Single- Atom Cu in Metal–Organic Frameworks for Selective Hydrogenation Reactions","authors":"Yushan Wu, Yawen Tong, Yao Luo, Junchen Xu, Xiang-Kui Gu, Mingyue Ding","doi":"10.1021/acscatal.4c05097","DOIUrl":"https://doi.org/10.1021/acscatal.4c05097","url":null,"abstract":"Selective hydrogenation of unsaturated carbonyl compounds into alcohols is of great importance in the fine chemical industry. Herein, we reported a robust and reusable single-atom Cu catalyst, Cu1@MOF-303, fabricated by a covalent attachment of Cu atoms to the adjacent pair of unsaturated N atoms from two neighboring organic ligands in a metal–organic framework for the selective hydrogenation of aldehydes/ketones, exhibiting high activity with complete conversion and 95% selectivity accompanied by a high product formation rate of 23.6 h–1. A combination of experimental and theoretical studies revealed that the distinctive electronic and structural attributes rendered Cu1@MOF-303 capable of adsorbing targeted functional groups in reactants and desorbing desired products preferentially due to the atomically dispersed Cu species chelated and stabilized by N atoms as well as the dynamic changes by breaking the interfacial Cu–N bonds on reactant adsorption and making these bonds on product desorption, thereby enhancing the catalytic activity and stability.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142405534","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

Covalent Organic Framework-Derived B/N Co-Doped Carbon FLPs Metal-Free Catalysts for the Selective Hydrogenation of α,β-Unsaturated Aldehydes to Unsaturated Alcohols 共价有机框架衍生的 B/N 共掺杂碳 FLPs 用于将 α、β-不饱和醛选择性加氢转化为不饱和醇的无金属催化剂

IF 12.9 1区化学

ACS Catalysis Pub Date : 2024-10-10 DOI: 10.1021/acscatal.4c04537

Linhao Zhong, Xiaoqing Liao, Haishuai Cui, Jinmei Huang, He’an Luo, Yang Lv, Pingle Liu

{"title":"Covalent Organic Framework-Derived B/N Co-Doped Carbon FLPs Metal-Free Catalysts for the Selective Hydrogenation of α,β-Unsaturated Aldehydes to Unsaturated Alcohols","authors":"Linhao Zhong, Xiaoqing Liao, Haishuai Cui, Jinmei Huang, He’an Luo, Yang Lv, Pingle Liu","doi":"10.1021/acscatal.4c04537","DOIUrl":"https://doi.org/10.1021/acscatal.4c04537","url":null,"abstract":"An ongoing challenge is to precisely tailor the frustrated Lewis pairs (FLPs) sites to construct all-solid-state FLPs metal-free catalysts that are as effective as or even more effective than homogeneous/metal catalysts in H2 activation. In this study, B/N codoped carbon (SNW-BCN) catalysts were prepared by precisely tailoring FLPs sites by targeted doping of B atoms in the nitrogen-rich covalent organic framework (SNW-1) using the ligand-exchange strategy and self-templated carbonization. The catalysts were then applied in the selective hydrogenation of α,β-unsaturated aldehydes to unsaturated alcohols. It was found that a significant amount of pyridinic-N sites could be obtained from nitrogen-rich SNW-1. Moreover, targeted doping of B atoms can be accomplished by introducing organic ligands (4-formylphenylboronic acid) with Lewis acid heteroatoms to pre-empt the ligand site of SNW-1. Additionally, the B–N covalent bond, which preferentially forms between B and neighboring N at high temperature, can function as a Lewis acid site. DFT calculations and in situ characterizations show that the neighboring electron-rich pyridinic-N and the electron-deficient B–N site can form B–N/pyridinic-N FLPs sites, which can effectively activate H2 and the C═O of α,β-unsaturated aldehydes, with only 0.36 eV of H–H bond dissociation energy. This work encourages the environmentally friendly synthesis of unsaturated alcohols and offers fresh concepts for the development and synthesis of all-solid-state FLPs metal-free catalysts. Additionally, experiments on catalyst scale-up were also investigated because they might shed light on catalyst production on a large scale.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398244","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

Porous Cu1/TiO2–x Catalytic Binding Pocket for Near-Unity Nitrate-to-Ammonia Conversion 多孔 Cu1/TiO2-x 催化结合袋实现硝酸盐到氨气的近自然转化

IF 12.9 1区化学

ACS Catalysis Pub Date : 2024-10-10 DOI: 10.1021/acscatal.4c03006

Li-Ying Zhang, Wenzhe Shang, Sen Qiao, Wei Liu, Yantao Shi

{"title":"Porous Cu1/TiO2–x Catalytic Binding Pocket for Near-Unity Nitrate-to-Ammonia Conversion","authors":"Li-Ying Zhang, Wenzhe Shang, Sen Qiao, Wei Liu, Yantao Shi","doi":"10.1021/acscatal.4c03006","DOIUrl":"https://doi.org/10.1021/acscatal.4c03006","url":null,"abstract":"Electrocatalytic nitrate reduction reaction (NO3RR) provides unique opportunities to mitigate nitrate wastewater pollution and green ammonia production, yet the sluggish kinetics regarding 8e– transfer and collective activation of multiple reactants and intermediates remain a fundamental challenge. In this study, we present a cooperative catalyst design of atomically dispersed Cu1 species embedding onto reduced anatase TiO2–x with rich multistage pores and oxygen vacancies (POVs), affording the target POVs-Cuδ+-TiO2 with a multisite nature. Particularly, the oxygen vacancies and Cu1 sites in proximity feature a conformational enzyme-mimicking nanopocket, which essentially governs the binding fit of mutative nitrogenate intermediates in the context of synergistic catalysis. The POVs-Cuδ+-TiO2 delivers a near-unity Faradaic efficiency (product basis 95.0%) and remarkable ammonia yield rate up to 1321.2 μmol h–1 mgcat–1 at −0.7 V vs RHE. This study underscores the surface topography engineering on reduced metal oxides and the promising synergistic effects over the NO3RR electrocatalysis, providing a better alternative for nitrate wastewater pollution treatment and ammonia production.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398242","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