ACS Catalysis 最新文献

{"title":"Oxidative Dehydrogenation of Ethane Combined with CO2 Splitting via Chemical Looping on In2O3 Modified with Ni–Cu Alloy","authors":"Kosuke Watanabe,&nbsp;Takuma Higo,&nbsp;Koki Saegusa,&nbsp;Sakura Matsumoto,&nbsp;Hiroshi Sampei,&nbsp;Yuki Isono,&nbsp;Akira Shimojuku,&nbsp;Hideki Furusawa and Yasushi Sekine*,&nbsp;","doi":"10.1021/acscatal.4c0773710.1021/acscatal.4c07737","DOIUrl":"https://doi.org/10.1021/acscatal.4c07737https://doi.org/10.1021/acscatal.4c07737","url":null,"abstract":"<p >Modified In₂O₃ has the potential to be a better oxygen storage material due to its readily reducible surface and abundant bulk lattice oxygen released with a marked valence change from In³⁺ to In⁰. This work describes that In₂O₃ modified with a Ni–Cu alloy supports a chemical looping system consisting of oxidative dehydrogenation of ethane and CO₂ splitting at the low temperature of 873 K with a large oxygen capacity (&gt;4 wt %). This reaction system is achieved through dynamic changes between Ni–Cu binary alloy and Ni–Cu–In ternary alloy associated with the redox of indium species. Meticulous material screening, characterization, and theoretical calculations have revealed that the Ni–Cu alloy promotes the redox of In₂O₃ by activating ethane and by incorporating reduced indium species.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 7","pages":"5876–5885 5876–5885"},"PeriodicalIF":11.3,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscatal.4c07737","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143767270","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"CO2 Reduction Over Iron–Nickel Alloy Catalysts─Tandem Effect of Support and Alloy Composition","authors":"Kin de Kock, Shaine Raseale, Wijnand Marquart, Thierry Verfaille, Michael Claeys, Nico Fischer","doi":"10.1021/acscatal.4c07514","DOIUrl":"https://doi.org/10.1021/acscatal.4c07514","url":null,"abstract":"The effect of the Fe:Ni ratio in metallic nanoalloys and the nature of metal oxide overlayer supports (MO_<i>x</i>@Al₂O₃) on catalytic activity, selectivity, and stability in the reverse water–gas shift reaction (RWGS) was investigated. To obtain the Fe_<i>y</i>Ni alloy phase, oxidic (Ni_<i>y</i>Fe_1–<i>y</i>)Fe₂O₄ precursor nanoparticles of varying composition were synthesized (Fe:Ni = 3, 4, and 6, as well as pure iron oxide) with a narrow size distribution and without the use of surfactants. The effect of the varying physical properties of the respective bulk oxides on catalyst performance was circumvented via the preparation of bespoke support materials by impregnating a γ-Al₂O₃ carrier with MO_<i>x</i> overlayers (<i>M</i> = Cr or Ga). The surface of the prepared materials is related to the chemical and electronic properties of the respective MO_<i>x</i>, but the pore geometry of γ-Al₂O₃ is maintained. An inert high-surface-area SiO₂ support material was also tested to isolate the performance of the Fe_<i>y</i>Ni phases. The reduced catalysts contain a mixture of the bcc and fcc alloy phases irrespective of the support material. The relative concentrations of each phase are a function of iron content, with an increase in iron content increasing the concentration of the bcc alloy phase. The bcc phase has a high affinity toward reoxidation via CO₂ activation, while the fcc phase was only found to be partially reoxidized at elevated temperatures (above 600 °C). When exposed to RWGS conditions, all samples tested show &gt;99.5% CO selectivity. The SiO₂-supported samples deactivate rapidly, while the alloys supported on the MO_<i>x</i>@Al₂O₃ overlayers, specifically when supported on CrO_<i>x</i>@Al₂O₃, form a tandem system, supporting high activity and stability. The catalytic performance is dependent on both the alloy composition and the MO_<i>x</i> support, with the surprising observation of a reversal of the trend in activity with iron content between CrO_<i>x</i>@Al₂O₃ and GaO_<i>x</i>@Al₂O₃. Spent catalyst characterization showed that the rapid deactivation seen on SiO₂ cannot be explained by sintering, oxidation, or carbon deposition. The deactivation is instead attributed to the consumption of the bcc phase under reaction conditions. The results show that there is a beneficial interaction between the fcc phase, an exsoluted amorphous Fe-oxide formed from the bcc phase, and the active support, which enhances the catalytic performance in the RWGS.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"183 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703268","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}

{"title":"Late-Stage N-Atom Deletion of Multisubstituted 2-Azabicyclo[2.1.1]Hexanes","authors":"Ken Lin,&nbsp;Qi Sun,&nbsp;Pengcheng Tang,&nbsp;Saizhou Wang,&nbsp;Mengjie Jiao,&nbsp;Tao Zhang* and Hongjian Lu*,&nbsp;","doi":"10.1021/acscatal.5c0173410.1021/acscatal.5c01734","DOIUrl":"https://doi.org/10.1021/acscatal.5c01734https://doi.org/10.1021/acscatal.5c01734","url":null,"abstract":"<p >Rigid three-dimensional scaffolds such as 2-azabicyclo[2.1.1]hexanes (aza-BCHs) and bicyclo[1.1.1]pentanes (BCPs) serve as unique saturated isosteres of arenes, offering distinct substitution patterns due to their differing molecular exit vectors. This study introduces a skeletal editing strategy that efficiently transforms multisubstituted aza-BCHs into BCPs via an O-diphenylphosphinylhydroxylamine-promoted N-atom deletion process. This method effectively addresses the challenge of creating sterically hindered (2°)C–C(3°) bonds by removing a nitrogen atom encased within bulky alkyl groups, and reconstructing the strained aza-BCH structure into a more strained BCP without generating undesired ring-opening diene byproducts. The aza-BCHs used can be prepared from a modified intermolecular [3 + 2] cycloaddition between bicyclo[1.1.0]butanes and imines, making this method practical. This approach achieves remarkable efficiency, with yields up to 99% and scalability to decagram quantities. The resulting BCP carboxylates can be further functionalized through decarboxylation, highlighting the potential for programmed and divergent synthesis of multisubstituted BCPs. The broad substrate scope and high functional group tolerance of this protocol emphasize its versatility, making it particularly valuable for late-stage skeletal editing of aza-BCHs contained peptides, natural products, and pharmaceuticals.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 7","pages":"5825–5834 5825–5834"},"PeriodicalIF":11.3,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143767376","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}

{"title":"Influence of Local Chemical Environment on the Catalytic Properties of Ir1/CeO2 Single-Atom Catalysts in CO Oxidation","authors":"Carlo Federico Pauletti, Matteo Farnesi Camellone, Simone Piccinin","doi":"10.1021/acscatal.5c01147","DOIUrl":"https://doi.org/10.1021/acscatal.5c01147","url":null,"abstract":"Supported single-atom catalysts (SACs) are of great interest in catalysis due to their highly efficient use of costly noble metals and unique reactivities, which are deeply influenced by the local coordination environment of the active site. Herein, the catalytic properties of single Ir adatoms on CeO₂ have been simulated at finite temperature with ab initio thermodynamics and microkinetic modeling, deriving analytical expressions for the turnover frequency of the catalyst at different operative regimes, compatible with experimental conditions. According to our findings, the adsorption geometry of single Ir adatoms on CeO₂ is governed by the surface termination, resulting in remarkably different catalytic activities: on the (110) surface, the high stability of square-planar IrO_<i>x</i>(CO)_<i>y</i> units results in a high propensity toward CO poisoning. On the (111) surface, the local environment of the Ir adatom allows for a greater number of ligands, resulting in greater catalytic activity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"57 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703278","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}

{"title":"Late-Stage N-Atom Deletion of Multisubstituted 2-Azabicyclo[2.1.1]Hexanes","authors":"Ken Lin, Qi Sun, Pengcheng Tang, Saizhou Wang, Mengjie Jiao, Tao Zhang, Hongjian Lu","doi":"10.1021/acscatal.5c01734","DOIUrl":"https://doi.org/10.1021/acscatal.5c01734","url":null,"abstract":"Rigid three-dimensional scaffolds such as 2-azabicyclo[2.1.1]hexanes (aza-BCHs) and bicyclo[1.1.1]pentanes (BCPs) serve as unique saturated isosteres of arenes, offering distinct substitution patterns due to their differing molecular exit vectors. This study introduces a skeletal editing strategy that efficiently transforms multisubstituted aza-BCHs into BCPs via an O-diphenylphosphinylhydroxylamine-promoted N-atom deletion process. This method effectively addresses the challenge of creating sterically hindered (2°)C–C(3°) bonds by removing a nitrogen atom encased within bulky alkyl groups, and reconstructing the strained aza-BCH structure into a more strained BCP without generating undesired ring-opening diene byproducts. The aza-BCHs used can be prepared from a modified intermolecular [3 + 2] cycloaddition between bicyclo[1.1.0]butanes and imines, making this method practical. This approach achieves remarkable efficiency, with yields up to 99% and scalability to decagram quantities. The resulting BCP carboxylates can be further functionalized through decarboxylation, highlighting the potential for programmed and divergent synthesis of multisubstituted BCPs. The broad substrate scope and high functional group tolerance of this protocol emphasize its versatility, making it particularly valuable for late-stage skeletal editing of aza-BCHs contained peptides, natural products, and pharmaceuticals.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"35 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703280","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}

{"title":"Influence of Local Chemical Environment on the Catalytic Properties of Ir1/CeO2 Single-Atom Catalysts in CO Oxidation","authors":"Carlo Federico Pauletti,&nbsp;Matteo Farnesi Camellone and Simone Piccinin*,&nbsp;","doi":"10.1021/acscatal.5c0114710.1021/acscatal.5c01147","DOIUrl":"https://doi.org/10.1021/acscatal.5c01147https://doi.org/10.1021/acscatal.5c01147","url":null,"abstract":"<p >Supported single-atom catalysts (SACs) are of great interest in catalysis due to their highly efficient use of costly noble metals and unique reactivities, which are deeply influenced by the local coordination environment of the active site. Herein, the catalytic properties of single Ir adatoms on CeO₂ have been simulated at finite temperature with ab initio thermodynamics and microkinetic modeling, deriving analytical expressions for the turnover frequency of the catalyst at different operative regimes, compatible with experimental conditions. According to our findings, the adsorption geometry of single Ir adatoms on CeO₂ is governed by the surface termination, resulting in remarkably different catalytic activities: on the (110) surface, the high stability of square-planar IrO_<i>x</i>(CO)_<i>y</i> units results in a high propensity toward CO poisoning. On the (111) surface, the local environment of the Ir adatom allows for a greater number of ligands, resulting in greater catalytic activity.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 7","pages":"5806–5824 5806–5824"},"PeriodicalIF":11.3,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143767325","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}

{"title":"Asymmetric Trapping of Siloxyketenes In Situ Generated from [1,3]-Silyl Migration of α-Ketoacylsilanes: A Visible-Light-Driven Palladium-Catalyzed [4 + 2] Cycloaddition","authors":"Lingyun Yao, Xinlan Zou, Jian Zhang, Yang-Zi Liu, Quannan Wang, Hanliang Zheng, Xusheng Shao, Wei-Ping Deng","doi":"10.1021/acscatal.5c01239","DOIUrl":"https://doi.org/10.1021/acscatal.5c01239","url":null,"abstract":"The transition metal-catalyzed asymmetric [<i>n</i> + 2] cycloaddition reaction with oxy-substituted ketene intermediates remains a synthetic challenge due to the limited availability of suitable ketene precursors. Herein, we report a visible-light-driven, palladium-catalyzed asymmetric [4 + 2] cycloaddition of vinyl benzoxazinanones with siloxyketene intermediates, generating structurally diverse chiral quinolinone derivatives with satisfactory diastereo- and enantioselectivities. The transient generation of siloxyketenes from α-ketoacylsilylanes through visible-light-induced Brook rearrangement is important for the success of the present cycloaddition. The ¹³C-labeling experiments reveal a Brook rearrangement pathway involving a [1,3]-silyl migration process. The side arm effects of BOX ligand and silyl steric hindrance of α-ketoacylsilanes play crucial roles in the stereoselectivity control, and theoretical calculations provide crucial insights into the stereochemical outcome in the reaction.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"24 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695885","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}

{"title":"Asymmetric Trapping of Siloxyketenes In Situ Generated from [1,3]-Silyl Migration of α-Ketoacylsilanes: A Visible-Light-Driven Palladium-Catalyzed [4 + 2] Cycloaddition","authors":"Lingyun Yao,&nbsp;Xinlan Zou,&nbsp;Jian Zhang,&nbsp;Yang-Zi Liu,&nbsp;Quannan Wang*,&nbsp;Hanliang Zheng*,&nbsp;Xusheng Shao and Wei-Ping Deng*,&nbsp;","doi":"10.1021/acscatal.5c0123910.1021/acscatal.5c01239","DOIUrl":"https://doi.org/10.1021/acscatal.5c01239https://doi.org/10.1021/acscatal.5c01239","url":null,"abstract":"<p >The transition metal-catalyzed asymmetric [<i>n</i> + 2] cycloaddition reaction with oxy-substituted ketene intermediates remains a synthetic challenge due to the limited availability of suitable ketene precursors. Herein, we report a visible-light-driven, palladium-catalyzed asymmetric [4 + 2] cycloaddition of vinyl benzoxazinanones with siloxyketene intermediates, generating structurally diverse chiral quinolinone derivatives with satisfactory diastereo- and enantioselectivities. The transient generation of siloxyketenes from α-ketoacylsilylanes through visible-light-induced Brook rearrangement is important for the success of the present cycloaddition. The ¹³C-labeling experiments reveal a Brook rearrangement pathway involving a [1,3]-silyl migration process. The side arm effects of BOX ligand and silyl steric hindrance of α-ketoacylsilanes play crucial roles in the stereoselectivity control, and theoretical calculations provide crucial insights into the stereochemical outcome in the reaction.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 7","pages":"5796–5805 5796–5805"},"PeriodicalIF":11.3,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143767324","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}

{"title":"Steering the Selectivity of Electrochemical CO2 Reduction on the Cu Catalyst via the Interplay between the Electrode Morphology and Electrolyte Anion Identity","authors":"Cornelius A. Obasanjo, Gelson T. S. T. da Silva, Fatima Gonzalez Marin, Lucia H. Mascaro, Cao-Thang Dinh","doi":"10.1021/acscatal.4c08113","DOIUrl":"https://doi.org/10.1021/acscatal.4c08113","url":null,"abstract":"Electrochemical carbon dioxide (CO₂) reduction (ECR) holds promise as a viable pathway for the generation of fuels and chemicals. Several strategies have been explored to enhance the product selectivity of ECR on copper (Cu) catalysts. A systematic approach to optimize the local reaction microenvironment, however, remains elusive. Engineering the electrode structure and reaction microenvironment is a facile but effective strategy for steering the product selectivity of ECR reactions and can enable the rational design of highly selective Cu electrodes. Herein, we demonstrate that the synergy between an optimized Cu gas diffusion electrode (GDE) morphology and electrolyte anion identity can steer ECR product selectivity toward ethylene (C₂₊) or methane via the local CO₂ availability, pH, and electrode morphology regulation. We show that using a relatively thin 100 nm Cu catalyst layer (CL) sputtered on an optimized macropore-sized hydrophobic poly(tetrafluoroethylene) substrate promotes methane selectivity at high reaction rates. We achieved a methane partial current density of 126 mA cm^–2 and a Faradaic efficiency (FE) of 42%. In contrast, a relatively thick 500 nm Cu CL favors ethylene production, reaching a high FE of 52% at 250 mA cm^–2 (with a total C₂₊ value of 77%) in a near-neutral KHCO₃ electrolyte. Utilizing KI electrolyte significantly enhances methane selectivity, achieving ca. 56% at a partial current density of 168 mA cm^–2 while effectively suppressing the hydrogen evolution reaction (HER) on the thin CL. Furthermore, on the relatively thick CL, a higher C₂₊ FE of 84% was achieved at 250 mA cm^–2, demonstrating the impact of electrolyte anion identity and CL thickness on product selectivity in ECR. In addition, we find that a further increase in the Cu CL thickness does not result in a superior C₂₊ performance in KI compared to the KHCO₃ electrolyte. Our result highlights the critical role of the interplay between Cu electrode morphology and the electrolyte anion identity, which can facilitate efficient CO₂ mass transport, enable selective Cu sites, and tune local pH – thereby steering ECR product selectivity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"97 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678085","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}

{"title":"Covalent Organic Frameworks Enhance Photocatalytic Hydrogen Peroxide Production through Synergistic Effects","authors":"Lin Wang, Changzhi Han, Shiyong Gao, Jia-Xing Jiang, Yong Zhang","doi":"10.1021/acscatal.4c08060","DOIUrl":"https://doi.org/10.1021/acscatal.4c08060","url":null,"abstract":"Covalent organic frameworks (COFs) are promising photocatalytic materials due to their high crystallinity, ordered porous structures, and customizable functionality. However, their photocatalytic performance is often hampered by challenges such as charge carrier recombination and suboptimal reactant adsorption. In this study, we aim to enhance the photocatalytic hydrogen peroxide production performance by introducing fluorine atoms into the pore walls of an imine-bonded COF, synthesizing two imine-bonded COFs: HITMS-COF-20 and HITMS-COF-21. The high electronegativity and small atomic size of fluorine atoms significantly improve light absorption, exciton delocalization, charge-carrier separation, and oxygen molecule adsorption. Analyses revealed that fluorine doping reduces charge recombination and enhances oxygen activation, thereby improving hydrogen peroxide production efficiency. These findings provide important insights into the mechanism of photocatalytic hydrogen peroxide production in COFs and offer pathways for the design of advanced photocatalysts for chemical synthesis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"183 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678087","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}