ACS Catalysis 最新文献_第4页

Nucleophilic Sulfur Dioxide Insertion-Enabled Enantioselective Michael Additions to Access α-Chiral Sulfones 亲核二氧化硫插入使能对映选择性Michael加成物以获得α-手性砜

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-10-06 DOI: 10.1021/acscatal.5c06163

Xinhua Wang, Yuyuan Mao, Shengqing Ye, Xiaoyu Zhou, Jie Wu, Shaoyu Li

引用次数: 0

Synergistic Band Gap Narrowing and Interfacial Electron Flow in Pd-Embedded NiCo-LDH for High-Efficiency Glycerol Electrooxidation pd包埋NiCo-LDH用于甘油高效电氧化的协同带隙缩小和界面电子流

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-10-06 DOI: 10.1021/acscatal.5c04378

Fazhan Sun, Guihao Liu, Tianqi Nie, Zhaohui Wu, Yihang Hu, Ziheng Song, Yu-Fei Song

{"title":"Synergistic Band Gap Narrowing and Interfacial Electron Flow in Pd-Embedded NiCo-LDH for High-Efficiency Glycerol Electrooxidation","authors":"Fazhan Sun, Guihao Liu, Tianqi Nie, Zhaohui Wu, Yihang Hu, Ziheng Song, Yu-Fei Song","doi":"10.1021/acscatal.5c04378","DOIUrl":"https://doi.org/10.1021/acscatal.5c04378","url":null,"abstract":"Synergistic processes of oxidation and adsorption of glycerol as a nucleophilic reagent during electrooxidation are of great importance, underscoring the need for a more comprehensive understanding of the adsorption and oxidation processes during glycerol electrooxidation. Herein, a unique structure of PdNP/NiCo, in which the Pd nanoparticles (NPs) (2.38 nm) were embedded in NiCo-layered double hydroxides (NiCo-LDH, denoted as NiCo), was constructed to synergistically enhance the oxidation and adsorption of glycerol molecules through narrowing the band gap and promoting the electronic metal–support interaction (EMSI)-induced interfacial electron-directed flow of the catalyst. The PdNP/NiCo achieved outstanding glycerol oxidation reaction (GOR) performance, requiring only 1.30 and 1.36 V (vs RHE) to achieve current densities of 10 mA cm–2 and 100 mA cm–2, respectively. Furthermore, comprehensive experimental and spectroscopic characterization confirmed that the successful embedding of Pd NPs into the NiCo-LDH effectively induced band gap narrowing of NiCo from 2.85 to 2.30 eV and promoted the formation of the oxidatively active Ni3+–O species, thereby enhancing the electrooxidation process. Concurrently, the incorporated Pd nanoparticles significantly improved the glycerol adsorption capacity. The density functional theory (DFT) calculations revealed a significantly lower deprotonation energy barrier of 0.15 eV and easier generation of the active species Ni3+–O for PdNP/NiCo compared to NiCo. In addition, the glycerol molecules located at the Pd–NiCo interface showed the most negative adsorption energy barrier compared with those of NiCo and Pd NPs, which was due to the strong electronic metal–support interaction (EMSI) at the interface between Pd NPs and NiCo-LDH.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"86 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145235248","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

Enhanced Electron Transfer via RuO2/TiO2 Lattice Matching Drives High-Performance Deacon Catalysis 通过RuO2/TiO2晶格匹配增强电子转移驱动高性能执事催化

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-10-06 DOI: 10.1021/acscatal.5c04277

Yuchen Zhang, Songpei Zhang, Yuxue Yue, Mingyi Xiao, Guangyu Cheng, Yilun Pan, Shitong Liu, Chunfa Li, Jia Zhao, Xiaonian Li

引用次数: 0

Correction to “Mechanism of Bicarbonate-Enhanced Solar Oxidation of Water to Hydrogen Peroxide over BiVO4” 对“碳酸氢盐增强水在BiVO4上太阳氧化生成过氧化氢的机理”的修正

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-10-06 DOI: 10.1021/acscatal.5c05896

Payal Chaudhary, Vitaly Alexandrov

引用次数: 0

Prospects for Forming C–N Bonds from Dinitrogen 二氮形成C-N键的前景

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-10-06 DOI: 10.1021/acscatal.5c05366

Nereida Hidalgo, Ryan Walser-Kuntz, Patrick L. Holland

引用次数: 0

Photoinduced and Copper-Catalyzed Asymmetric Alkylation of Glycine Derivatives via a Synergistic Electron/Atom Transfer Process 通过协同电子/原子转移过程光诱导和铜催化的甘氨酸衍生物的不对称烷基化

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-10-06 DOI: 10.1021/acscatal.5c05723

Qingsong Zhou, Yixuan Zhang, Jinlong Shang, Rupeng Qi, Xiaoyu Ren, Zhaoqing Xu, Chao Wang

{"title":"Photoinduced and Copper-Catalyzed Asymmetric Alkylation of Glycine Derivatives via a Synergistic Electron/Atom Transfer Process","authors":"Qingsong Zhou, Yixuan Zhang, Jinlong Shang, Rupeng Qi, Xiaoyu Ren, Zhaoqing Xu, Chao Wang","doi":"10.1021/acscatal.5c05723","DOIUrl":"https://doi.org/10.1021/acscatal.5c05723","url":null,"abstract":"As a fundamental building block for unnatural amino acids, photoinduced stereoselective functionalization at glycine’s C(sp3)–H bond provides a mild and effective route to synthesize aliphatic unnatural amino acids. Despite significant progress, developing alkylating reagents that avoid prefunctionalization and are readily available remains challenging. Herein, we report a photoinduced synergistic catalytic strategy merging single-electron transfer and atom transfer to efficiently achieve stereoselective cross-coupling between glycine derivatives and inactivated hydrocarbons or alkyl iodides. The key advantages of this strategy are 3-fold: 1) employing aryl sulfonium salts as aryl radical precursors demonstrates atom economy, with the additional benefits of straightforward synthesis and convenient recovery of raw materials; 2) the synergistic interplay between the photoreducing capability of dual-functional copper complexes and the atom-transfer proficiency of aryl radicals overcomes substrate redox potential limitations; and 3) the hydrogen atom abstraction capability of aryl radicals circumvents the requirement for strong external oxidants in conventional cross-dehydrogenative coupling reactions.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"21 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145235254","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 the Coordination Environment’s Impact on O–O Activation in Dicopper Enzymes: Computational Insights from AhyBURP Peptide Cyclase 解读配位环境对二铜酶O-O活化的影响：来自AhyBURP肽环化酶的计算见解

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-10-06 DOI: 10.1021/acscatal.5c05262

Yao Wu, Rulin Feng, Tai-Ping Zhou, Igor Ying Zhang, Binju Wang

{"title":"Deciphering the Coordination Environment’s Impact on O–O Activation in Dicopper Enzymes: Computational Insights from AhyBURP Peptide Cyclase","authors":"Yao Wu, Rulin Feng, Tai-Ping Zhou, Igor Ying Zhang, Binju Wang","doi":"10.1021/acscatal.5c05262","DOIUrl":"https://doi.org/10.1021/acscatal.5c05262","url":null,"abstract":"Copper active sites are pivotal in oxygen activation processes, generating diverse copper–oxygen species that drive various biological transformations. AhyBURP, a peptide cyclase, contains a dicopper active center that is involved in the biosynthesis of lyciumin I and legumenin. In this study, we employed a combined quantum mechanics/molecular mechanics (QM/MM) approach with the TPSS functional to elucidate the catalytic mechanism of AhyBURP. To rigorously assess the accuracy of these calculations─particularly for strongly correlated systems─we benchmarked the QM/MM results against the high-level multireference NEVPT2 method and the advanced DFT methods tB4LYP and R-xDH7, with an emphasis on strong correlation effects. Unlike conventional dicopper enzymes, AhyBURP is capable of mediating direct O–O bond cleavage within the μ-η2:η2-peroxide dicopper(II) species, yielding the active bis-μ-oxo dicopper(III) intermediate. This intermediate subsequently abstracts hydrogen atoms from both tryptophan and glycine substrates, generating a biradical intermediate that facilitates subsequent intermolecular C–N coupling. Furthermore, our study reveals that the ligand coordination architecture critically determines the efficiency of O–O bond activation, providing valuable insights for the rational design of dicopper active sites with tailored reactivity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"10 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145235251","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

Correction to “FAlen-Zn Complexes for the Cycloaddition of CO2 to Epoxide and the Ring-Opening Polymerization of Lactide” 对“CO2环氧化物环加成和丙交酯开环聚合用FAlen-Zn配合物”的修正

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-10-06 DOI: 10.1021/acscatal.5c06538

Thu-Van Nguyen, Benjamin Théron, Lukáš Vlk, Valentin Vaillant-Coindard, Cédric Balan, Jérôme Bayardon, Laurent Plasseraud, Yoann Rousselin, Paul Fleurat-Lessard, Raluca Malacea-Kabbara, Pierre Le Gendre

引用次数: 0

Carbon-Doped Lattice Interstitial Sites Enable Water-Driven Electrocatalytic Alkyne Semihydrogenation by Suppressing Subsurface Hydrogen 碳掺杂晶格间隙位通过抑制地下氢实现水驱动的电催化炔半氢化

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-10-06 DOI: 10.1021/acscatal.5c05096

Yuan Ren, Ruiyun Guo, Yanan Li, Zixin Ge, Yaohui Zhao, Jiapeng Huang, Qian Wang, Junhao Lu, Mingshang Jin

{"title":"Carbon-Doped Lattice Interstitial Sites Enable Water-Driven Electrocatalytic Alkyne Semihydrogenation by Suppressing Subsurface Hydrogen","authors":"Yuan Ren, Ruiyun Guo, Yanan Li, Zixin Ge, Yaohui Zhao, Jiapeng Huang, Qian Wang, Junhao Lu, Mingshang Jin","doi":"10.1021/acscatal.5c05096","DOIUrl":"https://doi.org/10.1021/acscatal.5c05096","url":null,"abstract":"While electrochemical semihydrogenation (ESH) of alkynes using water-derived hydrogen presents an eco-friendly alternative to traditional thermocatalytic methods, achieving high alkene selectivity remains fundamentally constrained by subsurface hydrogen accumulation in palladium (Pd)-based electrocatalysts. To address this challenge, we developed a class of carbon-doped Pd nanocubes (PdCx NCs) with precisely modulated interstitial carbon occupancy in lattice interstitial sites. The optimized PdC0.15 NCs achieved high catalytic performance with 95.4% alkene selectivity at −1.0 V (vs Hg/HgO) and full conversion, representing a 3-fold selectivity enhancement over pure Pd counterparts without activity compromise. Through comprehensive structural and electrochemical characterization, we identified two critical mechanistic advantages: (1) carbon intercalation effectively suppresses subsurface hydrogen formation through lattice occupation effects, and (2) strategically weakened intermediate adsorption energetics prevent overhydrogenation pathways. In situ spectroscopic analysis and deuterium isotope tracing elucidated water-derived H* as the active hydrogen species, facilitating radical-mediated hydrogenation that preserves sensitive functional groups (e.g., C–Cl bonds) while achieving complete Z-selectivity for challenging internal alkynes. This interstitial doping strategy fundamentally resolves the inherent selectivity limitations of Pd catalysts, establishing an energy-efficient platform for ambient-condition synthesis of high-yield alkenes with preserved functionality.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"79 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145235249","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

Bioinspired Oxidations of C–H Groups Mediated by Nonheme Complexes of Late Transition Metals Co, Ni, and Cu 晚过渡金属Co， Ni和Cu的非血红素配合物介导的C-H基团的生物激发氧化

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-10-06 DOI: 10.1021/acscatal.5c05705

Oleg Y. Lyakin, Evgenii P. Talsi, Konstantin P. Bryliakov

{"title":"Bioinspired Oxidations of C–H Groups Mediated by Nonheme Complexes of Late Transition Metals Co, Ni, and Cu","authors":"Oleg Y. Lyakin, Evgenii P. Talsi, Konstantin P. Bryliakov","doi":"10.1021/acscatal.5c05705","DOIUrl":"https://doi.org/10.1021/acscatal.5c05705","url":null,"abstract":"Deliberately selective activation and functionalization of the abundant and poorly reactive C–H bonds have long been a major challenge, as well as inspiration, for synthetic and catalytic chemists. In recent years, this interest has boosted due to the growing demands of medicinal chemistry for the efficient, environmentally benign, and atom-economic methods of late-stage functionalization/molecular editing of complex organic substrates. One promising general approach relies on biomimetic, or bioinspired, transition metal-based catalysts that mimic the catalytic reactivity of naturally occurring metalloenzymes oxygenases. So far, Fe- and Mn-based catalysts have dominated this area; however, complexes of late transition metals, such as Co, Ni, and Cu, have been attracting increasing attention in both synthetic and mechanistic aspects, mostly due to their tunable catalytic reactivity complementing the reactivity patterns of their Fe and Mn counterparts. Another point of interest is their location in the periodic table, beyond the so-called “oxo-wall”─which entails peculiarities in the electronic structures of the active species responsible for C–H activation and oxygen transfer. This contribution is aimed at surveying the existing systems based on bioinspired nonheme complexes of Co, Ni, and Cu, discussing their catalytic reactivity patterns, the nature of the active species, and the overall mechanisms of catalysis. Contributions since 2005 are considered.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"30 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145235253","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