ACS Catalysis 最新文献_第3页

Polarizability-Induced Oxygen Vacancies and Electronic Exchange Synergy Effect in Cs-Doped SrFe0.9Nb0.1O3−δ for Efficient CO2 Electrolysis in Symmetrical Cells 极化诱导的氧空位和cs掺杂SrFe0.9Nb0.1O3−δ在对称电池中高效电解CO2的电子交换协同效应

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-09-08 DOI: 10.1021/acscatal.5c05626

Caichen Yang, Chao Wang, Ziling Wang, Yunfeng Tian, Kaisheng Xia, Jian Pu, Ruzhi Wang, Bo Chi

{"title":"Polarizability-Induced Oxygen Vacancies and Electronic Exchange Synergy Effect in Cs-Doped SrFe0.9Nb0.1O3−δ for Efficient CO2 Electrolysis in Symmetrical Cells","authors":"Caichen Yang, Chao Wang, Ziling Wang, Yunfeng Tian, Kaisheng Xia, Jian Pu, Ruzhi Wang, Bo Chi","doi":"10.1021/acscatal.5c05626","DOIUrl":"https://doi.org/10.1021/acscatal.5c05626","url":null,"abstract":"In designing symmetrical solid oxide electrolysis cell (SSOEC) perovskite electrodes, modulating the electronic structure of constituent elements holds significant potential for enhancing both the CO2 reduction and oxygen evolution reactions. Among various strategies, Cs-doping is distinguished by its large polarizability, which allows it to effectively alter the electronic structure of surrounding ions in the perovskite lattice. Herein, we develop Cs-doped Sr0.9Cs0.1Fe0.9Nb0.1O3−δ (SCsFNb) as a bifunctional electrode for SSOEC. Driven by the unique polarizability of Cs+, SCsFNb exhibits significantly enhanced oxygen vacancy formation (δ = 0.379) and CO2 adsorption capacity compared to the undoped and K-doped analogues. First-principles calculations reveal that Cs-doping selectively lowers the Nb d-band center and promotes the Nb5+-mediated Fe3+–O2––Nb5+ electronic double exchange effect and further significantly reduces the energy barriers for the rate-determining step in CO2 dissociation. Consequently, the SSOEC with the SCsFNb–Gd0.1Ce0.9O1.95 composite electrode delivers superior CO2 electrolysis performance with 4.23 A·cm–2 at 1.8 V and 850 °C and profound durability over 500 h at 0.6 A·cm–2 and 800 °C. This work establishes the significant potential of Cs+ polarizability in modulating electronic structure for SSOEC bifunctional electrodes.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"38 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145009286","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

CH4 Decomposition over Carbon for CO2-Free Hydrogen Production: A Combined DFT and Experimental Investigation on the Role of Carbon CH4在碳上分解生成无co2制氢：DFT与碳作用的联合实验研究

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-09-08 DOI: 10.1021/acscatal.5c04541

Peng Zhao, Chee Kok Poh, Jiajian Gao, Jiren Zeng, Saifudin Abubakar, Guang Cao, Lili Zhang, Jia Zhang

{"title":"CH4 Decomposition over Carbon for CO2-Free Hydrogen Production: A Combined DFT and Experimental Investigation on the Role of Carbon","authors":"Peng Zhao, Chee Kok Poh, Jiajian Gao, Jiren Zeng, Saifudin Abubakar, Guang Cao, Lili Zhang, Jia Zhang","doi":"10.1021/acscatal.5c04541","DOIUrl":"https://doi.org/10.1021/acscatal.5c04541","url":null,"abstract":"Carbon-based self-catalysis for methane pyrolysis is of great interest for producing H2 and carbon materials without CO2 emissions and the need for catalyst regeneration, but atomic-level insights into this process remain limited. Here, building on experimental observations of layered carbon synthesis during CH4 pyrolysis and the catalytic role of carbon in accelerating CH4 decomposition, we employ density functional theory (DFT) and ab initio atomistic thermodynamics to systematically investigate the adsorption, dehydrogenation, and reaction mechanisms involved in CH4 pyrolysis on armchair-edged graphene (Gr_arm). Our study highlights the unique catalytic properties of Gr_arm under varying temperature, pressure, and radical partial pressures. Equilibrium analyses of adsorption–desorption and dehydrogenation–desorption revealed the unique ability of Gr_arm to stabilize and activate key intermediates across varying conditions. The initial dehydrogenation of CH4 is a critical step where the presence of carbon markedly enhances the reaction rate under low-temperature and high-pressure conditions. The reaction mechanism study indicates that the CH* + H* co-adsorbed species corresponds to the most stable state in the overall CH4(g) → 2H2(g) + C* reaction, with CH* dehydrogenation requiring the highest activation free energy (Ga = 3.65 eV), suggesting potential for CH*–CH* coupling reactions. Moreover, varying CHx• and H• radical partial pressures alters the thermodynamic preference between dehydrogenation and desorption, reshaping the most favorable reaction pathways. These findings underscore the significant role of carbon in methane pyrolysis, offering critical insights for designing efficient carbon-based catalysts and advancing their practical applications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"69 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145009263","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

Ketonization of Acetic Acid over Iron Oxide: Intertwined In Situ Changes of Active Sites and the Contradictory Role of Oxygen Vacancies 醋酸在氧化铁上的酮化：活性位点的原位变化和氧空位的矛盾作用

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-09-08 DOI: 10.1021/acscatal.5c04123

Jinxing Gu, Sasha Yang, Jefferson Zhe Liu, Lian Zhang

{"title":"Ketonization of Acetic Acid over Iron Oxide: Intertwined In Situ Changes of Active Sites and the Contradictory Role of Oxygen Vacancies","authors":"Jinxing Gu, Sasha Yang, Jefferson Zhe Liu, Lian Zhang","doi":"10.1021/acscatal.5c04123","DOIUrl":"https://doi.org/10.1021/acscatal.5c04123","url":null,"abstract":"Iron oxides are catalytically active for the ketonization of acetic acid in bio-oil upgrading. However, due to the complex reaction pathway and phase evolution of iron oxide, the underpinning catalytic mechanism is still far from fully understood. Through purposely designed experiments, advanced characterization, and density functional theory (DFT) modeling, this work confirmed a higher activity of magnetite than hematite for a lower activation energy and a higher reaction order with respect to acetic acid vapor pressure. For pristine hematite, the oxidation of acetic acid causes a gradual loss of lattice oxygen and an in situ phase change of hematite into magnetite. The α-H abstraction step on the (001) surface of hematite is the most energy-intensive, limiting the whole ketonization reaction rate. In contrast, once magnetite forms, its (111) surface becomes active, with β-keto acid decarboxylation as the rate-limiting step for a lower energy barrier. Additionally, on the surface of pristine hematite, the ketene species could be a precursor for the formation of β-keto acid, which, however, was not observed on the magnetite surface. The oxygen vacancy plays a controversial role in the two different oxides. Its presence on hematite facilitates α-H abstraction from the acetate adsorbate. In contrast, its presence on magnetite is detrimental, as it removes the tricoordinated lattice oxygen─the most active site for the initial α-H abstraction. These fundamental results provide practical insights into the optimization of iron oxide catalysts for prior H2-reduction and the controlled manipulation of oxygen vacancies to mitigate in situ acetic acid oxidation and associated coke deposition apart from the aldol condensation.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"24 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145009253","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

Engineered Alcohol Dehydrogenases-Catalyzed Enantiodivergent Atroposelective Synthesis of Axially Chiral Biaryl Phenols via Dynamic Kinetic Resolution 工程醇脱氢酶催化轴手性联芳基酚的对映发散性氨选择性合成

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-09-08 DOI: 10.1021/acscatal.5c04645

Jie Chen, Xiaolong Gao, Zhuoting Peng, Yongzhen Peng, Wei He, Zheng Fang, Yujing Hu, Kai Guo

引用次数: 0

Hybrid Catalytic Systems: Integrating Biocatalysis in the Chemical Space 混合催化系统：在化学空间整合生物催化

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-09-07 DOI: 10.1021/acscatal.5c04375

David Lim, Francesca Paradisi

引用次数: 0

Structural and Mechanistic Basis for Nitrile Synthetase by an Argininosuccinate Synthetase-Like Enzyme 精氨酸琥珀酸合成酶类酶合成丁腈酶的结构和机理基础

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-09-05 DOI: 10.1021/acscatal.5c04243

Yujing Zeng, Keke Zhang, Tiantian Lu, Xinjian Yin, Qiang Wang, Longwei Xiong, Heng Guo, Jing Li, Xuefeng Lu, Lan Liu, Honglei Ma, Zhizeng Gao

{"title":"Structural and Mechanistic Basis for Nitrile Synthetase by an Argininosuccinate Synthetase-Like Enzyme","authors":"Yujing Zeng, Keke Zhang, Tiantian Lu, Xinjian Yin, Qiang Wang, Longwei Xiong, Heng Guo, Jing Li, Xuefeng Lu, Lan Liu, Honglei Ma, Zhizeng Gao","doi":"10.1021/acscatal.5c04243","DOIUrl":"https://doi.org/10.1021/acscatal.5c04243","url":null,"abstract":"The enzymatic origins of nitrile groups in fungal natural products have recently been linked to argininosuccinate synthetase (ASS)-like enzymes, but the structural basis for their unique catalytic function remained unknown. Here, we provide the structural and mechanistic elucidation of this enzyme class by characterizing ArtA, the nitrile synthetase from the auranthine biosynthetic pathway. High-resolution crystal structures of ArtA, combined with mutagenesis and molecular dynamics simulations, reveal how the canonical ASS active site is remodeled to selectively bind l-glutamine and catalyze nitrile formation through an elegant ATP-dependent elimination reaction. Furthermore, phylogenetic analysis and functional validation of homologues from another fungus (Fusarium) and a bacterium (Streptomyces) demonstrate that ArtA belongs to a widespread family of nitrile synthetases, likely acquired by fungi via horizontal gene transfer. Our work provides the molecular blueprint for this new enzyme family and opens avenues for genome mining and biocatalyst engineering.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"17 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145007239","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

Organocatalytic Asymmetric Synthesis of Tetrasubstituted Axially Chiral Allenylphosphines 四取代轴手性烯基膦的有机催化不对称合成

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-09-05 DOI: 10.1021/acscatal.5c04741

Rui Lin, Yifei Zhang, Ting Xiong, Hongkai Huang, Peng Xie, Yaxin Zhang, Nan Huang, Wenhao Hu, Jun Jiang

{"title":"Organocatalytic Asymmetric Synthesis of Tetrasubstituted Axially Chiral Allenylphosphines","authors":"Rui Lin, Yifei Zhang, Ting Xiong, Hongkai Huang, Peng Xie, Yaxin Zhang, Nan Huang, Wenhao Hu, Jun Jiang","doi":"10.1021/acscatal.5c04741","DOIUrl":"https://doi.org/10.1021/acscatal.5c04741","url":null,"abstract":"Albeit notable endeavors in enantioselective allenyl C–X bond formation reactions (X = C, O, S, Si, etc.), the catalytic asymmetric synthesis of tetrasubstituted axially chiral allenylphosphines via C–P bond formation still stands for a long-lasting challenge. Herein, we report an intriguing chiral phosphoric acid (CPA)-catalyzed asymmetric 1,8-addition reaction between tertiary propargylic alcohol derivatives and H-phosphine oxides, which enables the synthesis of a series of tetrasubstituted axially chiral allenylphosphines through the construction of C–P bonds in good yields with high stereoselectivity. Avoiding the use of transition metals, this method represents a unique example of organocatalytic asymmetric axially chiral allenyl C–P bond formation, showcasing the extraordinary potential of the organocatalytic asymmetric synthesis of fully substituted allenes. Control experiments and density functional theory calculations suggested that the process involves the in situ generation of imine methide intermediate and efficient remote control of regioselectivity and enantioselectivity by a bifunctional CPA catalyst.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"26 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145007217","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

Single-Atom Centers of MXenes for Electrochemical Ammonia Oxidation: Moving Beyond Thermodynamic Descriptors 电化学氨氧化的MXenes单原子中心：超越热力学描述符

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-09-05 DOI: 10.1021/acscatal.5c03419

Totan Mondal, Ebrahim Tayyebi, Kai S. Exner

{"title":"Single-Atom Centers of MXenes for Electrochemical Ammonia Oxidation: Moving Beyond Thermodynamic Descriptors","authors":"Totan Mondal, Ebrahim Tayyebi, Kai S. Exner","doi":"10.1021/acscatal.5c03419","DOIUrl":"https://doi.org/10.1021/acscatal.5c03419","url":null,"abstract":"The ammonia oxidation reaction (AOR) presents a promising route for clean energy conversion and wastewater remediation, yet it currently relies on scarce and expensive platinum-based catalysts. In this study, we explore electrochemically formed single-atom centers on MXenes (MXene-SACs) under anodic polarization as a material class of Earth-abundant elements for electrochemical ammonia oxidation. These systems offer well-defined active sites at the atomic scale, providing benefits in controlling the catalytic interface and guiding selective N–N coupling. To investigate the kinetics of N–N bond formation as a function of the coupling position in the reaction mechanism, a comprehensive series of transition state calculations was performed. Electrocatalytic activity is assessed by employing two key descriptors, namely Gmax(U) ─ a thermodynamic representation of the free-energy span model ─ and G‡(U), which considers the N–N coupling transition state relative to the most stable intermediate in the definition of the energetic span. This dual-descriptor approach reveals that different MXene-SACs engage in N–N coupling through distinct mechanistic pathways and at different stages of hydrogenation. In particular, W- and Mo-based MXene-SACs, particularly in their nitride forms, exhibit low N–N coupling barriers and favorable mechanistic profiles, making them promising candidates for AOR. Distinct Brønsted–Evans–Polanyi (BEP) relationships are observed for the different reaction intermediates in the AOR. While a strong correlation between thermodynamics and kinetics is witnessed for hydrogen-rich intermediates such as *NH2–*NH2, these correlations deteriorate as the degree of hydrogenation decreases, emphasizing the inadequacy of thermodynamic analysis alone. In this context, the G‡(U) descriptor serves as a mechanistically relevant metric that bridges the gap between thermodynamic favorability and kinetic feasibility and provides guidance for the rational design of advanced AOR catalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"24 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145007242","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

Synthesis of Chiral Sulfinamides Enabled by Polycyclic Ketone Monooxygenase Catalyzed Asymmetric Oxidation of Sulfenamides 多环酮单加氧酶催化亚砜胺不对称氧化合成手性亚砜胺

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-09-05 DOI: 10.1021/acscatal.5c04242

Wanqing Xue, Yuqi Lin, Xiaomin Lin, Xinqi Xu, Jingjing Chen, Juan Lin, Ke-Yin Ye

引用次数: 0

Dynamic Kinetic Resolution of Azlactones with Hydrazines via Negative Catalysis: Synthesis of α-Chiral Amino Acid Hydrazides and Their Preferential Enrichment Phenomenon 氮唑内酯与肼的负催化动力学分解：α-手性氨基酸肼的合成及其优先富集现象

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-09-05 DOI: 10.1021/acscatal.5c02848

Sungyong Won, Yuta Yamaguchi, Yasutaka Kawai, Yuki Kono, Masato Ichikawa, Eiji Yamamoto, Takashi Kamachi, Akina Yoshizawa, Makoto Tokunaga

{"title":"Dynamic Kinetic Resolution of Azlactones with Hydrazines via Negative Catalysis: Synthesis of α-Chiral Amino Acid Hydrazides and Their Preferential Enrichment Phenomenon","authors":"Sungyong Won, Yuta Yamaguchi, Yasutaka Kawai, Yuki Kono, Masato Ichikawa, Eiji Yamamoto, Takashi Kamachi, Akina Yoshizawa, Makoto Tokunaga","doi":"10.1021/acscatal.5c02848","DOIUrl":"https://doi.org/10.1021/acscatal.5c02848","url":null,"abstract":"Enantioselective nucleophilic ring-opening reactions of azlactones have been extensively investigated. However, using nitrogen nucleophiles for these reactions remains challenging because of their inherently high reactivity. Herein, we report the catalytic dynamic kinetic resolution of α-chiral azlactones using hydrazines as nucleophiles and bifunctional quinine-thiourea organocatalysts. The reactions proceeded under mild conditions and provided α-chiral amino acid hydrazides with excellent yields (up to 99%) and enantioselectivity (up to 99:1 enantiomeric ratio). Mechanistic studies revealed that the catalyst plays dual roles of enhancing the enantioselectivity and slowing down the reaction by modulating the hydrazine reactivity, which is a rare case of reaction rate suppression in asymmetric catalysis. Computational studies at the M06-2X/TZVP level elucidated the transition-state structures governing the stereocontrol, while independent gradient model analysis highlighted the key noncovalent interactions stabilizing the preferred transition state. Furthermore, a unique preferential enrichment phenomenon was observed during recrystallization, where the solution phase exhibited enhanced optical purity while the crystalline phase formed as a racemate. This work provides new insights into enantioselective negative catalysis and a promising strategy for the synthesis of α-chiral amino acid hydrazides.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"12 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145007241","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