ACS Catalysis 最新文献_第4页

Machine Learning-Accelerated Prediction of Lewis Acid Site Positioning for Long-Chain Mono-olefin Aromatization on Zn2+/HZSM-5 Catalysts Zn2+/HZSM-5催化剂上长链单烯烃芳构化刘易斯酸定位的机器学习加速预测

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-05-30 DOI: 10.1021/acscatal.5c00459

Jing Wang, Yusheng Jia, Rui Li, Yupeng Zhang, Caiping Ma, Yang Zhang, Riguang Zhang, Xiaofeng Li, Baojun Wang, Lixia Ling

{"title":"Machine Learning-Accelerated Prediction of Lewis Acid Site Positioning for Long-Chain Mono-olefin Aromatization on Zn2+/HZSM-5 Catalysts","authors":"Jing Wang, Yusheng Jia, Rui Li, Yupeng Zhang, Caiping Ma, Yang Zhang, Riguang Zhang, Xiaofeng Li, Baojun Wang, Lixia Ling","doi":"10.1021/acscatal.5c00459","DOIUrl":"https://doi.org/10.1021/acscatal.5c00459","url":null,"abstract":"Long-chain mono-olefin aromatization is an important reaction during synthesis of coal to aromatics, in which the positioning of Lewis acid in ZSM-5 zeolite determines the performance. This study aims to reveal the relationship between the location of Lewis acid and catalytic performance during the aromatization of C6–C8 mono-olefins and to rapid-screen the optimized positioning of Lewis acid to enhance the efficiency and selectivity of aromatic production. Based on density functional theory (DFT) to obtain high-quality data sets of C6 and C7 dehydrogenation reactions in Zn2+/HZSM-5 catalysts, a data-driven ML model is developed to predict the C8 dehydrogenation energy barriers and screen the Lewis acid sites T5-T3 or T11-T3 with high dehydrogenation activity, while DFT confirms the accuracy of the results. The BTX (benzene, toluene, and xylene) selectivity reached 64.1% among various products via microkinetic analysis after investigating the cyclization process and cracking reactions on the Lewis acid site positioning, where the dehydrogenation activity of the catalyst is optimal. The six-membered ring is found to be the key cyclic intermediate due to the pore confinement effect, which effectively stabilizes cyclic intermediates, and toluene and p-xylene show a small steric effect through weak interactions analysis. This can provide important clues and research paradigms for the rational design of ZSM-5 zeolite modified with different metal species.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"27 2 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144176912","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

Lattice Strain Engineering in Ru-Based Electrocatalysts for Efficient Acidic Overall Water Splitting and Ru Dissolution Suppression 基于栅格应变工程的Ru基电催化剂的高效酸性全水分解和Ru溶解抑制

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-05-30 DOI: 10.1021/acscatal.5c01502

Xiaoxiao Duan, Ning Wen, Shu Liu, Haiping Li, Xiuling Jiao, Dairong Chen, Yuguo Xia

{"title":"Lattice Strain Engineering in Ru-Based Electrocatalysts for Efficient Acidic Overall Water Splitting and Ru Dissolution Suppression","authors":"Xiaoxiao Duan, Ning Wen, Shu Liu, Haiping Li, Xiuling Jiao, Dairong Chen, Yuguo Xia","doi":"10.1021/acscatal.5c01502","DOIUrl":"https://doi.org/10.1021/acscatal.5c01502","url":null,"abstract":"Developing efficient and durable electrocatalysts for PEMWE is essential for advanced hydrogen production. Here, we introduce a lattice strain manipulation strategy through multiphase interface engineering, demonstrating its effectiveness in enhancing water-splitting efficiency while mitigating Ru dissolution in acidic environments. Specifically, an in situ combustion method is employed to synthesize the Ru-based hybrid (Ru/RuS2/RuO2), increasing the density of crystal boundaries and optimizing the lattice strain within the Ru/RuS2/RuO2 structure. The two-electrode system consisting of the bifunctional Ru/RuS2/RuO2 hybrid exhibits superior overall water-splitting performance (19 mV@10 mA cm–2 for HER and 177 mV@10 mA cm–2 for OER), achieving an impressive low cell voltage of 1.468 V at a current density of 10 mA cm–2 with only 14 ppb of Ru ion dissolution even after 500 h. Experimental analyses and theoretical calculations highlight the critical role of the multiphase interfaces in modulating electronic structures, enhancing hydrophilicity, and accelerating water-splitting reactions. Density functional theory calculations further reveal reduced energy barriers and increased Ru dissociation energy, attributed to the shortened Ru–O/Ru–S bonds as well as the decreased bonding band energy of these interactions. This work underscores the transformative potential of multiphase interface engineering in overcoming durability and efficiency challenges for Ru-based electrocatalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"244 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144176698","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

Ultraselective C–O Hydrogenolysis of Biomass-Based Compounds under Ambient Pressure and at Low Temperature via Hydrogen Spillover over the Pd–SO42– Interface 低温常压下Pd-SO42 -界面氢溢出对生物质基化合物超选择性C-O氢解的影响

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-05-29 DOI: 10.1021/acscatal.5c01074

Yao Zhong, Zhihao Ouyang, Jun Wang, Jianxin Cai, Shuguang Deng, Ji-Jun Zou, Qiang Deng

{"title":"Ultraselective C–O Hydrogenolysis of Biomass-Based Compounds under Ambient Pressure and at Low Temperature via Hydrogen Spillover over the Pd–SO42– Interface","authors":"Yao Zhong, Zhihao Ouyang, Jun Wang, Jianxin Cai, Shuguang Deng, Ji-Jun Zou, Qiang Deng","doi":"10.1021/acscatal.5c01074","DOIUrl":"https://doi.org/10.1021/acscatal.5c01074","url":null,"abstract":"Developing an efficient catalyst for the selective hydrogenolysis of aromatic alcohol and diphenyl ether derivatives is important for synthesizing biofuels and fine chemicals. However, it possesses challenges because of the complex reaction network. Herein, a series of Pd nanoparticle and sulfate ion (SO42–)-supported catalysts were fabricated, catalyzing the hydrogenolysis of benzyl alcohol selectively to methylbenzene with a 99.6% yield at 30 °C under ambient pressure. Furthermore, they showed generality for synthesizing methyl aromatic derivatives from various furfuryl, benzyl, and heterocyclic alcohols under the same reaction conditions. Moreover, the hydrogenolysis of diphenyl ethers was catalyzed at 90 °C under ambient pressure. The catalytic mechanism study revealed that hydrogen spillover from Pd nanoparticles to the Pd–SO42– interface generated the S–O–H+···H––Pd pairs, which could simultaneously activate O and C atoms in the C–O bonds of aromatic alcohol and diphenyl ether derivatives based on the SN2 mechanism, thus accelerating the hydrogenolysis activity. This study presents interesting bifunctional catalysis, offering uncommon hydrogenolysis efficiency under ambient pressure and at low temperature via in situ-generated transient H+–H– pairs.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"5 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144176703","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

Monolayer Fullerene Networks for High-Performance Lithium–Sulfur and Sodium–Sulfur Batteries 高性能锂硫电池和钠硫电池的单层富勒烯网络

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-05-29 DOI: 10.1021/acscatal.4c07268

Jiguang Du, Mingyang Shi, Xuying Zhou, Xiujuan Cheng, Kunyang Cheng, Gang Jiang

{"title":"Monolayer Fullerene Networks for High-Performance Lithium–Sulfur and Sodium–Sulfur Batteries","authors":"Jiguang Du, Mingyang Shi, Xuying Zhou, Xiujuan Cheng, Kunyang Cheng, Gang Jiang","doi":"10.1021/acscatal.4c07268","DOIUrl":"https://doi.org/10.1021/acscatal.4c07268","url":null,"abstract":"In light of the detrimental effects of conventional energy sources on the environment, there is an imperative need to innovate energy storage systems. Lithium–sulfur (Li–S) and sodium–sulfur (Na–S) batteries are regarded as highly promising candidates for energy storage due to their high theoretical energy densities. Nevertheless, their practical commercialization has been impeded by several unresolved challenges. This study presents a comprehensive assessment of three types of fullerene monolayers as potential electrode materials for Li–S and Na–S batteries, utilizing first-principles calculations. The findings indicate that these monolayers can effectively immobilize Li2Sn and Na2Sn species while preserving their geometric conformation, and preventing dissolution into the electrolytes. Furthermore, the electrical conductivity of the fullerene monolayers is significantly enhanced following the adsorption of Li2Sn and Na2Sn clusters. The minimal free energy change associated with the sulfur reduction reaction (SRR) suggests that the fullerene monolayer demonstrates excellent catalytic performance, alongside a low energy barrier for the dissociation of Li2S and Na2S. Our research thus posits that fullerene monolayers possess considerable potential as electrode materials for lithium–sulfur and sodium–sulfur batteries.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"58 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165349","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

Synergistic Cobaloxime Catalysis for Photo-Dehydrogenative Transformations 协同钴肟催化光脱氢转化

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-05-29 DOI: 10.1021/acscatal.5c00343

Aindrila Mandal, Matthew Lim, Lili Zhang, Kuo-Wei Huang, Shashikant U. Dighe

引用次数: 0

Anomalous Enhancement of the Electrocatalytic Hydrogen Evolution Reaction in AuPt Nanoclusters AuPt纳米团簇中电催化析氢反应的异常增强

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-05-29 DOI: 10.1021/acscatal.4c07859

Jiahui Kang, Jan Kloppenburg, Jiali Sheng, Zhenyu Xu, Kristoffer Meinander, Hua Jiang, Zhong-Peng Lv, Esko I. Kauppinen, Qiang Zhang, Xi Chen, Milla Vikberg, Olli Ikkala, Miguel A. Caro, Bo Peng

{"title":"Anomalous Enhancement of the Electrocatalytic Hydrogen Evolution Reaction in AuPt Nanoclusters","authors":"Jiahui Kang, Jan Kloppenburg, Jiali Sheng, Zhenyu Xu, Kristoffer Meinander, Hua Jiang, Zhong-Peng Lv, Esko I. Kauppinen, Qiang Zhang, Xi Chen, Milla Vikberg, Olli Ikkala, Miguel A. Caro, Bo Peng","doi":"10.1021/acscatal.4c07859","DOIUrl":"https://doi.org/10.1021/acscatal.4c07859","url":null,"abstract":"Energy- and resource-efficient electrocatalytic water splitting is of paramount importance to enable hydrogen production. The best bulk catalyst for the hydrogen evolution reaction (HER), platinum, is one of the scarcest elements on Earth. The use of nanoclusters significantly reduces the amount of raw material required for HER, while nanoalloying further enhances performance by modulating hydrogen adsorption. However, the interplay between the atomic structure and HER performance in alloyed nanoclusters remains unclear. In this study, we report an anomalous HER enhancement at low and intermediate Au contents in monodisperse AuPt nanoclusters immobilized on carbon nanotubes. This enhancement is driven by the segregation of Au atoms toward the nanocluster surface and a synergistic effect, whereby the ability of surface Pt atoms to bind hydrogen is increased in the presence of adjacent Au atoms. This enhancement is noteworthy and “anomalous”, given that the overall hydrogen adsorption activity significantly decreases for pure Au nanoclusters compared to pure Pt nanoclusters. We rationalize these observations by combining extensive experimental characterization data with detailed atomistic simulations based on purpose-built machine learning interatomic potential and Markov-chain Monte Carlo simulations with variable chemical potential. The agreement between simulation and experiment allows us to develop a mechanistic understanding of the atomic-scale processes underlying the enhanced HER activity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"3 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165350","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

Peroxidation Activation of Ethane with Hydrogen and Oxygen by Au-Based MWW Zeolite Acidic Catalyst 金基MWW沸石酸性催化剂对乙烷氢氧过氧化活化的研究

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-05-29 DOI: 10.1021/acscatal.5c01446

Kui Xu, Yao Xiao, Sijia Liu, Guiying Wu, Bingbing Luo, Jingru Jin, Xianfeng Yi, Aoqiang Peng, Jianhong Gong, Anmin Zheng, Fang Jin

{"title":"Peroxidation Activation of Ethane with Hydrogen and Oxygen by Au-Based MWW Zeolite Acidic Catalyst","authors":"Kui Xu, Yao Xiao, Sijia Liu, Guiying Wu, Bingbing Luo, Jingru Jin, Xianfeng Yi, Aoqiang Peng, Jianhong Gong, Anmin Zheng, Fang Jin","doi":"10.1021/acscatal.5c01446","DOIUrl":"https://doi.org/10.1021/acscatal.5c01446","url":null,"abstract":"The oxidative activation of ethane to produce ethene and oxygenates has attracted wide interest. An alternative reaction process for peroxidation activation of ethane in the presence of H2 and O2 at mild temperatures is performed by Au-based MWW zeolite acidic catalysts to produce acetic acid and ethene without the COx generation. A nanometal oxide encapsulated Au nanoparticle catalyst was synthesized by homogeneously distributing Au nanoparticles on the atom-planting introduced TiOx or SnOx in the hydroxyl group of MWW zeolite. The Au cluster size, the catalyst Brønsted, and Lewis acidity determine the stability of in situ generated H2O2 and control acetic acid and ethene selectivity. We propose a heterogeneous catalytic mechanism in which the Au cluster can promote ethane activation through α-H cracking of the C–H bond; this activated ethane then interacts with hydroperoxyl radicals (HOO*) on the Au cluster surface or the hydroxyl radicals (OH*) from decomposition of the in situ generated H2O2, and ethylhydrogen peroxide and ethanol are formed as key reaction intermediates for acetic acid. The Au surface OH* can promote β-H scission of ethane dehydrogenation for ethene. The Brønsted acid and Au–Ti in aluminosilicate MWW zeolite can activate ethane at 623 K and stabilize hydroperoxyl radicals with an acetic acid productivity of 4.04 mol gAu–1 h–1 and 87.08% selectivity. At 823 K, Au–Sn in deborosilicate MWW zeolite promotes ethane dehydrogenation to ethene with a productivity of 4.33 mol gAu–1 h–1 and 98.5% selectivity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"5 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165386","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

Streamlined Carbonylation of Csp3–H Bonds: Divergent Synthesis of Diverse Carbonyl Compounds Csp3-H键的流线型羰基化：不同羰基化合物的发散合成

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-05-29 DOI: 10.1021/acscatal.5c02925

Le-Cheng Wang, Hefei Yang, Qiangwei Li, Xiao-Feng Wu

{"title":"Streamlined Carbonylation of Csp3–H Bonds: Divergent Synthesis of Diverse Carbonyl Compounds","authors":"Le-Cheng Wang, Hefei Yang, Qiangwei Li, Xiao-Feng Wu","doi":"10.1021/acscatal.5c02925","DOIUrl":"https://doi.org/10.1021/acscatal.5c02925","url":null,"abstract":"Transition metal-catalyzed carbonylation reactions present a promising strategy for synthesizing valuable carbonyl-containing compounds. However, a significant limitation is the need for stepwise optimization of reaction conditions for different carbonyl types due to the inherent reactivity differences among coupling partners. In this context, we introduce a general photochemical strategy that facilitates the efficient synthesis of a diverse range of carbonyl compounds. This approach minimizes the need for extensive optimization by maintaining consistent reaction conditions, effectively addressing the challenges posed by varying reactivity and providing a versatile tool for organic synthesis. Moreover, this mild and practical method establishes a distinctive approach for obtaining valuable carbonyl compounds from abundant and low-cost starting materials while showcasing its flexibility with various coupling partners. By leveraging readily available aliphatic C–H bonds, this protocol offers a complementary approach to traditional Csp3–H carbonylation, positioning it as a crucial asset in the research toolkit for carbonyl synthesis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"3 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144176705","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

Stability of Single Atom Alloys Catalyst: A Theoretical and Experimental Perspective 单原子合金催化剂的稳定性：理论和实验的观点

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-05-29 DOI: 10.1021/acscatal.5c01586

Tianwei He, Ran Shi, Tong Zhou, Alain Rafael Puente Santiago, Qingju Liu

{"title":"Stability of Single Atom Alloys Catalyst: A Theoretical and Experimental Perspective","authors":"Tianwei He, Ran Shi, Tong Zhou, Alain Rafael Puente Santiago, Qingju Liu","doi":"10.1021/acscatal.5c01586","DOIUrl":"https://doi.org/10.1021/acscatal.5c01586","url":null,"abstract":"Single-atom alloys (SAAs) catalysts, consisting of reactive metal atoms embedded within a less reactive metal host, have garnered significant attention due to their excellent catalytic activity, selectivity, and high atomic efficiency. However, at elevated temperatures, the migration and aggregation of single atoms can lead to catalyst deactivation. In operational environments, especially in the presence of oxidizing agents or reaction intermediates, surface reconstruction may further undermine the stability. The interaction between the doped metal atoms and the host metal surface is crucial for stabilizing single atoms and preventing aggregation. Despite substantial progress in this field, the factors influencing the stability of SAAs remain poorly understood. This review provides a timely and comprehensive overview of the key factors affecting the stability of SAAs, addressing both intrinsic structural stability and catalytic performance. Strategies to enhance SAAs stability, such as surface modification and optimization of the reaction conditions, are discussed in detail. Additionally, the roles of advanced characterization techniques and theoretical simulations in understanding SAAs stability and reaction mechanisms are explored. The review also highlights the challenges of scaling up SAAs for industrial applications and outlines future research directions for developing more stable and efficient SAAs. Overall, this work emphasizes the critical importance of stability for the practical application of SAAs catalysts from both theoretical and experimental perspectives.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"48 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144176709","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

Beyond Equilibrated Structures: Sequential Lattice Oxygen Evolution Shapes Mars–van Krevelen Catalytic Oxidation on β-MnO2(110) 超越平衡结构：顺序晶格析氧形成β-MnO2的Mars-van Krevelen催化氧化（110）

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-05-29 DOI: 10.1021/acscatal.5c00169

Yuan Fang, Bohua Wang, Zhangyun Liu, Zheng Chen, Mingfeng Li, Xin Xu

{"title":"Beyond Equilibrated Structures: Sequential Lattice Oxygen Evolution Shapes Mars–van Krevelen Catalytic Oxidation on β-MnO2(110)","authors":"Yuan Fang, Bohua Wang, Zhangyun Liu, Zheng Chen, Mingfeng Li, Xin Xu","doi":"10.1021/acscatal.5c00169","DOIUrl":"https://doi.org/10.1021/acscatal.5c00169","url":null,"abstract":"Catalytic oxidation on a large number of reducible transition metal oxides can be described by the Mars–van Krevelen (MvK) mechanism, wherein the redox behavior of lattice oxygen (Olat) plays a central role. As a result, the formation energy (Evac) of the oxygen vacancy (OV), typically derived from a stoichiometric or thermodynamically equilibrated surface, is widely used as a descriptor of the catalytic activity. However, this approach overlooks the dynamic evolution of the surface due to the continuous consumption of Olat during the reaction. In this work, using CO oxidation on β-MnO2(110) as a probe, we combine density functional theory and kinetic Monte Carlo simulations to demonstrate the importance of sequential consumption and regeneration of Olat in dictating catalytic performance. We find that Evac is not static but varies with OV concentration, altering the equilibrium between Olat reduction and regeneration. As the accumulation of OV shifts the reaction mechanism from being reduction-dominated to regeneration-dominated, the steady-state surface composition deviates significantly from the prediction based on the thermodynamic equilibrium model. Only by accounting for the dynamic variation of Olat can the simulated apparent activation energies and reaction orders be closely reconciled with experimental observations. This work challenges the traditional reliance on the initial Evac and offers a more accurate portrayal of catalytic oxidation within the MvK mechanism, which provides useful guidance for predicting and optimizing catalytic activity toward real-world applications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"57 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165381","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