ACS Catalysis 最新文献

{"title":"Refining Electrocatalyst Design for 5-Hydroxymethylfurfural Oxidation: Insights into Electrooxidation Mechanisms, Structure–Property Correlations, and Optimization Strategies","authors":"Xupo Liu, Jiashu Tang, Ye Chen, Xiangjia Song, Junpo Guo, Gongke Wang, Shixing Han, Xin Chen, Congcong Zhang, Shixue Dou, Huaiyu Shao, Deli Wang","doi":"10.1021/acscatal.4c06577","DOIUrl":"https://doi.org/10.1021/acscatal.4c06577","url":null,"abstract":"Electrooxidation of biomass-derived 5-hydroxymethylfurfural (HMF) is a green and economically viable approach to produce the valuable chemical 2,5-furandicarboxylic acid (FDCA). Given the significance of this transformation, there is a pressing demand for efficient electrocatalysts to expedite the HMF electrooxidation. This article provides a comprehensive overview of the electrooxidation mechanisms, structure–property correlations, and optimization strategies for catalysts involved in converting HMF into FDCA. Initially, the selectivity of reaction pathways, electrooxidation mechanisms, and thermodynamic and kinetic principles governing HMF oxidation are discussed, along with strategies to hinder the competitive oxygen evolution reaction. Subsequently, the structure–property correlations of electrocatalysts based on precious metals and transition metals are introduced in detail, emphasizing the promotion effects of various metal elements on the HMF oxidation process. Furthermore, an in-depth analysis of performance optimization strategies for electrocatalysts is also conducted, including tailoring surface adsorption, regulating dehydrogenation, accelerating proton transfer, integrating catalytic sites, and regenerating active species. Additionally, we critically assess the current challenges faced in developing highly effective HMF electrooxidation catalysts and propose future directions for overcoming these obstacles. This review article aims to provide insightful inspiration for developing high-efficiency electrocatalysts to expedite biomass conversion applications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"75 5 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846738","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":"Buffer Effects on Nitrite Reduction Electrocatalysis","authors":"Yair Shahaf, Thierry K. Slot, Shaked Avidan, Jeffrey E. Dick, David Eisenberg","doi":"10.1021/acscatal.4c07765","DOIUrl":"https://doi.org/10.1021/acscatal.4c07765","url":null,"abstract":"The Haber-Bosch process has provided an energy-intensive way to produce ammonia for over 100 years. However, alternative methods are required to lower pollution and enhance energy efficiency. Unfortunately, key mechanistic insights into the heterogeneous reduction of nitrogen and its intermediates are lacking. The nitrite reduction reaction (NO<sub>2</sub>RR) is an important electrochemical reaction in the nitrogen cycle, playing a significant role in ammonia-based energy storage and wastewater remediation. Although the NO<sub>2</sub>RR involves the transfer of multiple protons competing with the hydrogen evolution reaction (HER), the effect of the proton donor has not been investigated in heterogeneous electrocatalysis. We now present an electrochemical study of nitrite reduction in four buffer systems acting as proton donors: citrate, phosphate, 2-(<i>N</i>-morpholino)ethanesulfonic acid, and borate buffers. The chosen catalyst was a typical iron- and nitrogen-codoped carbon (FeNC) with atomically dispersed FeN<sub>4</sub> sites. All buffers except borate enhanced the NO<sub>2</sub>RR considerably, while the reduction mechanism was independent of buffer identity. The kinetics of the reaction depended more strongly on buffer concentration than on the <i></i><span style=\"color: inherit;\"></span><span data-mathml='<math xmlns=\"http://www.w3.org/1998/Math/MathML\" display=\"inline\"><msubsup><mrow><mi>NO</mi></mrow><mrow><mn>2</mn></mrow><mrow><mo>−</mo></mrow></msubsup></math>' role=\"presentation\" style=\"position: relative;\" tabindex=\"0\"><nobr aria-hidden=\"true\"><span style=\"width: 2.219em; display: inline-block;\"><span style=\"display: inline-block; position: relative; width: 1.991em; height: 0px; font-size: 110%;\"><span style=\"position: absolute; clip: rect(1.196em, 1001.99em, 2.616em, -999.997em); top: -2.156em; left: 0em;\"><span><span><span style=\"display: inline-block; position: relative; width: 1.991em; height: 0px;\"><span style=\"position: absolute; clip: rect(3.128em, 1001.42em, 4.151em, -999.997em); top: -3.974em; left: 0em;\"><span><span style=\"font-family: STIXMathJax_Main;\">NO</span></span><span style=\"display: inline-block; width: 0px; height: 3.98em;\"></span></span><span style=\"position: absolute; clip: rect(3.412em, 1000.57em, 4.207em, -999.997em); top: -4.372em; left: 1.423em;\"><span><span style=\"font-size: 70.7%; font-family: STIXMathJax_Main;\">−</span></span><span style=\"display: inline-block; width: 0px; height: 3.98em;\"></span></span><span style=\"position: absolute; clip: rect(3.355em, 1000.46em, 4.151em, -999.997em); top: -3.69em; left: 1.423em;\"><span><span style=\"font-size: 70.7%; font-family: STIXMathJax_Main;\">2</span></span><span style=\"display: inline-block; width: 0px; height: 3.98em;\"></span></span></span></span></span><span style=\"display: inline-block; width: 0px; height: 2.162em;\"></span></span></span><span style=\"di","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"108 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846735","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":"MOF-Derived PdCo and PdMn Systems as Versatile Catalysts in Alkyne Semihydrogenation","authors":"Jordan Santiago Martinez, Luigi Carpisassi, Gonzalo Egea, Jaime Mazarío, Christian Wittee Lopes, Carmen Mora-Moreno, Susana Trasobares, Luigi Vaccaro, Jose Juan Calvino, Giovanni Agostini, Pascual Oña-Burgos","doi":"10.1021/acscatal.4c07149","DOIUrl":"https://doi.org/10.1021/acscatal.4c07149","url":null,"abstract":"This study investigates the structure and catalytic properties of bimetallic nanocomposites derived from PdCo- and PdMn-based metal–organic frameworks. These materials, synthesized via chemical (Q) and thermal treatments (T), resulted in <b>PdCo-QT</b> and <b>PdMn-QT</b> catalysts containing Pd-based nanoparticles modified with Co or Mn and supported on N-doped carbon. Detailed characterization techniques confirm these complex structures, including high-resolution transmission electron microscopy, scanning transmission electron microscopy energy-dispersive X-ray spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy. The catalytic performances of these materials were evaluated for the selective semihydrogenation of phenylacetylene and 4-octyne under soft conditions (1 H₂ bar, room temperature) in batch reactors, demonstrating very high selectivity (≥95 mol %) toward alkenes at high conversion levels (≥94 mol %). Moreover, they displayed significant stability after five catalytic cycles with minimal leaching and highly competitive values of alkyne productivity in the semihydrogenation of phenylacetylene. The study also explored the potential of these catalysts in continuous gas-phase reactions, where <b>PdCo-QT</b> demonstrated remarkable catalytic activity and selectivity with a high gas hourly space velocity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"1 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846734","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":"Impact of Tungsten Loading on the Activation of Zeolite-Based Catalysts for Methane Dehydroaromatization","authors":"Josepha J.G. Kromwijk, Job G.A. Vloedgraven, Fleur Neijenhuis, Ward van der Stam, Matteo Monai, Bert M. Weckhuysen","doi":"10.1021/acscatal.4c07228","DOIUrl":"https://doi.org/10.1021/acscatal.4c07228","url":null,"abstract":"To improve the performance of zeolite-based catalysts for the methane dehydroaromatization (MDA) reaction, it is of importance to understand the nature of the catalytically active phase. Although many studies have been devoted to unraveling the structure of the active site, there is still no consensus. Monomeric, dimeric, and/or clusters of molybdenum oxide or tungsten oxide are proposed precatalyst structures. This precatalyst is activated under reaction conditions, to form (oxy)carbidic species which are believed to be the active site. In this study, we investigated the effect of tungsten dispersion on the activation of W/ZSM-5 catalysts. We observed unexpected long activation times that could be shortened by inert or reductive pretreatment. Based on our investigations, we hypothesize that W/ZSM-5 catalysts with low weight loadings (i.e., 2 wt %) cannot be activated due to the presence of monomeric tungsten. For catalysts with medium weight loadings (i.e., 5 and 7 wt %), restructuring of the tungsten is required for the formation of the active site, which can be achieved through performing a thermal pretreatment. For higher weight loadings (i.e., 10 wt %), reduction plays a key role in the activation of the catalyst. We show that the activation of the catalyst is impacted by the precatalyst structure. These insights aid in the development of suitable activation treatments which could save time and energy if the reaction would be performed at an industrial scale.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"24 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846742","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":"SPOCK Tool for Constructing Empirical Volcano Diagrams from Catalytic Data","authors":"Manu Suvarna, Rubén Laplaza, Romain Graux, Núria López, Clémence Corminboeuf, Kjell Jorner, Javier Pérez-Ramírez","doi":"10.1021/acscatal.5c00412","DOIUrl":"https://doi.org/10.1021/acscatal.5c00412","url":null,"abstract":"Volcano plots, stemming from the Sabatier principle, visualize descriptor–performance relationships, allowing rational catalyst design. Manually drawn volcanoes originating from experimental studies are potentially prone to human bias as no guidelines or metrics exist to quantify the goodness of fit. To address this limitation, we introduce a framework called SPOCK (systematic piecewise regression for volcanic kinetics) and validate it using experimental data from heterogeneous, homogeneous, and enzymatic catalysis to fit volcano-like relationships. We then generalize this approach to DFT-derived volcanoes and evaluate the tool’s robustness against noisy kinetic data and in identifying false-positive volcanoes, i.e., cases where studies claim a volcano-like relationship exists, but such correlations are not statistically significant. Once the SPOCK’s functional features are established, we demonstrate its potential to identify descriptor–performance relationships, exemplified via the ceria-promoted water–gas shift and single-atom-catalyzed electrocatalytic carbon dioxide reduction reactions. In both cases, the model uncovers descriptors previously unreported, revealing insights that are not easily recognized by human experts. Finally, we showcase SPOCK’s capabilities to formulate multivariable descriptors, an emerging topic in catalysis research. Our work pioneers an automated and standardized tool for volcano plot construction and validation, and we release the model as an open-source web application for greater accessibility and knowledge generation in catalysis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"1 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846739","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":"Quantitative Elucidation of Catalytic Reaction of Truncated Aldehyde Dehydrogenase Based on Linear Free Energy Relationship","authors":"Konatsu Ichikawa, Taiki Adachi, Yuki Kitazumi, Osamu Shirai, Keisei Sowa","doi":"10.1021/acscatal.4c07978","DOIUrl":"https://doi.org/10.1021/acscatal.4c07978","url":null,"abstract":"Some oxidoreductases can communicate directly and electrically with electrodes; this process is called direct electron transfer (DET)-type bioelectrocatalysis. Understanding its detailed mechanisms is essential for developing and improving DET-based bioelectrochemical devices. In this study, we investigated the pH dependence of kinetic and thermodynamic characteristics of a variant of an aldehyde dehydrogenase (ALDH) without the cytochrome <i>c</i> subunit (ΔC_ALDH) and compared it with that of a wild-type recombinant ALDH (rALDH). Owing to the pronounced DET activity of ΔC_ALDH at multi-walled carbon nanotubes, the voltammograms were analyzed to obtain the enzymatic parameters. The potential difference between the electrode-active site of the enzyme and electron donor (<i>E</i>°′_E – <i>E</i>°′_D) and the limiting catalytic current density (<i>j</i>_cat) exhibited an ideal linear free energy relationship (LFER), suggesting that the catalytic reaction of ΔC_ALDH was controlled by the thermodynamic driving force without any specific interactions. We also measured the ferricyanide reductase activity in solution (<i>k</i>_sol) to investigate the effect of electron acceptors (electrode and ferricyanide) on the enzymatic properties. The <i>k</i>_sol of ΔC_ALDH has a pH dependence similar to that of <i>j</i>_cat; therefore, the experimental data were kinetically analyzed based on the LFER by considering the potential difference between the electron acceptor and electrode-active site of the enzyme (<i>E</i>°′_A – <i>E</i>°′_E). By integrating the analytical results obtained from the DET-type acetaldehyde oxidation using an electrode and ferricyanide reduction in solution, the catalytic constant for the DET-type bioelectrocatalysis (<i>k</i>_DET) and the surface concentration of the effective enzyme immobilized on the electrode (Γ_E,eff) of ΔC_ALDH were calculated to be 5000 ± 2000 s^–1 and 13 ± 7 pmol cm^–2, respectively. This study achieved a detailed evaluation of the multi-step catalytic reactions of redox enzymes and can help elucidate the reaction mechanisms of DET-type bioelectrocatalysis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"136 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846740","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":"Computational Design of a Thermostable and Highly Active Terminal Deoxynucleotidyl Transferase for Synthesis of Long De Novo DNA Molecules","authors":"Yadan Niu, Binbin Chen, Huijun Zhang, Wenlong Zheng, Jianping Wu, Lirong Yang, Meng Yang, Haoran Yu","doi":"10.1021/acscatal.5c01571","DOIUrl":"https://doi.org/10.1021/acscatal.5c01571","url":null,"abstract":"It remains challenging for enzymatic synthesis of long DNA using a terminal deoxynucleotidyl transferase (TdT) due to its limited activity against intermediates containing a 3′ terminal hairpin structure that occurred during synthesis. Reverting DNA to a single strand at high temperature is a solution, while TdT exhibits limited thermostability. Here, we explored a computational design strategy to enhance the thermostability of TdT. Ten sequences designed by ProteinMPNN improved the <i>T</i>_m value by up to 24.3 °C. Two rounds design using PROSS generated the most stable and active variant M7–8 with a half-life improved by 77-fold. The M7–8 variant was successfully used for highly efficient extension of a 52 nt DNA oligonucleotide containing a hairpin structure, which makes it promising for use in the de novo synthesis of long DNA.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"6 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846668","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":"Mechanistic Insights into Ammonia Oxidation over Electron Transfer-Induced Pt–O–Cu Dual Sites","authors":"Yifan Li, Jiaxing Li, Lin Chen, Yunpeng Long, Xing Yuan, Junhua Li, Yue Peng","doi":"10.1021/acscatal.5c00862","DOIUrl":"https://doi.org/10.1021/acscatal.5c00862","url":null,"abstract":"The low selectivity for N₂ in the oxidation of NH₃ over commercial Pt/Al₂O₃ catalysts is primarily due to the overoxidation of NH₃ facilitated by Pt sites, leading to the formation of unwanted byproducts such as N₂O and NO. In this study, we present a novel strategy to enhance N₂ selectivity while maintaining NH₃ conversion by constructing Pt–O–Cu dual sites. These dual sites exhibit synergistic acid-redox characteristics through surface electron transfer mediated by bridged lattice oxygen. Additionally, the ability of surface-adsorbed oxygen to exchange with lattice oxygen is significantly improved. The electron-deficient Cu sites enhance NH₃ adsorption by providing empty 3d orbitals, while the electron-rich Pt sites promote NH₃ dehydrogenation. Subsequently, the formation of –NH or –N intermediates at the Pt sites can react with adsorbed NH₃ on the Cu sites to produce N₂, predominantly following the integrated selective catalytic reduction mechanism. The optimized dual-site catalyst achieves over 95% NH₃ conversion and N₂ selectivity at 180 °C.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"27 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143842114","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":"Enhancing the Reactivity of Cu/Al2O3 for Methanol Steam Reforming through adding CrOx: Unraveling Reaction Pathways and the Mechanism for Improvement","authors":"Lifang Jiang, Shaoteng Yuan, Jiamei Ma, Shaorong Deng, Xiuzhong Fang, Xianglan Xu, Hao Meng, Xiang Wang","doi":"10.1021/acscatal.5c00438","DOIUrl":"https://doi.org/10.1021/acscatal.5c00438","url":null,"abstract":"Copper-based catalysts are widely utilized for methanol steam reforming (MSR) reactions. However, improving their performance and achieving a deeper understanding of the reaction mechanism remain significant challenges. Herein, a series of Cu-<i>y</i>%CrO_<i>x</i>/Al₂O₃ catalysts were synthesized. The optimal Cu-7%CrO_<i>x</i>/Al₂O₃ catalyst achieved a high CH₃OH conversion of 93.2%, a low CO selectivity of 0.16%, and a competitive hydrogen production rate of 1142.7 mmol g_cat^–1 h^–1 at 260 °C with a weight space velocity of 14.6 h^–1, significantly outperforming the Cu/Al₂O₃ catalyst. Combined <i>in situ</i> spectroscopy and surface reaction experiments revealed that the MSR reaction on both catalysts predominantly followed the HCOO* pathway. This involves the dehydrogenation of CH₃OH to CH₃O*, followed by oxidation to HCOO*, and then decomposition to produce H₂ and CO₂, with the conversion of CH₃O* to HCOO* being the rate-determining step (RDS). The steam acted as a promoter for the conversions of CH₃O* and HCOO*. A small amount of formaldehyde (HCHO) derived from CH₃O* dehydrogenation tends to dissociate, forming the byproduct CO rather than converting to HCOO*. Due to the promoting effect of CrO_<i>x</i>, improved Cu dispersion, the Cu⁺/Cu⁰ ratio of around 1.0, and increased active oxygen species facilitate the RDS of CH₃O* to HCOO* and the oxidation of CO, leading to an enhanced hydrogen production rate and CO₂ selectivity on Cu-7%CrO_<i>x</i>/Al₂O₃ compared to Cu/Al₂O₃.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"90 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143842109","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":"Proximity Effects in Electronic Metal–Support Interactions: O-Vacancy Formation and CO Adsorption on Ru/ZrO2 Model Catalysts","authors":"Mengru Li, Axel Groß, R. Jürgen Behm","doi":"10.1021/acscatal.5c00519","DOIUrl":"https://doi.org/10.1021/acscatal.5c00519","url":null,"abstract":"Continuing our investigation of electronic metal–support interactions (EMSIs) in heterogeneous catalysis, we have investigated the influence of the position and the number of O-vacancies on their stabilization by the Ru nanorod, on the charge transfer from the support to the metal, and on CO adsorption on the Ru nanorod. Employing density functional theory-based calculations and using a model system consisting of a ZrO₂(111) support and a three-layer Ru nanorod, we find that O-vacancies are significantly stabilized only if they are in direct contact with the Ru nanorod, with the extent of stabilization depending on the distance between vacancy and the nearest Ru atom at the interface. Vacancy formation beside the Ru nanorod or in deeper layers of the support is not enhanced by the metal. The Ru-induced stabilization of the O-vacancies is closely coupled with the charge transfer from the support to the metal upon vacancy formation, which is true also in the presence of neighboring O-vacancies. The CO adsorption energy can be substantially modified by four characteristic effects, including charge transfer from the support to the metal, coordination effects, a combination of CO_ad-induced deformation energies and changes in the interface energy and direct interactions between CO and partly reduced Zr surface ions directly neighboring to an O-vacancy, depending on the adsorption site and on the number and positions of the O-vacancies. Thus, it is not possible to completely describe the adsorption properties by using the d-band model, in particular, not for adsorption on the interface sites. The general relevance of these findings for adsorption and catalytic reactions is discussed.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"128 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143842110","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}