ACS Catalysis 最新文献

{"title":"Effect of Iron Doping in Ordered Nickel Oxide Thin Film Catalyst for the Oxygen Evolution Reaction","authors":"Ane Etxebarria, Mauricio Lopez Luna, Andrea Martini, Uta Hejral, Martina Rüscher, Chao Zhan, Antonia Herzog, Afshan Jamshaid, David Kordus, Arno Bergmann, Helmut Kuhlenbeck, Beatriz Roldan Cuenya","doi":"10.1021/acscatal.4c02572","DOIUrl":"https://doi.org/10.1021/acscatal.4c02572","url":null,"abstract":"Water splitting has emerged as a promising route for generating hydrogen as an alternative to conventional production methods. Finding affordable and scalable catalysts for the anodic half-reaction, the oxygen evolution reaction (OER), could help with its industrial widespread implementation. Iron-containing Ni-based catalysts have a competitive performance for the use in commercial alkaline electrolyzers. Due to the complexity of studying the catalysts at working conditions, the active phase and the role that iron exerts in conjunction with Ni are still a matter of investigation. Here, we study this topic with NiO(001) and Ni_0.75Fe_0.25O_<i>x</i>(001) thin film model electrocatalysts employing surface-sensitive techniques. We show that iron constrains the growth of the oxyhydroxide phase formed on top of the Ni or NiFe oxide, which is considered the active phase for the OER. Besides, <i>operando</i> Raman and grazing incidence X-ray absorption spectroscopy experiments reveal that the presence of iron affects both, the disorder level of the active phase and the oxidative charge around Ni during OER. The observed compositional, structural, and electronic properties of each system have been correlated with their electrochemical performance.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142166589","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":"Chemoselective Cu-Catalyzed Cross-Nucleophile Alkylarylation of Alkenes","authors":"SangHyun Lee, Jianyang D. Yu, Alex L. Monterde, Sarah E. Tung, Ya-Nong Wang, Brittany L. Gay, Kami L. Hull","doi":"10.1021/acscatal.4c03955","DOIUrl":"https://doi.org/10.1021/acscatal.4c03955","url":null,"abstract":"We report a general cross-nucleophile alkene alkylarylation that adds two different boronic acids, an alkyl and an aryl, across a vinylarene to afford 1,1-diarylalkanes. The high chemoselectivity originates from the distinct reactivities of the two boronic acids: the alkylboronic acid is selectively oxidized to an alkyl radical, while the arylboronic acid favors transmetalation with the Cu(II) catalyst. Mechanistic studies suggest that Lewis acid–Lewis base interactions between in situ generated boroxines and added amine are critical for selectivity. A scope of 37 examples is presented with structurally and electronically diverse alkyl, vinyl, and aryl coupling partners. The synthetic utility is demonstrated in the preparation of pimozide and anticancer agent analogues.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142171150","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":"Size Dependent Photocatalytic Activity of Mesoporous ZnIn2S4 Nanocrystal Networks","authors":"Evangelos K. Andreou,&nbsp;Ioannis Vamvasakis,&nbsp;Andreas Douloumis,&nbsp;Georgios Kopidakis and Gerasimos S. Armatas*,&nbsp;","doi":"10.1021/acscatal.4c0419510.1021/acscatal.4c04195","DOIUrl":"https://doi.org/10.1021/acscatal.4c04195https://doi.org/10.1021/acscatal.4c04195","url":null,"abstract":"<p >Understanding of the band-edge electronic structure and charge-transfer dynamics in size-confined nanostructures is vital in designing new materials for energy conversion applications, including green hydrogen production, decomposition of organic pollutants and solar cells. In this study, a series of mesoporous materials comprising continuous networks of linked zinc indium sulfide (ZnIn₂S₄) nanocrystals with a tunable diameter (ranging from 4 to 12 nm) is reported. These nanomaterials demonstrate intriguing size-dependent electronic properties, charge-transfer kinetics and photocatalytic behaviors. Our extensive characterizations uncover strong size effects on the catalytic activity of constituent ZnIn₂S₄ nanocrystals in the photochemical hydrogen evolution reaction. As an outcome, the optimized single-component ZnIn₂S₄ mesostructure produces hydrogen at a 7.8 mmol g_cat^–1 h^–1 release rate under ultraviolet (UV)–visible light irradiation associated with an apparent quantum yield (AQY) of 17.2% at 420 ± 10 nm, far surpassing its microstructured counterpart by a factor of 10.7×. These findings provide a valuable perspective for the rational design of semiconductor nanostructures through synthetic engineering, aiming at the development of high-performance catalysts for zero-carbon energy-related applications.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":11.3,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscatal.4c04195","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142270216","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":"Progress in Enzyme-Catalyzed C(sp3)–H Amination","authors":"Wei-Nan Xu,&nbsp;Ya-Dong Gao,&nbsp;Ping Su,&nbsp;Luqi Huang,&nbsp;Zhao-Lin He* and Li-Cheng Yang*,&nbsp;","doi":"10.1021/acscatal.4c0494710.1021/acscatal.4c04947","DOIUrl":"https://doi.org/10.1021/acscatal.4c04947https://doi.org/10.1021/acscatal.4c04947","url":null,"abstract":"<p >Amine structures are widely present in various biologically active natural products, drug molecules, and material structures. Among the various strategies of amine synthesis, C(sp³)–H amination has become a powerful strategy due to its atom economy and multiple potential reaction sites compared with conventional amine synthesis methods. Due to the advantages of high catalytic efficiency, high selectivity, environmental friendliness, and high modifiability of the enzyme, the enzymatic C(sp³)–H amination is of great research significance. However, it was not until recent years that natural enzymes capable of catalyzing the amination of C(sp³)–H bonds were discovered. Modifying enzymes to confer unnatural C(sp³)–H amination activity holds great potential. In the past decade, a series of protocols for the amination of C(sp³)–H bonds using engineered enzymes have been developed, several of which showed comparable properties to those of natural enzymes.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":11.3,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142270215","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":"Intramolecular C–H Oxidation in Iron(V)-oxo-carboxylato Species Relevant in the γ-Lactonization of Alkyl Carboxylic Acids","authors":"Andrea Álvarez-Núñez, Rudraditya Sarkar, Valeria Dantignana, Jin Xiong, Yisong Guo, Josep M. Luis, Miquel Costas, Anna Company","doi":"10.1021/acscatal.4c01258","DOIUrl":"https://doi.org/10.1021/acscatal.4c01258","url":null,"abstract":"High-valent oxoiron species have been invoked as oxidizing agents in a variety of iron-dependent oxygenases. Taking inspiration from nature, selected nonheme iron complexes have been developed as catalysts to elicit C–H oxidation through the mediation of putative oxoiron(V) species, akin to those proposed for Rieske oxygenases. The addition of carboxylic acids in these iron-catalyzed C–H oxidations has proved highly beneficial in terms of product yields and selectivities, suggesting the direct involvement of iron(V)-oxo-carboxylato species. When the carboxylic acid functionality is present in the alkane substrate, it acts as a directing group, enabling the selective intramolecular γ-C–H hydroxylation that eventually affords γ-lactones. While this mechanistic frame is solidly supported by previous mechanistic studies, direct spectroscopic detection of the key iron(V)-oxo-carboxylato intermediate and its competence for engaging in the selective γ–C–H oxidation leading to lactonization have not been accomplished. In this work, we generate a series of well-defined iron(V)-oxo-carboxylato species (<b>2c</b>–<b>2f</b>) differing in the nature of the bound carboxylate ligand. Species <b>2c</b>–<b>2f</b> are characterized by a set of spectroscopic techniques, including UV–vis spectroscopy, cold-spray ionization mass spectrometry (CSI-MS), and, in selected cases, EPR and Mössbauer spectroscopies. We demonstrate that <b>2c</b>–<b>2f</b> undergo site-selective γ-lactonization of the carboxylate ligand in a stereoretentive manner, thus unequivocally identifying metal-oxo-carboxylato species as the powerful yet selective C–H cleaving species in catalytic γ-lactonization reactions of carboxylic acids. Reactivity experiments confirm that the intramolecular formation of γ-lactones is in competition with the intermolecular oxidation of external alkanes and olefins. Finally, mechanistic studies, together with DFT calculations, support a mechanism involving a site-selective C–H cleavage in the γ-position of the carboxylate ligand by the oxo moiety, followed by a fast carboxylate rebound, eventually leading to the selective formation of γ-lactones.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142166592","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":"Hydrogen Peroxide Generation and Hydrogen Oxidation Reaction on Pt/Co/Pt(111) and Pt/Co/Pt(100) Single-Crystal Model Catalyst Surface","authors":"Kenta Hayashi, Takeru Tomimori, Yoshihiro Chida, Naoto Todoroki, Toshimasa Wadayama","doi":"10.1021/acscatal.4c03106","DOIUrl":"https://doi.org/10.1021/acscatal.4c03106","url":null,"abstract":"To mitigate proton-exchange membrane (PEM) degradation, suppressing hydrogen peroxide (H₂O₂) generation is desired for the anode catalyst of PEM fuel cells (PEMFCs), while keeping the hydrogen oxidation reaction (HOR) activity. In this study, Pt/Co/Pt(111) and Pt/Co/Pt(100), approximately 2 nm-thick epitaxially stacked layers of Pt and Pt–Co alloy deposited on Pt(111) and Pt(100) single-crystal surfaces, respectively, were used as microstructural surface models of the Pt–Co anode catalyst, and the H₂O₂ generation and HOR mechanisms were discussed using the substrate generation/tip collection and tip generation/substrate collection modes of a scanning electrochemical microscope. We found that H₂O₂ generation on Pt/Co/Pt(111) was much lower than that on clean Pt(111), whereas the H₂O₂ generation property of Pt/Co/Pt(100) was similar to that of clean Pt(100). The influence of the underlying Co (Pt–Co) layers on H₂O₂ generation is discussed from the viewpoints of two previously proposed mechanisms: the adsorbed hydrogen (H_ads)-related and water-adlayer-related mechanisms. Considering the applied potential dependence of H₂O₂ generation, the former H_ads-related mechanism could not explain the H₂O₂ generation behavior of Pt/Co/Pt(100), whereas the latter water-adlayer-related mechanism could apply to both Pt/Co/Pt(111) and Pt/Co/Pt(100). Regarding the HOR, Pt/Co/Pt(100) showed a higher activity than that of clean Pt(100), whereas the activity of Pt/Co/Pt(111) was lower than that of the corresponding clean Pt(111). Such surface-atomic-arrangement-dependent HOR activities of Pt induced by the underlaid Co (Pt–Co) layers can be explained by weakened hydrogen adsorption energy, which can be rationalized by cyclic voltammogram features. The results clarify the alloying effect of Pt with Co for suppressing H₂O₂ generation while maintaining substantial HOR activity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142171298","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":"Iridium-Catalyzed Asymmetric Cascade Allylation/[1,4]-Phospha-Brook Rearrangement Reaction","authors":"Zhi-Yuan Yi, Hui Xu, Xin Chang, Yanfeng Dang, Xiu-Qin Dong, Chun-Jiang Wang","doi":"10.1021/acscatal.4c04078","DOIUrl":"https://doi.org/10.1021/acscatal.4c04078","url":null,"abstract":"Chiral δ-carbonyl phosphates and their derivatives represent important structural units frequently found in natural products and biologically active molecules and have been extensively employed as key intermediates in organic synthesis. Herein, an unprecedented iridium-catalyzed asymmetric cascade allylation/[1,4]-phospha-Brook rearrangement of β-keto phosphonates with vinyl ethylene carbonate was established, offering an efficient synthetic strategy to access highly functionalized chiral δ-carbonyl phosphates that are difficult to access via known methods. This protocol features easily available starting materials, mild reaction conditions, high chemo-/regio-/enantioselectivity, and a wide substrate scope. Notably, this methodology can be extended to various β-functionalized phosphonates. The gram-scale reaction, diverse functional transformations, and stereodivergent synthesis of chiral δ-hydroxyl phosphates containing two nonadjacent stereocenters demonstrated the synthetic potential of this method. The synthetic utility of this cascade reaction was further confirmed in the concise formal synthesis of natural products hormosirene, dictyopterene A, and biologically active (<i>R</i>)-MCPA-CoA. Control experiments and density field theory computational mechanistic studies revealed that this transformation undergoes asymmetric allylation via kinetic resolution followed by a unique [1,4]-phospha-Brook rearrangement. Ligand–substrate interactions were identified to rationalize the kinetic resolution and chiral induction. The stronger σ-bond of P–O than that of O–C makes the [1,4]-phospha-Brook rearrangement kinetically and thermodynamically favorable.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142160923","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 the Dealumination of an H-ZSM-5 Zeolite Using Reactive Molecular Dynamics Simulations","authors":"E. Grajales-González*,&nbsp;M. Monge-Palacios*,&nbsp;Sirio Brunialti and S. Mani Sarathy,&nbsp;","doi":"10.1021/acscatal.3c0516810.1021/acscatal.3c05168","DOIUrl":"https://doi.org/10.1021/acscatal.3c05168https://doi.org/10.1021/acscatal.3c05168","url":null,"abstract":"<p >Zeolites are among the most successful catalysts used in the petrochemical industry, as well as in more environment-friendly processes such as biomass conversion to fuels and chemicals. A major challenge in bioresource utilization is the presence of water, so addressing fundamental aspects of zeolite-water interactions is imperative. Among the different zeolite water-driven phenomena, dealumination is ubiquitous and affects several stages of the catalyst lifetime. To better understand this phenomena, this contribution investigates the dealumination mechanism of an H-ZSM-5 catalyst using reactive molecular dynamics simulations and implementing the ReaxFF force field. The strength of the approach used here relies on its capability to consider entropic and dynamic effects, which are usually ignored by the widespread static density functional theory (DFT) calculations that are often conducted on this kind of materials. Simulations were run at 1000, 1300, and 1600 K, and for H₂O:Al loads of 4:1, 6:1, and 8:1 during 1 ns using a constant number of molecules, pressure, and temperature (<i>NPT</i> ensemble). The results show a percentage of framework-associated aluminum (FAAl) between 40 and 50%, in good agreement with the experimental range reported in the literature of 30–40%. The mechanism of zeolite dealumination displayed three relevant dynamic features not reported in previous theoretical studies but that are supported by experiments: water-assisted proton transport, framework flexibility, and silicon-assisted aluminum dislodging. The dynamic chemistry of the dealumination also showed the most relevant step demonstrated by previous DFT studies, namely, the water adsorption and its subsequent dissociation to form silanol and adsorbed hydroxyl groups. This reaction is favored in the last stages of the dealumination and at high water loads. Static DFT calculations performed in this work and others reported in the literature indicate that water adsorption on the aluminum atom is spontaneous at high temperatures, including those above 1000 K, when the ideal gas phase reference state of water is modified to include effects of the zeolite environment, that is, enthalpy and entropy loses. Kinetic factors in heating protocols similar to calcination also appear to promote water adsorption and dealumination over transport to the gas phase, which should still be significant at temperatures as high as 1000 K. Besides, the structure of the identified extra-framework aluminum and FAAl matches the documented descriptions drawn from nuclear magnetic resonance spectroscopy analysis. The results of this work complement the body of research about zeolite dealumination aimed at the rational design of biomass conversion processes.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":11.3,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142273848","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":"Saccharide-Assisted Resolution of Bioactive Chiral Carboxylic Acids via NHC-Catalyzed Regioselective Transesterification","authors":"Shuolu Dai,&nbsp;Juan Zou,&nbsp;Haiqi Wang,&nbsp;Min Xu,&nbsp;Erjuan Xu,&nbsp;Jia Song,&nbsp;Yu Hong,&nbsp;Shaojun Li,&nbsp;Wen-Xin Lv* and Yonggui Robin Chi*,&nbsp;","doi":"10.1021/acscatal.4c0407610.1021/acscatal.4c04076","DOIUrl":"https://doi.org/10.1021/acscatal.4c04076https://doi.org/10.1021/acscatal.4c04076","url":null,"abstract":"<p >The utility of unprotected saccharides as chiral auxiliaries in asymmetric synthesis remains largely undeveloped despite their ready availability, configurational diversity, and chiral purity. Here, we disclose an efficient achiral NHC catalytic strategy to regioselectively install racemic α,α-disubstituted carboxylic esters on specific OH groups of saccharides and simultaneously achieve their dynamic kinetic resolution, which makes unprotected saccharides effective chiral auxiliaries. Multiple controlling parameters, including stereoelectronic and steric effects, are employed to ensure regioselectivity amplification and stereodifferentiation. By varying the structures of NHC catalysts, this strategy is suitable for dynamic kinetic resolution of diverse racemic targets by installing them on different OH sites of structurally diverse unprotected saccharides, greatly expanding the application of saccharides in asymmetric synthesis.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":11.3,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142270062","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":"On the Structure Sensitivity of CO2 Hydrogenation over Cu/ZrO2: Insights into the Role of the Support and the Active Sites","authors":"Tomás Vergara, Daviel Gómez, Lucas Warmuth, Annika E. Enss, Martin Peterlechner, Rodrigo Pallacán, Vlad Martin Diaconescu, Laura Simonelli, Felix Studt, Patricia Concepción, Romel Jiménez, Alejandro Karelovic","doi":"10.1021/acscatal.4c03803","DOIUrl":"https://doi.org/10.1021/acscatal.4c03803","url":null,"abstract":"The well-known structure sensitivity of CO₂ hydrogenation to methanol has shown to be an impactful topic for the performance of the catalyst and yet remains unaddressed for Cu nanoparticles supported on ZrO₂, a material that has shown to be involved in the active site and the reaction mechanism of methanol formation. Herein, Cu/ZrO₂ catalysts were studied to unravel the underlying structure–activity relationships by combining surface and bulk characterization techniques, kinetic measurements, operando<i>-</i>DRIFTS and DFT calculations. Contrary to Cu over inert supports, the results showed different trends and two distinct kinetic regimes. For Cu nanoparticles larger than 2 nm, they are in accordance with previously reported results, this is, a change in the number of active sites, without affecting the nature of them. Conversely, it is demonstrated that the active sites are markedly different over the regime of nanoparticles smaller than 2 nm, accessed for ultralow Cu contents of 0.1 wt %, as evidenced from the systematic change of kinetic parameters and from operando<i>-</i>DRIFTS. The distinct active sites were identified as isolated Cu species (i.e., single atoms and Cu incorporated into the lattice of ZrO₂) and highly stable Cu clusters, both of which would allocate the formation of products for low metal contents. The results are certainly related to the interaction between Cu and ZrO₂ and unequivocally disclose the relationship between activity regimes and the nature of active sites as a function of the Cu particle size. Furthermore, they demonstrate that distinct active sites can be accessed just by varying the metal content on active reducible supports. As such, the findings are of particular relevance for the fundamental understanding of the interaction between Cu and ZrO₂ and its interdependence with the size of the Cu nanoparticles, as well as for the rational design of catalysts for CO₂ hydrogenation to methanol.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142166563","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}