Lang Xu , Michael Rebarchik , Saurabh Bhandari, Manos Mavrikakis
{"title":"Adsorbate-induced adatom formation on Au-Cu bimetallic alloys and its possible consequences for CO2 electroreduction","authors":"Lang Xu , Michael Rebarchik , Saurabh Bhandari, Manos Mavrikakis","doi":"10.1016/j.susc.2024.122613","DOIUrl":null,"url":null,"abstract":"<div><div>The adsorbate-induced formation of sub-nanometer clusters on transition-metal single crystals observed in previous high-pressure microscopic studies hinted at the <em>in-situ</em> formation of unique active sites even on large nanoparticle catalysts. We propose that the adatom formation energy can be used as an energetic descriptor for the initial step toward the adsorbate-induced metal-cluster formation process. This descriptor can be efficiently computed using density functional theory (DFT) calculations and applied for screening and identification of metal catalysts where this phenomenon may play an important role in generating active sites <em>in-situ</em>. As a proof of concept, here, we construct an adatom formation energy database for three Au<sub>x</sub>Cu<sub>y</sub> alloys (<em>x:y</em> = 3:1, 1:1, or 1:3) and eighteen adsorbates (H, C, N, O, F, S, Cl, Br, I, CH<sub>x</sub>, NH<sub>x</sub> (<em>x</em> = 1 – 3), CO, NO, and OH) commonly involved in catalytic reactions. The energetics of adatom formation were examined in all cases where the (111) terrace, (211) step-edge, and (874) kink were the sources of the adatom. We demonstrate that the presence of an adsorbate could alter not only the energetics for adatom formation but also the elemental nature of the preferred adatom being formed. Using our database, we identified promising systems which favor adsorbate-induced adatom formation under near-ambient conditions. Specifically, CO-induced adatom formation on all three Au-Cu alloy surfaces could occur under CO<sub>2</sub> electroreduction (CO<sub>2</sub>RR) conditions. This phenomenon offers a qualitative explanation for the experimentally observed CO<sub>2</sub>RR activity on Au-Cu alloy catalysts. Our methodology offers an easily expandable and efficient approach for large-scale catalyst screening with regards to adatom/cluster formation under reaction conditions and provides insight into the possible nature of active sites on alloy catalysts from a novel perspective.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"751 ","pages":"Article 122613"},"PeriodicalIF":2.1000,"publicationDate":"2024-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Surface Science","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S003960282400164X","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
The adsorbate-induced formation of sub-nanometer clusters on transition-metal single crystals observed in previous high-pressure microscopic studies hinted at the in-situ formation of unique active sites even on large nanoparticle catalysts. We propose that the adatom formation energy can be used as an energetic descriptor for the initial step toward the adsorbate-induced metal-cluster formation process. This descriptor can be efficiently computed using density functional theory (DFT) calculations and applied for screening and identification of metal catalysts where this phenomenon may play an important role in generating active sites in-situ. As a proof of concept, here, we construct an adatom formation energy database for three AuxCuy alloys (x:y = 3:1, 1:1, or 1:3) and eighteen adsorbates (H, C, N, O, F, S, Cl, Br, I, CHx, NHx (x = 1 – 3), CO, NO, and OH) commonly involved in catalytic reactions. The energetics of adatom formation were examined in all cases where the (111) terrace, (211) step-edge, and (874) kink were the sources of the adatom. We demonstrate that the presence of an adsorbate could alter not only the energetics for adatom formation but also the elemental nature of the preferred adatom being formed. Using our database, we identified promising systems which favor adsorbate-induced adatom formation under near-ambient conditions. Specifically, CO-induced adatom formation on all three Au-Cu alloy surfaces could occur under CO2 electroreduction (CO2RR) conditions. This phenomenon offers a qualitative explanation for the experimentally observed CO2RR activity on Au-Cu alloy catalysts. Our methodology offers an easily expandable and efficient approach for large-scale catalyst screening with regards to adatom/cluster formation under reaction conditions and provides insight into the possible nature of active sites on alloy catalysts from a novel perspective.
期刊介绍:
Surface Science is devoted to elucidating the fundamental aspects of chemistry and physics occurring at a wide range of surfaces and interfaces and to disseminating this knowledge fast. The journal welcomes a broad spectrum of topics, including but not limited to:
• model systems (e.g. in Ultra High Vacuum) under well-controlled reactive conditions
• nanoscale science and engineering, including manipulation of matter at the atomic/molecular scale and assembly phenomena
• reactivity of surfaces as related to various applied areas including heterogeneous catalysis, chemistry at electrified interfaces, and semiconductors functionalization
• phenomena at interfaces relevant to energy storage and conversion, and fuels production and utilization
• surface reactivity for environmental protection and pollution remediation
• interactions at surfaces of soft matter, including polymers and biomaterials.
Both experimental and theoretical work, including modeling, is within the scope of the journal. Work published in Surface Science reaches a wide readership, from chemistry and physics to biology and materials science and engineering, providing an excellent forum for cross-fertilization of ideas and broad dissemination of scientific discoveries.