Federico Loi, Luca Bignardi, Deborah Perco, Andrea Berti, Paolo Lacovig, Silvano Lizzit, Aras Kartouzian, Ulrich Heiz, Dario Alfè, Alessandro Baraldi
{"title":"揭示超小铂团簇中原子的不平等性:氧吸附仅限于原子最上层","authors":"Federico Loi, Luca Bignardi, Deborah Perco, Andrea Berti, Paolo Lacovig, Silvano Lizzit, Aras Kartouzian, Ulrich Heiz, Dario Alfè, Alessandro Baraldi","doi":"10.1002/sstr.202400250","DOIUrl":null,"url":null,"abstract":"The concept of preferential atomic and molecular adsorption site is of primary relevance in heterogeneous catalysis. In the case of ultrasmall size-selected clusters, distinguishing the role played by each atom in a reaction is extremely challenging due to their reduced size and peculiar structures. Herein, it is revealed how the inequivalent atoms composing graphene-supported Pt<sub>12</sub> and Pt<sub>13</sub> clusters behave differently in the photoinduced dissociation of O<sub>2</sub>, with only those in the uppermost layer of the clusters being involved in the reaction. In this process, the epitaxial graphene support plays a fundamental active role: its corrugation and pinning induced by the presence of the clusters are crucial for defining the preferential adsorption site on the Pt atomic agglomerates, facilitating the lateral diffusion of physisorbed oxygen at a distance that induces its selective adsorption in the topmost layer of the clusters, and inducing an inhomogeneous charge distribution within the clusters which directly affects the O<sub>2</sub> adsorption. The inhomogeneous oxidation of the clusters is resolved by means of synchrotron-based X-ray photoelectron spectroscopy and supported by ab initio density functional theory calculations. The possibility to identify the active sites on Pt clusters induced by cluster–support interactions has the potential to enhance the experimentally supported design of nanocatalysts.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":null,"pages":null},"PeriodicalIF":0.0000,"publicationDate":"2024-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Unveiling Inequality of Atoms in Ultrasmall Pt Clusters: Oxygen Adsorption Limited to the Uppermost Atomic Layer\",\"authors\":\"Federico Loi, Luca Bignardi, Deborah Perco, Andrea Berti, Paolo Lacovig, Silvano Lizzit, Aras Kartouzian, Ulrich Heiz, Dario Alfè, Alessandro Baraldi\",\"doi\":\"10.1002/sstr.202400250\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The concept of preferential atomic and molecular adsorption site is of primary relevance in heterogeneous catalysis. In the case of ultrasmall size-selected clusters, distinguishing the role played by each atom in a reaction is extremely challenging due to their reduced size and peculiar structures. Herein, it is revealed how the inequivalent atoms composing graphene-supported Pt<sub>12</sub> and Pt<sub>13</sub> clusters behave differently in the photoinduced dissociation of O<sub>2</sub>, with only those in the uppermost layer of the clusters being involved in the reaction. In this process, the epitaxial graphene support plays a fundamental active role: its corrugation and pinning induced by the presence of the clusters are crucial for defining the preferential adsorption site on the Pt atomic agglomerates, facilitating the lateral diffusion of physisorbed oxygen at a distance that induces its selective adsorption in the topmost layer of the clusters, and inducing an inhomogeneous charge distribution within the clusters which directly affects the O<sub>2</sub> adsorption. The inhomogeneous oxidation of the clusters is resolved by means of synchrotron-based X-ray photoelectron spectroscopy and supported by ab initio density functional theory calculations. The possibility to identify the active sites on Pt clusters induced by cluster–support interactions has the potential to enhance the experimentally supported design of nanocatalysts.\",\"PeriodicalId\":21841,\"journal\":{\"name\":\"Small Structures\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2024-09-09\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Small Structures\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.1002/sstr.202400250\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Small Structures","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1002/sstr.202400250","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
Unveiling Inequality of Atoms in Ultrasmall Pt Clusters: Oxygen Adsorption Limited to the Uppermost Atomic Layer
The concept of preferential atomic and molecular adsorption site is of primary relevance in heterogeneous catalysis. In the case of ultrasmall size-selected clusters, distinguishing the role played by each atom in a reaction is extremely challenging due to their reduced size and peculiar structures. Herein, it is revealed how the inequivalent atoms composing graphene-supported Pt12 and Pt13 clusters behave differently in the photoinduced dissociation of O2, with only those in the uppermost layer of the clusters being involved in the reaction. In this process, the epitaxial graphene support plays a fundamental active role: its corrugation and pinning induced by the presence of the clusters are crucial for defining the preferential adsorption site on the Pt atomic agglomerates, facilitating the lateral diffusion of physisorbed oxygen at a distance that induces its selective adsorption in the topmost layer of the clusters, and inducing an inhomogeneous charge distribution within the clusters which directly affects the O2 adsorption. The inhomogeneous oxidation of the clusters is resolved by means of synchrotron-based X-ray photoelectron spectroscopy and supported by ab initio density functional theory calculations. The possibility to identify the active sites on Pt clusters induced by cluster–support interactions has the potential to enhance the experimentally supported design of nanocatalysts.