Thomas Haunold , Krešimir Anić , Alexander Genest , Christoph Rameshan , Matteo Roiaz , Hao Li , Thomas Wicht , Jan Knudsen , Günther Rupprechter
{"title":"通过原位常压 XPS 和 DFT 研究 Ir(100) 上超薄 Co3O4(111) 薄膜的羟基化过程","authors":"Thomas Haunold , Krešimir Anić , Alexander Genest , Christoph Rameshan , Matteo Roiaz , Hao Li , Thomas Wicht , Jan Knudsen , Günther Rupprechter","doi":"10.1016/j.susc.2024.122618","DOIUrl":null,"url":null,"abstract":"<div><div>In the present work, we have studied the interaction of water with spinel cobalt oxide (Co<sub>3</sub>O<sub>4</sub>), an effect which has been considered a major cause of its catalytic deactivation. Employing a Co<sub>3</sub>O<sub>4</sub>(111) model thin film grown on Ir(100) in (ultra)high vacuum, and ambient pressure X-ray photoelectron spectroscopy (APXPS), hydroxylation in 0.5 mbar H<sub>2</sub>O vapor at room temperature was monitored in real time. The surface hydroxyl (OH) coverage was determined <em>via</em> two different models based (i) on the termination of a pristine and OH-covered Co<sub>3</sub>O<sub>4</sub>(111) surface as derived from density functional theory (DFT) calculations, and (ii) on a homogeneous cobalt oxyhydroxide (CoO(OH)) overlayer. Langmuir pseudo-second-order kinetics were applied to characterize the OH evolution with time, suggesting two regimes of chemisorption at the mosaic-like Co<sub>3</sub>O<sub>4</sub>(111) film: (i) plateaus, which were quickly saturated by OH, followed by (ii) slow hydroxylation in the “cracks” of the thin film. H<sub>2</sub>O dissociation and OH formation, blocking exposed Co<sup>2+</sup> ions and additionally consuming surface lattice oxygen, respectively, may thus account for catalyst deactivation by H<sub>2</sub>O traces in reactive feeds.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"751 ","pages":"Article 122618"},"PeriodicalIF":2.1000,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Hydroxylation of an ultrathin Co3O4(111) film on Ir(100) studied by in situ ambient pressure XPS and DFT\",\"authors\":\"Thomas Haunold , Krešimir Anić , Alexander Genest , Christoph Rameshan , Matteo Roiaz , Hao Li , Thomas Wicht , Jan Knudsen , Günther Rupprechter\",\"doi\":\"10.1016/j.susc.2024.122618\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>In the present work, we have studied the interaction of water with spinel cobalt oxide (Co<sub>3</sub>O<sub>4</sub>), an effect which has been considered a major cause of its catalytic deactivation. Employing a Co<sub>3</sub>O<sub>4</sub>(111) model thin film grown on Ir(100) in (ultra)high vacuum, and ambient pressure X-ray photoelectron spectroscopy (APXPS), hydroxylation in 0.5 mbar H<sub>2</sub>O vapor at room temperature was monitored in real time. The surface hydroxyl (OH) coverage was determined <em>via</em> two different models based (i) on the termination of a pristine and OH-covered Co<sub>3</sub>O<sub>4</sub>(111) surface as derived from density functional theory (DFT) calculations, and (ii) on a homogeneous cobalt oxyhydroxide (CoO(OH)) overlayer. Langmuir pseudo-second-order kinetics were applied to characterize the OH evolution with time, suggesting two regimes of chemisorption at the mosaic-like Co<sub>3</sub>O<sub>4</sub>(111) film: (i) plateaus, which were quickly saturated by OH, followed by (ii) slow hydroxylation in the “cracks” of the thin film. H<sub>2</sub>O dissociation and OH formation, blocking exposed Co<sup>2+</sup> ions and additionally consuming surface lattice oxygen, respectively, may thus account for catalyst deactivation by H<sub>2</sub>O traces in reactive feeds.</div></div>\",\"PeriodicalId\":22100,\"journal\":{\"name\":\"Surface Science\",\"volume\":\"751 \",\"pages\":\"Article 122618\"},\"PeriodicalIF\":2.1000,\"publicationDate\":\"2024-09-26\",\"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/S0039602824001699\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Surface Science","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0039602824001699","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Hydroxylation of an ultrathin Co3O4(111) film on Ir(100) studied by in situ ambient pressure XPS and DFT
In the present work, we have studied the interaction of water with spinel cobalt oxide (Co3O4), an effect which has been considered a major cause of its catalytic deactivation. Employing a Co3O4(111) model thin film grown on Ir(100) in (ultra)high vacuum, and ambient pressure X-ray photoelectron spectroscopy (APXPS), hydroxylation in 0.5 mbar H2O vapor at room temperature was monitored in real time. The surface hydroxyl (OH) coverage was determined via two different models based (i) on the termination of a pristine and OH-covered Co3O4(111) surface as derived from density functional theory (DFT) calculations, and (ii) on a homogeneous cobalt oxyhydroxide (CoO(OH)) overlayer. Langmuir pseudo-second-order kinetics were applied to characterize the OH evolution with time, suggesting two regimes of chemisorption at the mosaic-like Co3O4(111) film: (i) plateaus, which were quickly saturated by OH, followed by (ii) slow hydroxylation in the “cracks” of the thin film. H2O dissociation and OH formation, blocking exposed Co2+ ions and additionally consuming surface lattice oxygen, respectively, may thus account for catalyst deactivation by H2O traces in reactive feeds.
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.