This study explores the adsorption and reac-tion of methanol on the CeO_(2)(111)and Ni/CeO_(2)(111)surfaces,highlighting the es-sential role of metal-support interaction in methanol decomposition by a synergistic ap-p...This study explores the adsorption and reac-tion of methanol on the CeO_(2)(111)and Ni/CeO_(2)(111)surfaces,highlighting the es-sential role of metal-support interaction in methanol decomposition by a synergistic ap-proach encompassing synchrotron radiation photoemission spectroscopy,X-ray photo-electron spectroscopy,infrared reflection and absorption spectroscopy,and temperature-programmed desorption.Our findings reveal that Ni deposited on the CeO_(2)(111)surface,followed by annealing to 700 K,leads to the formation of Ce-O-Ni mixed oxide as the dominant phase.The Ni^(2+)species facilitate the methoxy decomposition into CO and H_(2)within 300-430 K,with a small amount of formalde-hyde also forming at the edge sites of ceria.Additionally,some methoxy adsorbed on the bare CeO_(2)surface migrates to the Ce-O-Ni mixed oxide,where they decompose into CO and H_(2)at 500-600 K,accompanied by a portion of the methoxy interacting with ceria to generate formaldehyde.Upon exposure to methanol at 500 K,the Ni^(2+)species are reduced to metallic Ni^(0),alongside the formation of coke and Ni_(3)C,ultimately resulting in catalyst deactivation.However,reintroducing O_(2)reactivates these sites by oxidizing metallic Ni^(0)and Ni_(3)C species.This study highlights the pivotal role of metal-support interaction in promoting oxygen trans-fer from ceria to Ni,thereby enhancing methoxy decomposition and significantly improving the performance of Ni-based catalysts for methanol decomposition into CO and H_(2).展开更多
基金financially supported by the National Key R&D Program of China(2023YFA1509103)the National Natural Science Foundation of China(Nos.22272157,21872131,22106085,and U1932214)。
文摘This study explores the adsorption and reac-tion of methanol on the CeO_(2)(111)and Ni/CeO_(2)(111)surfaces,highlighting the es-sential role of metal-support interaction in methanol decomposition by a synergistic ap-proach encompassing synchrotron radiation photoemission spectroscopy,X-ray photo-electron spectroscopy,infrared reflection and absorption spectroscopy,and temperature-programmed desorption.Our findings reveal that Ni deposited on the CeO_(2)(111)surface,followed by annealing to 700 K,leads to the formation of Ce-O-Ni mixed oxide as the dominant phase.The Ni^(2+)species facilitate the methoxy decomposition into CO and H_(2)within 300-430 K,with a small amount of formalde-hyde also forming at the edge sites of ceria.Additionally,some methoxy adsorbed on the bare CeO_(2)surface migrates to the Ce-O-Ni mixed oxide,where they decompose into CO and H_(2)at 500-600 K,accompanied by a portion of the methoxy interacting with ceria to generate formaldehyde.Upon exposure to methanol at 500 K,the Ni^(2+)species are reduced to metallic Ni^(0),alongside the formation of coke and Ni_(3)C,ultimately resulting in catalyst deactivation.However,reintroducing O_(2)reactivates these sites by oxidizing metallic Ni^(0)and Ni_(3)C species.This study highlights the pivotal role of metal-support interaction in promoting oxygen trans-fer from ceria to Ni,thereby enhancing methoxy decomposition and significantly improving the performance of Ni-based catalysts for methanol decomposition into CO and H_(2).
