Mechanistic Understanding of Dissociated Hydrogen in Cu/CeO2-Catalyzed Methanol Synthesis

doi:10.1021/acsami.4c18915

	Mechanistic Understanding of Dissociated Hydrogen in Cu/CeO2-Catalyzed Methanol Synthesis
	Zhu, Liang1 ; Liu, Yang1 ; Gao, Yanhui1 ; Ding, Ningxujin1 ; Wang, Danyu1 ; Long, Liuliu1 ; Wang, Beibei2 ; Lang, Junyu1 ; Vovk, Evgeny.I1 ; Yang, Yong1,3
	2025-01
发表期刊	ACS APPLIED MATERIALS & INTERFACES
ISSN	1944-8244
EISSN	1944-8252
卷号	17 期号:4 页码:7151-7163
发表状态	已发表
DOI	10.1021/acsami.4c18915
摘要	The hydrogen dissociation and spillover mechanism on oxide-supported Cu catalysts play a pivotal role in the hydrogenation of carbon dioxide to methanol. This study investigates the hydrogen spillover mechanism on Cu/CeO2 catalysts using in situ spectral characterization under high-pressure reaction conditions and density functional theory (DFT) simulations. The research confirms that the Cu sites serve as the initial dissociation points for the hydrogen molecules. The chemically adsorbed hydrogen (H*) then spills over onto the CeO2 support and interacts with the lattice oxygen to form special hydroxyl groups, while simultaneously reducing the surrounding Ce4+ to form Ce3+. Interestingly, the temperature-programmed desorption (TPD) results found that heating the hydroxyl-containing surface mainly reverses H2 dissociation by desorbing H2 instead of forming H2O, while no significant vacancy formation was detected. The DFT calculation identified a subsurface pathway favoring hydrogen migration, which explained the dominating H2 in the TPD products. A chemical loop study after CO2/H2 cofeeding on the catalyst reveals that hydrogen spillover facilitates the highly reduced surface serving as the active centers, enabling a secondary methanol synthesis in a vacuum. This study provides a model of the formation and desorption pathways of hydrogen species on Cu/CeO2 catalysts and illustrates the key role of the hydrogen spillover mechanism in promoting the CO2 hydrogenation to methanol reaction through important experimental analysis. © 2025 American Chemical Society.
关键词	Bioremediation Catalysis Cerium oxide Dissociation Hydrogenolysis Photoionization Spectrum analyzers CeO 2 Cu/CeO2 Hydrogen spill overs Hydrogen spillover Hydrogen spillover mechanism Methanol synthesis Pre-treatments Spillover mechanisms Temperature-programmed desorption-MS Temperature-programmed desorptions XPS after in situ pretreatment
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收录类别	EI ; SCI
语种	英语
资助项目	National Natural Science Foundation of China["22272107","22072092"] ; National Natural Science Foundation of China[2023YFB4005200] ; HPC Platform of ShanghaiTech University[21DZ2260400]
WOS研究方向	Science & Technology - Other Topics ; Materials Science
WOS类目	Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary
WOS记录号	WOS:001401900100001
出版者	American Chemical Society
EI入藏号	20250417743627
EI主题词	Temperature programmed desorption
EI分类号	1502.1 ; 1502.4 ; 802.2 Chemical Reactions ; 802.3 Chemical Operations ; 804.2 Inorganic Compounds ; 942.1.3
原始文献类型	Journal article (JA)
文献类型	期刊论文
条目标识符	https://kms.shanghaitech.edu.cn/handle/2MSLDSTB/474163
专题	物质科学与技术学院_PI研究组_杨永组大科学中心_PI研究组_刘志组物质科学与技术学院_公共科研平台_分析测试平台物质科学与技术学院_硕士生物质科学与技术学院_博士生
共同第一作者	Liu, Yang
通讯作者	Lang, Junyu; Vovk, Evgeny.I; Yang, Yong
作者单位	1.School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, People’s Republic of China 2.Center for Transformative Science, ShanghaiTech University, Shanghai 201210, People’s Republic of China 3.Shanghai Key Laboratory of High-resolution Electron Microscopy, ShanghaiTech University, Shanghai 201210, People’s Republic of China
第一作者单位	物质科学与技术学院
通讯作者单位	物质科学与技术学院; 上海科技大学
第一作者的第一单位	物质科学与技术学院
推荐引用方式 GB/T 7714	Zhu, Liang,Liu, Yang,Gao, Yanhui,et al. Mechanistic Understanding of Dissociated Hydrogen in Cu/CeO2-Catalyzed Methanol Synthesis[J]. ACS APPLIED MATERIALS & INTERFACES,2025,17(4):7151-7163.
APA	Zhu, Liang.,Liu, Yang.,Gao, Yanhui.,Ding, Ningxujin.,Wang, Danyu.,...&Yang, Yong.(2025).Mechanistic Understanding of Dissociated Hydrogen in Cu/CeO2-Catalyzed Methanol Synthesis.ACS APPLIED MATERIALS & INTERFACES,17(4),7151-7163.
MLA	Zhu, Liang,et al."Mechanistic Understanding of Dissociated Hydrogen in Cu/CeO2-Catalyzed Methanol Synthesis".ACS APPLIED MATERIALS & INTERFACES 17.4(2025):7151-7163.