Structure of the catalytically active copper-ceria interfacial perimeter

被引:490
作者
Chen, Aling [1 ]
Yu, Xiaojuan [2 ]
Zhou, Yan [1 ]
Miao, Shu [1 ]
Li, Yong [1 ]
Kuld, Sebastian [3 ]
Sehested, Jens [3 ]
Liu, Jingyue [4 ]
Aoki, Toshihiro [5 ]
Hong, Song [6 ]
Camellone, Matteo Farnesi [7 ]
Fabris, Stefano [7 ]
Ning, Jing [1 ]
Jin, Chuanchuan [1 ]
Yang, Chengwu [2 ]
Nefedov, Alexei [2 ]
Woell, Christof [2 ]
Wang, Yuemin [2 ]
Shen, Wenjie [1 ]
机构
[1] Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian, Peoples R China
[2] Karlsruhe Inst Technol, Inst Funct Interfaces, Eggenstein Leopoldshafen, Germany
[3] Haldor Topsoe Res Labs, Lyngby, Denmark
[4] Arizona State Univ, Dept Phys, Tempe, AZ 85287 USA
[5] Arizona State Univ, LeRoy Eyring Ctr Solid State Sci, Tempe, AZ USA
[6] Beijing Univ Chem Technol, Ctr Instrumental Anal, Beijing, Peoples R China
[7] CNR, IOM, Trieste, Italy
基金
中国国家自然科学基金; 欧盟地平线“2020”;
关键词
WATER-GAS SHIFT; IN-SITU; METHANOL SYNTHESIS; OXYGEN VACANCIES; CARBON-MONOXIDE; CO OXIDATION; METAL-OXIDE; CATALYSTS; CU; ADSORPTION;
D O I
10.1038/s41929-019-0226-6
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Cu/CeO2 catalysts are highly active for the low-temperature water-gas shift-a core reaction in syngas chemistry for tuning the H-2/CO/CO2 proportions in feed streams-but the direct identification and quantitative description of the active sites remain challenging. Here we report that the active copper clusters consist of a bottom layer of mainly Cu+ atoms bonded on the oxygen vacancies (O-v) of ceria, in a form of Cu+-O-v-Ce3+, and a top layer of Cu-0 atoms coordinated with the underlying Cu+ atoms. This atomic structure model is based on directly observing copper clusters dispersed on ceria by a combination of scanning transmission electron microscopy and electron energy loss spectroscopy, in situ probing of the interfacial copper-ceria bonding environment by infrared spectroscopy and rationalization by density functional theory calculations. These results, together with reaction kinetics, reveal that the reaction occurs at the copper-ceria interfacial perimeter via a site cooperation mechanism: the Cu+ site chemically adsorbs CO whereas the neighbouring O-v-Ce3+ site dissociatively activates H2O.
引用
收藏
页码:334 / 341
页数:8
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