Citation: LIU Qiang, HAN Yong, CAO Yunjun, LI Xiaobao, HUANG Wugen, YU Yi, YANG Fan, BAO Xinhe, LI Yimin, LIU Zhi. In-situ APXPS and STM Study of the Activation of H₂ on ZnO(1010) Surface[J]. Acta Physico-Chimica Sinica, ;2018, 34(12): 1366-1372. doi: 10.3866/PKU.WHXB201804161 shu

In-situ APXPS and STM Study of the Activation of H₂ on ZnO(1010) Surface

LIU Qiang ^1,4 ,
HAN Yong ^1,3 ,
CAO Yunjun ² ,
LI Xiaobao ^1,4 ,
HUANG Wugen ² ,
YU Yi ³ ,
YANG Fan ² ,
BAO Xinhe ² ,
LI Yimin ^1,3,, ,
LIU Zhi ^1,3,,

1.
State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050, P. R. China
2.
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, P. R. China
3.
School of Physical Science and Technology, Shanghai Tech University, Shanghai 201203, P. R. China
4.
University of Chinese Academy of Sciences, Beijing 100049, P. R. China

Corresponding author: LI Yimin, liym1@shanghaitech.edu.cn LIU Zhi, zliu2@mail.sim.ac.cn
Received Date: 14 March 2018
Revised Date: 7 April 2018
Accepted Date: 9 April 2018
Available Online: 16 December 2018
Fund Project: the Ministry of Science and Technology of China 2016YFA0202803The project was supported by the National Natural Science Foundation of China 11227902the Ministry of Science and Technology of China 2017YFB0602205the Strategic Priority Research Program of the Chinese Academy of Sciences XDB17020200The project was supported by the National Natural Science Foundation of China (11227902), the Ministry of Science and Technology of China(2017YFB0602205, 2016YFA0202803), and the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB17020200)

Cu/ZnO/Al₂O₃ is one of the most widely used catalysts in industrial methanol synthesis. However, the reaction mechanism and the nature of the active sites on the catalyst for this reaction are still under debate. Thus, detailed information is needed to understand the catalytic processes occurring on the surface of this catalyst. H₂ is one of the reaction gases in methanol synthesis. Studies of the activation and dissociation behaviors of H₂ on ZnO surfaces are of great importance in understanding the catalytic mechanism of methanol synthesis. In this work, the activation and dissociation processes of H₂ on a ZnO(1010) single crystal surface were investigated in-situ using ambient-pressure X-ray photoelectron spectroscopy (APXPS) and scanning tunneling microscopy (STM), two powerful surface characterization techniques. In the APXPS experiments, results indicated the formation of hydroxyl (OH) species on the ZnO single crystal surface at room temperature in 0.3 mbar (1 mbar = 100 Pa) H₂ atmosphere. Meanwhile, STM measurements showed that the ZnO surface was reconstructed from a (1×1) to a (2×1) structure upon introduction of H₂. These observations revealed adsorption behaviors of H₂ the same as those of atomic H on a ZnO(1010) surface as seen in previous studies, which could be evidence of the dissociative adsorption of H₂ on a ZnO surface. However, H₂O adsorption on ZnO surfaces can also result in the formation of OH species, which can be observed using XPS. The STM results show that the exposure of H₂O also leads to the reconstruction from a (1×1) to a (2×1) structure on the ZnO(1010) surface upon H₂ introduction. Hence, it is necessary to exclude the influence of H₂O in this work, because there may be trace amounts of H₂O in the H₂ gas. Therefore, we performed a comparative study of H₂ and H₂O on ZnO(1010) single crystal surface. A downward band bending of 0.3 eV was observed on the ZnO surface in 0.3 mbar H₂ atmosphere using APXPS, while negligible band bending was shown in the case of the H₂O atmosphere. Moreover, thermal stability studies revealed that the OH group formed in the H₂ atmosphere desorbed at a higher temperature than the one resulting from H₂O adsorption, meaning that the two OH groups formed on the ZnO surface were different. Results in this work provide evidence of the dissociative adsorption of H₂ on the ZnO(1010) surface at room temperature and atmospheric pressure. This is in contrast to previous findings, in which no H₂ dissociation on a ZnO(1010) surface under ultra-high vacuum conditions was observed, indicating that the activation of H₂ on ZnO surfaces is a pressure dependent process.
- H₂,
- 10)')"> ZnO(1010),
- Activation,
- Dissociative adsorption,
- APXPS,
- STM
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In-situ APXPS and STM Study of the Activation of H2 on ZnO(1010) Surface

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通讯作者: 陈斌, bchen63@163.com

In-situ APXPS and STM Study of the Activation of H₂ on ZnO(1010) Surface