利用原位APXPS与STM研究H<sub>2</sub>在(10${\rm{\bar 1}}$0)表面的活化

doi:10.3866/PKU.WHXB201804161

所属专题：表面物理化学

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利用原位APXPS与STM研究H₂在(10${\rm{\bar 1}}$0)表面的活化

刘强^1,4, 韩永^1,3, 曹云君², 李小宝^1,4, 黄武根², 余毅³, 杨帆², 包信和², 李毅敏^1,3, 刘志^1,3

1 中国科学院上海微系统与信息技术研究所, 信息功能材料国家重点实验室, 上海 200050;
2 中国科学院大连化学物理研究所, 辽宁大连 116011;
3 上海科技大学物质科学与技术学院, 上海 201203;
4 中国科学院大学, 北京 100049

In-situ APXPS and STM Study of the Activation of H₂ on ZnO(10${\rm{\bar 1}}$0) Surface

LIU Qiang^1,4, HAN Yong^1,3, CAO Yunjun², LI Xiaobao^1,4, HUANG Wugen², YU Yi³, YANG Fan², BAO Xinhe², 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

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摘要： Cu/ZnO/Al₂O₃是工业中最广泛使用的甲醇合成催化剂。然而该催化反应的活性位点和机理目前仍存争议。H₂作为反应物之一，研究其在ZnO表面的活化和解离对于弄清甲醇合成反应的催化机理具有重要的帮助。本工作利用近常压光电子能谱（APXPS）和扫描隧道显微镜（STM）原位研究了H₂在ZnO（10${\rm{\bar 1}}$0）表面上的活化和解离。APXPS结果表明：在0.3 mbar （1 mbar=100 Pa）的H₂气氛中，室温下ZnO表面形成羟基（OH）吸附物种。STM实验发现通入H₂后ZnO表面发生了（1×1）到（2×1）的重构。上述结果和原子H在ZnO（10${\rm{\bar 1}}$0）表面的吸附结果一致。然而吸附H₂O可以导致同样的现象。因此，我们还开展了H₂O在ZnO（10${\rm{\bar 1}}$0）表面吸附的对比实验。结果表明：H₂气氛中ZnO表面发生0.3 eV的能带弯曲，而H₂O吸附实验中几乎观察不到能带弯曲发生。同时，热稳定性实验表明H₂气氛中ZnO表面的OH不同于H₂O解离吸附产生的OH，前者具有更高的脱附温度。因此，本工作的结果表明常温和常压下H₂在ZnO（10${\rm{\bar 1}}$0）表面发生解离吸附。这一结果和以往超高真空下未发现H₂在ZnO（10${\rm{\bar 1}}$0）表面上的解离不同，说明H₂的活化是一个压力依赖过程。

关键词： H₂; ZnO(10${\rm{\bar 1}}$0); 活化; 解离吸附; 近常压光电子能谱; 扫描隧道显微镜

Abstract: 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(10${\rm{\bar 1}}$0) single crystal surface were investigated in-situ using ambient-pressure X-ray photoelectron spectroscopy (APXPS) and scanning tunneling microscopy (STM), two powerful surface characterization techniques. In the APXPS experiments, results indicated the formation of hydroxyl (OH) species on the ZnO single crystal surface at room temperature in 0.3 mbar (1 mbar=100 Pa) H₂ atmosphere. Meanwhile, STM measurements showed that the ZnO surface was reconstructed from a (1×1) to a (2×1) structure upon introduction of H₂. These observations revealed adsorption behaviors of H₂ the same as those of atomic H on a ZnO(10${\rm{\bar 1}}$0) surface as seen in previous studies, which could be evidence of the dissociative adsorption of H₂ on a ZnO surface. However, H₂O adsorption on ZnO surfaces can also result in the formation of OH species, which can be observed using XPS. The STM results show that the exposure of H₂O also leads to the reconstruction from a (1×1) to a (2×1) structure on the ZnO(10${\rm{\bar 1}}$0) surface upon H₂ introduction. Hence, it is necessary to exclude the influence of H₂O in this work, because there may be trace amounts of H₂O in the H₂ gas. Therefore, we performed a comparative study of H₂ and H₂O on ZnO(10${\rm{\bar 1}}$0) single crystal surface. A downward band bending of 0.3 eV was observed on the ZnO surface in 0.3 mbar H₂ atmosphere using APXPS, while negligible band bending was shown in the case of the H₂O atmosphere. Moreover, thermal stability studies revealed that the OH group formed in the H₂ atmosphere desorbed at a higher temperature than the one resulting from H₂O adsorption, meaning that the two OH groups formed on the ZnO surface were different. Results in this work provide evidence of the dissociative adsorption of H₂ on the ZnO(10${\rm{\bar 1}}$0) surface at room temperature and atmospheric pressure. This is in contrast to previous findings, in which no H₂ dissociation on a ZnO(10${\rm{\bar 1}}$0) surface under ultra-high vacuum conditions was observed, indicating that the activation of H₂ on ZnO surfaces is a pressure dependent process.

Key words: H₂ ZnO(10${\rm{\bar 1}}$0) Activation Dissociative adsorption APXPS STM

收稿日期: 2018-03-14 出版日期: 2018-04-16

中图分类号:

O647

基金资助: 国家自然科学基金（11227902），科技部重点研发计划（2017YFB0602205，2016YFA0202803）和中国科学院战略优先研究项目（XDB17020200）资助

通讯作者: 李毅敏, 刘志 E-mail: liym1@shanghaitech.edu.cn;zliu2@mail.sim.ac.cn

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刘强, 韩永, 曹云君, 李小宝, 黄武根, 余毅, 杨帆, 包信和, 李毅敏, 刘志. 利用原位APXPS与STM研究H₂在(10${\rm{\bar 1}}$0)表面的活化[J]. 物理化学学报, 10.3866/PKU.WHXB201804161.

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(10${\rm{\bar 1}}$0) Surface. Acta Physico-Chimica Sinca, 10.3866/PKU.WHXB201804161.

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http://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201804161 或 http://www.whxb.pku.edu.cn/CN/Y0/V/I/0

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