基于DFT计算的Pt(111)表面氧覆盖度和水合质子模型对氧还原反应路径的影响(英文)

doi:10.13208/j.electrochem.130894

电化学（中英文） ›› 2014, Vol. 20 ›› Issue (3): 206-218. doi: 10.13208/j.electrochem.130894

• 基础电化学近期研究专辑(武汉大学陈胜利教授主编) • 上一篇下一篇

基于DFT计算的Pt(111)表面氧覆盖度和水合质子模型对氧还原反应路径的影响(英文)

欧利辉^1,2，陈胜利^2*

1. 湖南文理学院化学化工学院，湖南常德 415000; 2. 武汉大学化学与分子科学学院，湖北武汉 430072

收稿日期:2014-03-19 修回日期:2014-05-02 发布日期:2014-05-09 出版日期:2014-06-28
通讯作者: 陈胜利 E-mail:slchen@whu.edu.cn
基金资助:
This work was supported by Ministry of Science and Technology (Grant Nos. 2012CB932800 and 2013AA110201), the National Natural Science Foundation of China (Grant No. 21303048), Hunan Provincial Natural Science Foundation of China (Grant No. 13JJ4101), and Foundation of the Education Department of Hunan Province (Grant No. 12C0832)

Effects of Oxygen Coverage and Hydrated Proton Model on the DFT Calculation of Oxygen Reduction Pathways on the Pt(111) Surface

OU Li-hui^1,2, CHEN Sheng-li^2*

1. College of Chemistry and Chemical Engineering, Hunan University of Arts and Science, Changde 415000, Hunan, China; 2. College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China

Received:2014-03-19 Revised:2014-05-02 Online:2014-05-09 Published:2014-06-28
Contact: CHEN Sheng-li E-mail:slchen@whu.edu.cn
Supported by:
This work was supported by Ministry of Science and Technology (Grant Nos. 2012CB932800 and 2013AA110201), the National Natural Science Foundation of China (Grant No. 21303048), Hunan Provincial Natural Science Foundation of China (Grant No. 13JJ4101), and Foundation of the Education Department of Hunan Province (Grant No. 12C0832)

摘要/Abstract

摘要： 利用基于平面波的密度泛函理论（DFT）计算研究了氧气分子在Pt(111)表面的吸附和解离，以及解离产物进一步质子化形成H₂O的过程. 通过使用不同尺寸的平板模型和在表面预吸附不同数量的氧原子，研究了氧覆盖度对氧还原反应（ORR）路径的影响，并对使用不同水合质子模型的计算结果进行了比较. 研究结果表明：质子化的end-on化学吸附态OOH*的形成是ORR的初始步骤；OOH*能够转化形成非质子化的top-bridge-top化学吸附态O₂*，或者解离形成吸附的O*物种. 对不同氧覆盖度下各种可能步骤的活化能计算结果表明，O*的质子化形成OH*物种是ORR的速决步骤. 增加氧覆盖度时，该步骤的活化能减少. 此外，还发现使用比H₇O₃⁺更复杂的水合质子模型不会改变计算所得的反应路径.

关键词: 最小能量路径, ORR机理, 氧覆盖度, 水合质子模型

Abstract: DFT calculation is used to study various possible steps in the oxygen reduction reaction (ORR), including the adsorption and dissociation process of O₂and the serial protonation process of dissociated products to form H₂O on the Pt(111) surface. By using slabs of different sizes, and different numbers of pre-adsorbed oxygen atoms, the coverage effects on the pathways are investigated. The calculated results using different hydrated proton models are also compared. It is shown that the initial step of the ORR is the formation of a protonated end-on chemisorbed state of OOH*, which can transform to an unprotonated top-bridge-top state of O₂* or dissociate into adsorbed O* species with similar activation barrier. The calculated activation barriers for various possible steps at different oxygen coverages suggest that the protonation of O* to form OH* species is the rate-determining step in the ORR. With the increased oxygen coverage, the activation energy of this step decreases. It is found that the use of hydrated proton models more complicated than H₇O₃⁺ does not change the calculated pathways.

Key words: minimum energy path, ORR mechanism, oxygen coverage, hydrated proton model

中图分类号:

O646

欧利辉，陈胜利*. 基于DFT计算的Pt(111)表面氧覆盖度和水合质子模型对氧还原反应路径的影响(英文)[J]. 电化学（中英文）, 2014, 20(3): 206-218.

OU Li-hui, CHEN Sheng-li*. Effects of Oxygen Coverage and Hydrated Proton Model on the DFT Calculation of Oxygen Reduction Pathways on the Pt(111) Surface[J]. Journal of Electrochemistry, 2014, 20(3): 206-218.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.130894

https://electrochem.xmu.edu.cn/CN/Y2014/V20/I3/206

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基于DFT计算的Pt(111)表面氧覆盖度和水合质子模型对氧还原反应路径的影响(英文)

Effects of Oxygen Coverage and Hydrated Proton Model on the DFT Calculation of Oxygen Reduction Pathways on the Pt(111) Surface

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