水在Au1/CeO2单原子催化剂上吸附与解离的理论研究

doi:10.1016/S1872-2067(17)62829-8

催化学报 ›› 2017, Vol. 38 ›› Issue (9): 1558-1565.DOI: 10.1016/S1872-2067(17)62829-8

水在Au₁/CeO₂单原子催化剂上吸附与解离的理论研究

汤妍^a, 王阳刚^a, 梁锦霞^a,b, 李隽^a

a 清华大学化学系有机光电子与分子工程教育部重点实验室, 北京 100084;
b 贵州省纳米材料模拟与计算重点实验室, 贵州贵阳 550018

收稿日期:2017-03-10 修回日期:2017-04-01 出版日期:2017-09-18 发布日期:2017-09-06
通讯作者: 李隽, 王阳刚
基金资助:
国家自然科学基金（21590792，91645203，21521091）.

Investigation of water adsorption and dissociation on Au₁/CeO₂ single-atom catalysts using density functional theory

Yan Tang^a, Yang-Gang Wang^a, Jin-Xia Liang^a,b, Jun Li^a

a Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Tsinghua University, Beijing 100084, China;
b Guizhou Provincial Key Laboratory of Computational Nano‐Material Science, Guizhou Normal College, Guiyang 550018, China

Received:2017-03-10 Revised:2017-04-01 Online:2017-09-18 Published:2017-09-06
Contact: 10.1016/S1872-2067(17)62829-8
Supported by:
This work was supported by the National Natural Science Foundation of China (21590792, 91645203 and 21521091).

摘要/Abstract

摘要：

自Haruta和Hutchings发现负载的纳米金催化剂的催化活性后，负载型金催化剂一直是非均相催化的研究重点之一.近年来，单原子催化剂因其优异的活性、选择性，超高的原子利用效率，引起了科学家们的广泛关注.越来越多的单原子金催化剂被成功制备，并被证实具有很好的催化活性.水，作为环境中最常见的物质，在实际的催化体系中往往难以避免，即使在超高真空环境中也会有痕量的水气存在.水的解离不仅是水煤气反应的重要步骤之一，而且对别的反应也有一定的促进作用.尽管水和纳米团簇催化剂之间的研究已经颇有成效，但水和单原子金催化剂之间的作用还不是非常清晰.因此，我们采用密度泛函理论从原子尺度研究了水和Au₁/CeO₂单原子催化剂的相互作用.
我们首先研究了水在完美CeO₂表面和含有一个氧空位的CeO_2-x表面上的解离过程，研究发现分子态的水和解离态的水在完美CeO₂表面可以共存，而一旦在表面形成氧空位后，由于较低的能垒和极大的放热，解离态的水将占据绝对优势.接下来探索了水在完美Au₁/CeO₂表面和含有一个氧空位的Au₁/CeO_2-x表面上的解离过程，发现结论恰好和CeO₂表面相反.水的解离过程在完美的Au₁/CeO₂表面几乎是一个无能垒的过程，并且解离会放出大量的热量.而一旦在表面形成氧空位后，单原子Au的轨道处于满占状态，无法提供水的吸附位点.水的解离过程在Ce位点进行，分子吸附能与解离吸附能相当，分子态与解离态共存.
为了进一步理解单原子金在水的解离过程中起到的作用，我们分析了水和Au₁/CeO₂之间的电子相互作用.研究结果表明，单原子金不仅为水的吸附提供了位点，金的5d轨道和水的2p轨道之间的相互作用还有效减弱了水中氧氢键的强度，使水的解离更容易进行.由此可见，在涉及到水解离的反应中，以Au₁/CeO₂为代表的单原子催化剂有望带来新的突破.
最后，我们还测试了范德华力对研究体系的影响.研究发现尽管范德华力会使吸附能的绝对值增加，但是并不影响我们得到的结论.

关键词: 单原子催化剂, 金单原子, 二氧化铈, 水解离

Abstract:

We examined the water adsorption and dissociation on ceria surfaces as well as ceria-supported Au single-atom catalysts using density functional theory calculations. Molecular and dissociative water were observed to coexist on clean CeO₂ and reduced Au₁/CeO_2-x surfaces because of the small dif-ference in adsorption energies, whereas the presence of dissociative water was highly favorable on reduced CeO_2-xand clean Au₁/CeO₂ surfaces. Positively charged Au single atoms on the ceria surface not only provided activation sites for water adsorption but also facilitated water dissociation by weakening the intramolecular O-H bonds. In contrast, negatively charged Au single atoms were not reactive for water adsorption because of the saturation of Au 5d and 6s electron shells. This work provides a fundamental understanding of the interaction between water and single-atom Au cata-lysts.

Key words: Single-atom catalyst, Au single atom, Ceria, H₂O dissociation

汤妍, 王阳刚, 梁锦霞, 李隽. 水在Au₁/CeO₂单原子催化剂上吸附与解离的理论研究[J]. 催化学报, 2017, 38(9): 1558-1565.

Yan Tang, Yang-Gang Wang, Jin-Xia Liang, Jun Li. Investigation of water adsorption and dissociation on Au₁/CeO₂ single-atom catalysts using density functional theory[J]. Chinese Journal of Catalysis, 2017, 38(9): 1558-1565.

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水在Au₁/CeO₂单原子催化剂上吸附与解离的理论研究

Investigation of water adsorption and dissociation on Au₁/CeO₂ single-atom catalysts using density functional theory

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