单原子催化剂M1/FeOx(M=Pt,Fe)的理论研究:CO氧化反应

doi:10.1016/S1872-2067(17)62879-1

催化学报 ›› 2017, Vol. 38 ›› Issue (9): 1566-1573.DOI: 10.1016/S1872-2067(17)62879-1

单原子催化剂M1/FeO_x(M=Pt,Fe)的理论研究:CO氧化反应

梁锦霞^a,b, 杨小峰^c, 许聪俏^b, 张涛^c, 李隽^b

a 贵州师范学院贵州省纳米材料模拟与计算重点实验室科学云大数据开发及其产业应用协同创新中心, 贵州贵阳 550018;
b 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;
c 中国科学院大连化学物理研究所催化基础国家重点实验室, 辽宁大连 116023

收稿日期:2017-05-29 修回日期:2017-06-26 出版日期:2017-09-18 发布日期:2017-09-06
通讯作者: 杨小峰, 李隽
基金资助:
国家自然科学基金（21503046，21373206，21203182）；国家基础研究计划（2013CB834603）；贵州省自然科学基金（QKJ（2015）2122）；贵州省教育厅自然科学基金（QJTD（2015）55，ZDXK（2014）18）；贵州师范学院启动经费和陕西省催化重点实验室开放课题（SXKLC-2017-01）.

Catalytic ativities of single-atom catalysts for CO oxidation:Pt₁/FeO_x vs. Fe₁/FeO_x

JinxiaLiang^a,b, Xiaofeng Yang^c, Congqiao Xu^b, TaoZhang^c, JunLi^b

a Guizhou Provincial Key Laboratory of Computational Nano‐Material Science, Guizhou Synergetic Innovation Center of Scientific Big Data for Advanced Manufacturing Technology, Guizhou Education University, Guiyang 550018, Guizhou, China;
b Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Tsinghua University, Beijing 100084, China;
c State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China

Received:2017-05-29 Revised:2017-06-26 Online:2017-09-18 Published:2017-09-06
Contact: 10.1016/S1872-2067(17)62879-1
Supported by:
This work was supported by the National Natural Science Foundation of China (21503046, 21373206, 21203182), the National Basic Research Pro-gram of China (2013CB834603), the Natural Science Foundation of Guizhou Province of China (QKJ (2015)2122), Natural Science foundation of De-partment of Education of Guizhou Province (QJTD (2015)55 and ZDXK (2014)18), the GZEU startup package, the Open Fund of Shaanxi Key Labora-tory of Catalysis to JXL (SXKLC-2017-01).

摘要/Abstract

摘要：

负载型纳米贵金属催化剂是用于多相催化反应的重要的催化剂之一，也是各国催化科学与技术研发的重点，其工业应用也越来越广泛.理论和实验的研究结果均表明，当载体表面的金属粒子尺寸减小至亚纳米级乃至更小的低配位、不饱和的原子团簇时，它们常常成为诱发催化反应的活性中心，呈现更高的催化活性和选择性.将负载的金属尺寸由纳米量级减小至分散的金属团簇甚至单原子而使每个原子成为反应的活性位点已成为研究的重点.最近，由张涛等首次合成的单原子催化剂（SAC） Pt₁/FeO_x引起了国内外催化及表面科学工作者的极大关注.单原子催化剂作为连接均相催化剂和多相催化剂的桥梁，不仅具有非均相催化剂的稳定、易于与反应体系分离、易表征等优点，而且具有均相催化剂活性中心结构均一、活性中心原子利用率百分之百等优点.一方面，单原子催化剂给多相催化领域注入了新的活力，另一方面也更有利于运用量子与计算化学的研究方法建立与实验相匹配的理论模型并从原子水平上进一步理解多相催化反应的微观作用机理.
实验和理论的研究结果表明，其它单原子催化剂如Ir₁/FeO_x，Au₁/FeO_x和Ni₁/FeO_x催化CO氧化反应表现出不同的活性.然而，底物FeO_x中的Fe同样是第VⅢ族中的3d过渡金属，却在低温下对CO氧化反应没有催化活性.我们围绕这一问题，重点研究了底物FeO_x在负载单原子Pt₁前后催化CO氧化的反应机理和活性，解释了单原子催化剂Pt₁/FeO_x相比于底物FeO_x为何具有如此高的催化活性的原因.我们采用Vienna Ab-initio Simulation Package（VASP）从头算模拟软件和密度泛函理论（DFT）的广义梯度近似（GGA）进行了理论计算.其中，选择PBE泛函描述体系的交换关联相互作用，用投影缀加波（PAW）赝势基组方法描述体系中的电子和离子实之间的相互作用，对Fe原子采用了DFT+U方法进行d电子强相关校正，并使用Dimer计算方法搜寻反应过渡态.
研究结果表明，底物FeO_x中氧空位的再生伴随第二个CO₂分子从催化剂表面脱附的过程需要较高的活化势垒（1.09eV），这一过程是整个CO氧化反应的决速步.与此相比较，Pt₁/FeO_x催化剂中，由于Pt原子代替了表面Fe原子，导致电子结构及性质的显著变化，有利于CO的活化、氧化和CO₂的脱附.我们从电子能量态密度（DOS）和Bader电荷分析及模型分子团簇的轨道相互作用的角度进一步分析了两种催化剂存在差异的本质；揭示了单原子催化剂Pt₁/FeO_x中Pt₁和底物FeO_x之间的相互作用的机理及催化剂表面Pt单原子在催化反应过程中的关键作用.

关键词: 单原子催化剂, 氧化铁载体, 密度泛函理论, 非均相催化, 一氧化碳氧化

Abstract:

An FeO_x-based Pt single-atom catalyst (SAC), Pt₁/FeO_x, has stimulated significant recent interest owing to its extraordinary activity toward CO oxidation. The concept of SAC has also been success-fully extended to other FeO_x supported transition metal systems both experimentally and theoreti-cally. However, the FeO_x substrate itself (denoted by Fe₁/FeO_x following the same nomenclature of Pt₁/FeO_x) as a typical transition metal oxide possesses a very low catalytic activity toward CO oxida-tion, although it can be viewed as Fe₁/FeO_x SAC. Here, to understand the catalytic mechanism of FeO_x-based SACs for CO oxidation, we have performed density functional theory calculations on Pt₁/FeO_x and Fe₁/FeO_x for CO oxidation to address the differences between these two SACs in terms of the catalytic mechanism of CO oxidation and the chemical behavior of the catalysts. Our calcula-tion results indicated that the catalytic cycle of Fe₁/FeO_x is much more difficult to accomplish than that of SAC Pt₁/FeO_x because of a high activation barrier (1.09 eV) for regeneration of the oxygen vacancy formed when the second CO₂ molecule desorbs from the surface. Moreover, density of states and Bader charge analysis revealed differences in the catalytic performance for CO oxidation by the SACs Fe₁/FeO_x and Pt₁/FeO_x. This work provides insights into the fundamental interactions between the single-atom Pt₁ and FeO_x substrate, and the exceptional catalytic performance of this system for CO oxidation.

Key words: Single-atom catalyst, FeO_x substrate, Density functional theory, Heterogeneous catalysis, CO oxidation

梁锦霞, 杨小峰, 许聪俏, 张涛, 李隽. 单原子催化剂M1/FeO_x(M=Pt,Fe)的理论研究:CO氧化反应[J]. 催化学报, 2017, 38(9): 1566-1573.

JinxiaLiang, Xiaofeng Yang, Congqiao Xu, TaoZhang, JunLi. Catalytic ativities of single-atom catalysts for CO oxidation:Pt₁/FeO_x vs. Fe₁/FeO_x[J]. Chinese Journal of Catalysis, 2017, 38(9): 1566-1573.

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单原子催化剂M1/FeO_x(M=Pt,Fe)的理论研究:CO氧化反应

Catalytic ativities of single-atom catalysts for CO oxidation:Pt₁/FeO_x vs. Fe₁/FeO_x

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单原子催化剂M1/FeOx(M=Pt,Fe)的理论研究:CO氧化反应

Catalytic ativities of single-atom catalysts for CO oxidation:Pt1/FeOx vs. Fe1/FeOx

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单原子催化剂M1/FeO_x(M=Pt,Fe)的理论研究:CO氧化反应

Catalytic ativities of single-atom catalysts for CO oxidation:Pt₁/FeO_x vs. Fe₁/FeO_x