Co3O4纳米晶催化氧化甲烷的理论研究：C-H键活化的晶面效应及活性中心

doi:10.1016/S1872-2067(14)60043-7

催化学报 ›› 2014, Vol. 35 ›› Issue (4): 462-467.DOI: 10.1016/S1872-2067(14)60043-7

Co₃O₄纳米晶催化氧化甲烷的理论研究：C-H键活化的晶面效应及活性中心

王阳刚^a, 杨小峰^a,b, 胡林华^a, 李亚栋^a, 李隽^a

a 清华大学化学系, 北京100084;
b 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:2013-12-29 修回日期:2014-01-20 出版日期:2014-03-20 发布日期:2014-03-21
通讯作者: 李隽
基金资助:
国家纳米科技基础研究重大项目（2011CB932401）；国家自然科学基金（21221062，10979031）.

Theoretical study of the crystal plane effect and ion-pair active center for C-H bond activation by Co₃O₄ nanocrystals

Yanggang Wang^a, Xiaofeng Yang^a,b, Linhua Hu^a, Yadong Li^a, Jun Li^a

a Department of Chemistry, Tsinghua University, Beijing 100084, China;
b State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China

Received:2013-12-29 Revised:2014-01-20 Online:2014-03-20 Published:2014-03-21
Supported by:
This work was supported by the State Key Project of Fundamental Research for Nanoscience and Nanotechnology (2011CB932401) and the National Natural Science Foundation of China (21221062, 10979031).

摘要/Abstract

摘要：

甲烷是一种在自然界中大量存在的原材料，在取代原油和合成重要化工产品等许多领域具有潜在的应用价值. 然而，由于CH₄中C-H键的键能特别大（约~4.5 eV），如何实现甲烷的绿色有效转化在化学化工领域仍然是一个挑战. 本文采用密度泛函理论对Co₃O₄（001）和（011）晶面活化甲烷C-H键的机理进行了理论研究，得到了如下结论：（1） CH₄的C-H键在Co₃O₄晶面的解离具有很高的活性，只需要克服大约1 eV的能垒；（2）与Co²^＋相连的Co-O离子对是CH₄活化的活性位点，其中两个带正负电荷的离子对C-H解离起着协同作用，帮助产生Co-CH₃和O-H物种；（3）（011）面的反应活性明显大于（001）面，与实验的观察一致. 本文的计算结果表明，Co₃O₄纳米晶面对CH₄中C-H键的活化表现出明显的晶面效应和结构敏感效应，Co-O离子对活性中心对于活化惰性的C-H键发挥了关键作用.

关键词: C-H键活化, 甲烷氧化, 晶面效应, 微观动力学分析, 离子对活性中心

Abstract:

Methane has attracted extensive interest in recent years due to its potential application as a replacement of oil and a feedstock for valuable chemicals. Due to the large C-H bond energy, the conversion of methane into useful products has been a challenge. In the present study, density functional theory (DFT) calculations were performed to study the activation of the C-H bond of methane on the (001) and (011) planes of Co₃O₄, which showed that CH₄ activation on Co₃O₄ nanocrystals was fairly easy with only small energy barriers (less than 1.1 eV). Surface Co-O ion pairs are the active site for C-H bond activation, where the two ions provide a synergistic effect for the activation of the strong C-H bond and yield surface Co-CH₃ and O-H species. The Co₃O₄(011) surface is shown to be more reactive for C-H bond activation than the Co₃O₄(001) surface, which is consistent with previous experimental results. Our results suggest that methane oxidation on Co₃O₄ nanocrystals has strong crystal plane effect and structure sensitivity and the ion-pair active center plays a significant role in activating the strong C-H bond.

Key words: C-H bond activation, Methane conversion, Crystal plane effect, Microkinetic analysis, Ion-pair active center

王阳刚, 杨小峰, 胡林华, 李亚栋, 李隽. Co₃O₄纳米晶催化氧化甲烷的理论研究：C-H键活化的晶面效应及活性中心[J]. 催化学报, 2014, 35(4): 462-467.

Yanggang Wang, Xiaofeng Yang, Linhua Hu, Yadong Li, Jun Li. Theoretical study of the crystal plane effect and ion-pair active center for C-H bond activation by Co₃O₄ nanocrystals[J]. Chinese Journal of Catalysis, 2014, 35(4): 462-467.

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Co₃O₄纳米晶催化氧化甲烷的理论研究：C-H键活化的晶面效应及活性中心

Theoretical study of the crystal plane effect and ion-pair active center for C-H bond activation by Co₃O₄ nanocrystals

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