Co<sub>3</sub>O<sub>4</sub>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

引用本文: 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. doi: 10.1016/S1872-2067(14)60043-7 shu

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

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,
,}

通讯作者: 李隽

基金项目:
国家纳米科技基础研究重大项目(2011CB932401) (2011CB932401)

国家自然科学基金(21221062, 10979031). (21221062, 10979031)

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:

English

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

1.
a Department of Chemistry, Tsinghua University, Beijing 100084, China;

Corresponding author: 李隽

Received Date: 29 December 2013
Available Online: 20 April 2014
Fund Project:
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).

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:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

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

通讯作者: 李隽

English

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

Corresponding author: 李隽

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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

通讯作者: 李隽

English

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

Corresponding author: 李隽

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

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

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs