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OALib Journal期刊
ISSN: 2333-9721
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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
DOI: 10.1016/S1872-2067(14)60043-7, PP. 462-467
Keywords: 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:
？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~4.5eV），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1eV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.
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