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催化学报  2014 

过渡金属替代的CeO2(111)表面上NO+CO反应机理的理论研究

DOI: 10.1016/S1872-2067(14)60169-8, PP. 1937-1943

Keywords: 一氧化氮消除,选择性,单原子,单过渡金属原子/氧化铈,密度泛函理论+U

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Abstract:

?采用DFT+U方法研究了过渡金属替代的CeO2(111)表面上的NO+CO反应机理,以探求不同过渡金属对N2选择性的影响.结果表明,在反应过程中,反应活性中心由过渡金属单原子与其最近邻的氧空位组成.NO在过渡金属-氧空位上发生N-O断键,不同过渡金属上该还原步骤的难易程度不同.计算发现,右过渡金属Rh,Pd和Pt替代的CeO2(111)表面可以与吸附物之间形成较强的吸附作用,进而可以达到较高的N2选择性.其主要原因是右过渡金属具有较多的d电子,可以与吸附小分子之间形成有效的反馈键.而左过渡金属拥有较少的d电子,难以有效抓住吸附物,最终导致较低的N2选择性.

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