Key Laboratory for Advanced Materials, Centre for Computational Chemistry, and Research Institute of Industrial Catalysis, East China University of Science and Technology , Shanghai 200237, People's Republic of China.
J Am Chem Soc. 2015 Oct 21;137(41):13228-31. doi: 10.1021/jacs.5b07939. Epub 2015 Oct 9.
Vanadia/ceria supported catalysts exhibit ultrahigh catalytic activities in oxidative dehydrogenation (ODH) reactions. Here, we performed systematic density functional theory calculations to illustrate the underlying mechanisms. It is found that unique electronic and structural effects are both crucial in the catalytic processes. Calculations of the catalytic performance of different oxygen species in oxidation of methanol to formaldehyde suggested that the oxygen of the interface V-O-Ce group is catalytically more active, especially when H adsorption energy is small, indicating the strong structural effect in the vanadia/ceria supported catalyst. In addition, new empty localized states of O 2p generated in a ceria-supported system through depositing VO3- and VO4-type monomeric vanadia species are determined to participate in the whole ODH reaction processes and help to reduce the barriers at various steps.
担载型氧化钒/氧化铈催化剂在氧化脱氢（ODH）反应中表现出超高的催化活性。在这里，我们通过系统的密度泛函理论计算来阐明其潜在的反应机理。结果表明，独特的电子和结构效应在催化过程中都起着至关重要的作用。通过计算不同氧物种在甲醇氧化为甲醛反应中的催化性能，发现界面 V-O-Ce 基团中的氧具有更高的催化活性，尤其是当 H 吸附能较小时，这表明在担载型氧化钒/氧化铈催化剂中存在较强的结构效应。此外，通过沉积 VO3-和 VO4 型单体氧化钒物种，在氧化铈担载体系中产生的新的局域 O 2p 空态被确定参与整个 ODH 反应过程，并有助于降低各步骤的能垒。
