高效非贵金属氧还原催化剂的理性构筑及催化机理的研究

项目名称： 高效非贵金属氧还原催化剂的理性构筑及催化机理的研究

项目编号： No.21503212

项目类型： 青年科学基金项目

立项/批准年度： 2016

项目学科： 数理科学和化学

项目作者： 宋平

作者单位： 中国科学院长春应用化学研究所

项目金额： 21万元

中文摘要： 本项目拟采用理论结合实验的手段对新型高效的铁、锰和镁等廉价金属和硅掺杂的非金属氧还原催化剂进行理性设计与控制制备。理论构建可能的催化活性位点结构（M-Nx活性位点以及MxNy纳米粒子结构位点，Si-C/N掺杂结构等），预测其催化活性，指导实验制备氧还原催化剂，并结合透射电镜、X-射线衍射、X-射线光电子能谱以及拉曼光谱能物理表征手段来详细考察制备参数对催化剂结构和性能的影响；通过实验结合量子化学理论方法深入研究所制备的催化剂的氧还原催化机理，模拟氧气在催化剂表面的吸附中间体以及反应的活化能，描述可能的反应路径；并根据理论模拟来调整催化剂的活性位点结构，设计更高性能的催化剂来替代商业碳载铂，为合理构筑高性能的非贵金属氧还原催化剂提供理论支持

中文关键词： 非贵金属；氧还原；催化机理；理论研究；构效关系

英文摘要： We focus on the study on the rational design and the preparation of non-precious metal catalysts in oxygen reduction reaction (ORR), including cheap metal (Fe, Mn and Mg) and Si-doped non-metal catalysts. The possible catalytic active sites can be constructed at theoretical level to predict their activities, which can provide guidance of preparing ORR catalysts. For non-precious metal ones, the M-Nx (x=2, 4) structure and MxNy nanoparticle-type can be constructed, on the other hand, various Si-C and Si-N structures should be considered for Si-doped catalysts. We will investigate the effect of catalyst preparation parameters on the structures and performances of catalysts. Moreover, the combination of various experimental characterization methods (TEM, XRD, XPS and Raman spectra) with quantum chemical method has been performed to study the ORR mechanism. We will simulate the adsorbed intermediates on the surface of the catalysts, and the activation energies for elementary reaction. Then the possible reaction paths will be described. The catalytic active structures will be adjusted based on the theoretical calculations, which can be used to design new non-precious metal catalysts instead of commercial Pt/C ones. It will provide better theoretical foundation for promoting the performance of the non-precious metal catalysts.

英文关键词： non-precious metal;oxygen reduction reaction ;catalytic mechanism;quantum chemical study;relationship for structure and activity