非贵金属-氮-碳基催化材料的构建及其选择性氧化、加氢性能研究

Nanocarbon-based catalytic materials have been regarded as a promising candidate for next generation catalysts substituting for industrial metal/oxide catalysts, because of their potential in saving noble metal sources and improving sustainability of chemical processes. However, the applications of carbon-based catalysts are so far limited within the reactions involving activating oxygen, and associated with the lower activity compared with their metal counterparts. To address these issues, we propose a multifunctional Me-N-C carbon-based catalyst for the selective oxidation of alcohols and the selective hydrogenation of aromatic nitrocompounds, which are very important to the petrochemical and fine chemical industries. In addition, we will develop structured carbon-based catalysts to enhance the gas-liquid-solid reactor. On the aspect of fundamental catalysis science, this study will establish the structure-activity relationship and reveal the surface/interfacial catalysis mechanism on the molecular level. These knowledge guarantee the rational design of the carbon-based catalyst. Based on these insights into the catalytic mechanism, we will develop highly efficient, environmental benign and noble-metal-free novel chemical and reactor technologies.

碳基纳米材料新颖的催化特性有望对传统的金属/氧化物催化剂进行革命性的突破，在节约(贵)金属资源、提高化工过程可持续性方面具有巨大潜力。针对目前碳基催化剂的应用领域主要限于涉及氧活化的反应，且活性也有待提高的现状，本项目以石油化工、精细化学品生产过程中具有重要地位的醇类选择性氧化、芳硝基化合物加氢反应为目标，提出构建具有Me-N-C结构的多功能碳基催化剂，并发展结构化的碳基催化剂强化气液固三相反应器。在催化科学方面，探明先进纳米碳催化剂的结构-活性关系，揭示分子层次上表界面催化本质，为碳基催化材料设计提供科学依据；在技术方面，所形成的碳催化功能材料及反应器技术将提供可替代传统贵金属催化剂的、高效、环保的新颖催化工艺。

碳基纳米材料新颖的催化特性有望对传统的金属/氧化物催化剂进行革命性的突破，在节约(贵)金属资源、提高化工过程可持续性方面具有巨大潜力。过渡金属和非金属共掺杂的碳材料是一类具有优异性能的催化材料。本项目构建了过渡金属（Fe、Co、Ni）与氮共掺杂的碳基催化材料，该催化剂具有Me-N-C单原子活性位点，围绕该类单原子催化剂在苯甲醇选择性氧化等反应中的性能和机理展开了系统的研究。通过对CoNC催化剂合成过程的优化，获得了高活性的苯甲醇选择性氧化催化剂；研究还表明以CoNC为载体负载Pt可以显著提高贵金属分散度，并得到具有更高本征活性的甘油选择性氧化催化剂。通过反应动力学、DFT理论计算等手段，详细研究了CoNC上苯甲醇氧化、Pt/CoNC上甘油氧化反应的反应机理，揭示了用于催化多分子合成反应的单原子Me/N/C催化剂上底物间、底物与溶剂间竞争吸附等机制，为碳基单原子催化剂的设计提供了理论基础。在技术方面，项目研究了碳基结构型催化剂及其反应器设计，所提出的介孔碳基催化剂结合了催化性能与碳基材料的焦耳热特性，有效地实现了碳基催化反应器的过程强化。