H2、O2、N2、CH4、CO2等简单小分子的活化是诸多重要化学反应的关键步骤。受阻路易斯酸碱对(FLP)，作为一类新型的非金属有机催化剂，在多种小分子活化中表现出独特的催化性能，但均相催化剂热稳定性差、难以循环使用等缺点严重制约其规模化应用。本项目拟采用理论研究手段，将均相FLP催化的概念通过催化剂的理性设计引入多相催化中，实现均相FLP催化剂的多相化。首先，选择CeO2为设计基体，通过对CeO2表面的氧空穴调控、杂原子掺杂、有机分子/基团修饰，探索固体FLP催化剂的设计策略；其次，针对若干目标小分子设计特定组成和结构的固体FLP催化剂，研究其活化小分子的性能和规律，并建立催化剂结构与小分子活化的匹配关联；然后，通过研究CO2加氢甲烷化反应的微观机理，揭示固体FLP位点与表面其它位点协同催化多小分子反应的行为和机制。最终建立一套从目标小分子出发，理性设计固体FLP催化剂的普适性策略。

Activation of simple small molecules like H2, O2, N2, CH4 and CO2 is usually the key step of many important reactions. As a new perspective type of metal-free organic catalysts, frustrated Lewis pairs (FLPs) exhibit extraordinary properties in the activation of a variety of small molecules. However, the drawbacks of homogeneous catalysts such as poor thermo-stability and difficulty in recycling, severely limit the large-scale applications of FLP catalysts. Herein, in this proposal we propose to introduce the concept of homogeneous FLP into heterogeneous catalysis while designing solid catalysts by using theoretical modeling. The specific strategies are as follows: firstly, establishing a rational approach for creating solid frustrated Lewis pairs on CeO2 surfaces. To this end, three possible methods will be tried, (i) regulating the surface oxygen vacancies of CeO2 surfaces, (ii) doping hybrid atoms on the surfaces, and (iii) introducing organic molecules or functional groups onto the surfaces. Secondly, designing special solid FLP catalysts for several objective small molecules. By investigating the catalytic properties of the as-designed catalysts toward small molecules, we aim to establish the relationship between the catalyst structures and their catalytic performances. Thirdly, exploring the reaction mechanisms of CO2 methanation reaction (CO2 + 4H2 → CH4 + 2H2O) and revealing how solid FLP sites together with other active surface sites cooperatively catalyze reactions involving multiple small molecules. The final goal of this proposal is to build a universal strategy for designing solid FLP catalysts toward objective small molecules, which will be helpful in the development of highly-efficient and environmentally-benign catalysts for the activation of small molecules.