受阻路易斯酸碱对活化小分子的理论机理研究和催化剂设计

The activation of N2 and small alkanes is of great significance both in basic research and industrial applications. Frustrated Lewis pairs (FLP) have excellent performance in activating small molecules such as H2, CO, CO2, C2H4, and N2O. However, the nature of the activation is still under debating and waiting for further study. The study on the nature of the activation will help us to expand the scope of the FLP, such as to transition-metal FLP, to bases without lone-pair electrons, and even to metal-free Lewis acids. The study will then provide guidelines for the design of more effective catalysts. By first principle calculations this project will systematically study the nature and mechanism of the activation. With the in-depth understanding of the nature of the FLP catalysts, we will design several FLP or metal-free Lewis acid catalysts which are highly active and easy to realize by experiments in activating small molecules especially N2 and small alkanes. We hope our catalysts can be verified by cooperating with experiments.

N2和小分子烷烃的活化具有重要的基础研究意义以及工业应用价值。受阻路易斯酸碱对(FLP)在活化小分子（H2, CO, CO2, C2H4, N2O）方面具有非常优秀的催化性能，然而目前对其活化本质的研究并未尘埃落定，还有待继续深入研究。对其本质的深入了解，将有助于扩展FLP催化体系及其应用范围，如将碱中心扩展到非孤对电子型，将FLP扩展到过渡金属体系，甚至扩展到非金属路易斯酸催化剂，为设计更高效的催化剂提供理论指导。本项目将采用第一性原理计算，在深入研究FLP活化本质及机理的基础上，设计几个高效并有希望实现的FLP或非金属路易斯酸催化剂，用于小分子，主要是N2和小分子烷烃的活化，并希望能得到实验的验证。

通过理论计算模拟，我们从分子层面对一系列非金属路易斯或非金属路易酸碱对进行了系统设计，对它们的酸碱性进行调变，从而实现对CO2, CH4, N2和H3BNH3等小分子的有效活化。我们通过数学建模，建立了酸碱中心物性参数和反应活性间的统计模型，用于指导非金属路易斯或酸碱对的分子设计。该项目成功实现了CO2, CH4, N2和H3BNH3等小分子的高效活化或催化转化，大部分反应能够在温和的反应条件下实现。项目的发现加深了我们对路易斯酸碱活化小分子的规律的认识，为实验实现这些小分子的高效活化或转化奠定了坚实的理论基础。