多相催化是现代化学工业中的一个核心问题。从催化剂的传统实验“尝试”法到理性设计的转变，对计算方法的精确性和完善性有着较高的要求。当前的多相催化计算方法忽略了熵效应，尤其是其中的非简谐效应的重要作用。本项目拟围绕多相催化中的熵效应，以费托合成中CO的解离为模型反应，评估适用于多相催化反应的熵和自由能计算的动力学采样方法，在此基础上研究熵与多相催化中的三个重要因素间的关系：催化剂形貌，催化反应速率，催化反应环境。结合实验表征手段，利用基于分子动力学和Wulff理论的结构预测方法及晶格动力学研究熵和催化剂颗粒形貌的关系；利用微观动力学和密度泛函理论研究表面构象熵和反应速率之间的关系；利用量子力学/分子力学多尺度动力学研究反应环境与催化反应熵垒、自由能垒间的关系。该项目的实施不仅可指导费托合成油体系的进一步改性，而且将弥补常规计算方法的漏洞，对研究其它多相催化反应有重要的指导意义。

Heterogeneous catalysis is the central issue in modern chemical industry. However, the current methods in computational heterogeneous catalysis usually ignore entropy, especially the anharmonicity of the systems. Using the CO dissociation reaction in Fischer-Tropsch synthesis as model reaction, the current project aims to focus on the entropic effects in heterogeneous catalysis, benchmarking and evaluating the ab-initio molecular dynamics sampling approaches for entropy and free energy calculation, followed by the studying of the relationships between entropy and three key factors in heterogeneous catalysis: the morphology of catalyst particles, the rate of reaction, and the environments of reaction. With the help of experimental characterization, structure prediction method based on MD and Wulff theorem, combined with lattice dynamics will be used to study the relationship between entropy and the morphology of the catalyst. Microkinetic modeling and density functional theory calculations are to be used to study the role of entropy in reaction rate. Quantum chemical/molecular chemical multi-scale molecular dynamics will be used to study the effect of the solvent environment on the entropic and free energy barriers of the reactions. In addition to guiding further improvement of Fischer-Tropsch synthesis, the implementation of the project will be helpful for the integrity of the computational approach, providing guidance to the study of other heterogeneous catalytic reactions.