离子液体催化体系中二氧化碳转化的物理化学问题研究

This project is proposed based on the guide of chemistry division: “Physicochemical Basis on Resource and Energy Optimized Utilization ”. CO2 is an abundant C1 resource, and its chemical conversion to valued-added chemicals is of great importance, which has been paid worldwide attention. However, the chemical conversion of CO2 is challenge due to its thermodynamic stability and kinetic inertness, and many problems need to be resolved. For activation and conversion of CO2 to synthesize N-containing compounds, alcohols and carboxylic acids via formation of C-N, C-H, and C-C bond using CO2 as a starting material, this project intends to design various functional ionic liquids (ILs), and mainly construct two kinds of IL-based catalytic systems: metal-free IL catalytic systems and IL-metal catalytic systems, aiming at developing new approaches to synthesize value-added chemicals from CO2 and related highly efficient catalytic systems. The influences of various conditions on chemical reactions and reaction mechanism will be systematically investigated, and the activation of C=O bond in CO2 as well as the formation of various chemical bonds such as C-N, C-H and C-C will be explored. Moreover, the common and unique features of CO2 activation in different reaction systems will be explored as well, in order to uncover the synergistic effects between ILs and catalysts and the effects of the electrostatic interaction and hydrogen bonding in IL systems. Furthermore, the unique nature of the IL catalytic systems will be disclosed as well. From this project, a deep and systematic understanding about the related issues involving thermodynamics, kinetics and catalytic chemistry will be obtained, thus establishing reliable scientific basis for CO2 utilization.

本项目针对化学科学部申请指南中“资源或能源优化利用的物理化学基础”提出申请。CO2是丰富的C1资源，将其转化为高附加值化学品是国内外普遍关注的重大课题。由于CO2热力学稳定、动力学惰性，其高效化学转化有诸多科学难题有待解决。本项目针对CO2活化形成C-N、C-H、C-C键等合成含氮化合物、醇、酸等不同种类化学品，设计多种功能离子液体，构建阴阳离子协同作用的离子液体无金属催化体系和离子液体-金属催化体系，发展CO2转化合成高附加值化学品的新途径和高效催化体系；系统研究反应条件的影响规律和机理，探究C=O键活化和不同化学键形成的规律和机理以及反应中CO2活化的共性规律与特性，揭示离子液体和催化剂的协同作用机制，阐明离子液体催化体系中静电、氢键等作用对CO2活化转化的影响规律和机制，揭示离子液体催化体系的特殊本质；对相关热力学、动力学、催化化学问题取得新的认识，为CO2资源化利用奠定科学基础。

CO2是丰富的C1资源，将其转化为高附加值化学品是国内外普遍关注的重大课题。由于CO2热力学稳定、动力学惰性，其高效化学转化存在诸多科学难题有待解决。离子液体独特的物理化学性质为CO2的清洁高效转化提供了发展契机。本项目针对CO2活化转化形成C-N、C-H、C-C键等合成含氮化合物、醇、酸等不同种类化学品，设计了多种功能离子液体，构建了阴阳离子协同作用的离子液体无金属催化体系和离子液体-金属耦合催化体系，发展了CO2清洁转化合成高附加值化学品的新途径、新方法，探究了C=O键活化和不同化学键形成的规律和机理，揭示了离子液体和催化剂的协同作用机制，阐明了离子液体催化体系中静电、氢键等作用对CO2活化转化的影响规律和机制，揭示了离子液体催化体系的特殊本质；对相关热力学、动力学、催化化学问题取得新的认识，为CO2资源化利用奠定科学基础，推动了相关学科和技术的发展。.通过项目研究，取得一批重要创新性成果，如实现离子液体无金属催化CO2转化合成高附加值氮/氧杂环化合物，离子液体与金属催化剂耦合实现CO2还原合成醇、酸、酯等不同种类的化学品，离子液体电解液与自行设计的电催化材料耦合实现CO2电催化还原、高选择性制备C1产物/C2+产物，离子液体促进光催化还原CO2等，揭示了离子液体体系中各组分相互作用本质以及催化反应机制。发表SCI 收录论文90 篇，包括Nat. Commun. 3 篇、 Sci. Adv. 1 篇、Angew Chem. Int. Ed. 11 篇、Chem. Sci. 7 篇、Green Chem. 15 篇、National Chem. Rev. 1 篇等；申请专利21 件；编写中文专著1 部，英文专著1 部；组织国际学术会议3 次和国内学术会议3 次；在国际学术会议做邀请报告35 余次，国内学术会议邀请报告25 余次；培养博士毕业生12 名，出站博士后2 名，1 名参加人员获自然科学基金委优秀青年基金资助，培养了一批从事二氧化碳资源化转化利用的青年人才。