基于廉价金属的新型路易斯酸-过渡金属配合物设计合成及其催化CO2加氢还原反应研究

Design and synthesis of highly efficient transition-metal complexes for CO2 transformation is one of the most challenging subject in research area of catalysis. This project aims to synthesize novel Lewis acid-transition metal complexes (LA-TM) based on cheap transition metals and study their catalytic activity in selective hydrogenation of CO2 to formic acid and methanol. Bifunctional LA-TM complexes possess adjacent Lewis acid and Lewis base as catalytic sites, thus can synergistically activate small molecules such as H2. Therefore, it is featured with high catalytic activity, mild reaction conditions, and cheap metals. With the design and development novel LA-TM and research of their catalytic mechanism in this project, we will reveal the relationship between structures of LA, Lewis acidity of LA, type of metals and their catalytic activity, selectivity. Main influence factors of the catalytic reaction and principle for selective CO2 hydrogenation will also be disclosed. This research will open a new avenue for design and synthesis of highly efficient and cheap catalyst for CO2 hydrogenation. It will provide important theoretical and technical support for sustainable CO2 transformation to carbon-based energy materials such as formic acid and methanol. This project also has a great strategic significance for development of sustainable energy materials based on carbon.

设计、合成高效的过渡金属配合物催化CO2精准转化，是催化研究领域最具挑战性的难点之一。本项目拟开发基于廉价金属的新型路易斯酸-过渡金属双功能配合物（LA-TM），并应用于高效、选择性催化CO2还原制备碳基能源物质甲酸和甲醇。LA-TM双功能配合物具有毗邻的路易斯酸和路易斯碱催化位点，可以对H2等小分子协同活化。因此具有催化活性高、反应条件温和、可用廉价过渡金属构建等特点。通过本项目对新型LA-TM双功能催化剂的设计、开发及其催化机理的研究，将阐明催化剂活性与LA配体结构、路易斯酸性、金属中心种类的相关性，揭示影响催化剂活性的主要因素和选择性催化CO2还原的内在规律。该项目的实施将为廉价高效CO2转化催化剂的设计和制备提供新的思路，并为CO2向碳基能源的可再生转化提供重要的理论和技术支持，对于开发可再生碳基能源有着战略性意义。

在当前“双碳”背景下，新型功能化金属配合物的开发及其催化活化氢气和二氧化碳分子及相关转化成为研究的热点之一。本项目基于路易斯酸碱协同催化理念设计开发了多种催化体系实现了温和条件下催化二氧化碳向甲酸、甲醇和羧酸等的绿色转化。同时发现设计合成的新型功能化配合物在相关加氢、脱氢以及借氢反应中都展示出优良性能。在ChemSuschem、Journal of CO2 Utilization、Organic Chemistry Frontiers等权威期刊上发表相关论文10篇。受邀在国际著名出版社Wiley和Elsevier分别出版专著章节一部。申请发明专利12项，已授权 8项。培养硕士毕业生8人，在读博士生2人，在读硕士生3人。通过本项目的实施，拓展了功能化配合物的种类，揭示了配合物结构与其催化活性的相关规律，通过实验和理论计算对反应机理的研究，揭示功能化金属配合物对氢气和二氧化碳小分子的活化机制，为新型高效加氢放氢催化剂的开发奠定实验和理论基础。