二氧化碳光催化转化反应

Carbon dioxide conversion at low pressure still remains great challenge. This project is trying to design and synthesize efficient photocatalysts for selective CO2 reduction to carbon monoxide, which goes in situ carbonylation to produce value-added compounds, e.g. acrylic acid, carboxylic acid ester or carbonates. Other options are to light-activation of either substrate or carbon dioxide molecule to generate the high-energy active species, e.g. 1,3-dipolar, substrate/carbon dioxide radical anion, which proceeds carboxylation/carboxylative cyclization with CO2 to afford carboxylic acid derivatives or heterocycles. The overall objection is the development of new catalytic solutions for the low-energy conversion of CO2 into value-added chemicals using either unique substrate-induced CO2 activation or light as a source of renewable energy. . It is crucial to find out highly active catalysts on the basis of investigating influences of active groups, electronic and steric factors on the catalyst performance to selectively reduction of CO2. Main purpose of this project is to develop high effective photocatalyst systems such as Ni/Co based metal catalysts and organic catalysts including functionalized ionic liquid. Our strategy in this project is to integrate activation of CO2 or CO2 reduction with in situ reaction of the active species induced by light, expectedly resulting in improvement of both photo-catalytic activity and selectivity of the products. . This project would stimulate further interest in academic research and industrial development that may lead to utilizing CO2 as a renewable chemical feedstock in combination with use of solar energy in organic synthesis.

发展低压温和条件下二氧化碳的低能耗转化过程仍然是具有极具挑战的课题。本项目采用光作为可再生能源，通过高效光催化反应，将二氧化碳 选择性地还原至一氧化碳；再通过原位羰基化反应制备羧酸酯、碳酸酯等高附加值产品。基于二氧化碳与底物的光诱导产生活性物种（如自由基离子、1,3-偶极体等）的原理，设计光驱动的二氧化碳参与的羧化反应及环化反应，合成羧酸及其衍生物、杂环化合物。因此，可望同时改善光催化效率以及产物的选择性。. 探讨活性基团、电子效应、立体结构对催化性能的影响规律，通过调节金属中心、配体电子结构和立体效应、转金属试剂等参数调控反应选择性。构建二氧化碳的环境友好、高效催化体系例如廉价钴、镍等金属、功能化离子液体等是二氧化碳光化学反应的关键。将二氧化碳光活化/光还原反应与后续的原位反应相结合是本项目的特色。. 本项目研究对于利用光作为可再生能源二氧化碳的高效转化利用，具有重要意义和应用

利用太阳能驱动的二氧化碳定向资源化仍然是具有极具挑战的课题之一。本项目在光促进的CO2高值化新方法、新途径以制备重要化学品、平台分子（如CO）绿色合成方法取得了显著进展，获得同行好评；主要成果包括：光致自由基引发的烯丙胺与常压CO2的环化反应、光催化的CO2还原功能化策略、基于第二配位层结构优化的光催化剂设计、离子液体调控可见光驱动选择性还原二氧化碳新策略以及二氧化碳间接利用策略。采用光作为可再生能源，构建温和条件下CO2的原位光催化转化反应，可以将太阳能利用与CO2的定向转化相结合；并显著改善光催化效率以及产物的选择性。. 本项目研究对于利用光作为可再生能源，开发二氧化碳的高效转化利用，具有重要意义和应用前景。