有机胺功能化金属掺杂的介孔材料对CO2吸附活化并直接原位催化转化

Carbon dioxide, responsible for climate change, is the subject in increased attention in both academic and industrial research. Extensive efforts are being devoted to carbon capture and sequestration. On the other hand, CO2 is very attractive as an environmental friendly and economical feedstock to replace the poisonous carbon source for making value-added chemicals and fuels. Nowadays, CO2 absorption and CO2 conversion are conducted separately. After CO2 absorption, CO2 is desorbed at high temperature and compressed for further catalytic conversion, which render the critical problems in application, such as high energy for desorption, complex procedure, CO2 transportation, compression, and disposal. Thus coupling the CO2 capture and subsequent CO2 conversion, avoiding the desorption step, is very important from the view points of application and energy. The essence of our strategy is to develop the materials that can absorb CO2 then activate and catalyze the captured CO2. We aim to design amine functionalized metal loaded mesoporous materials due to their specific features such as large mesopore, high surface area, abundant surface functional groups and basic components, which can both absorb CO2 and activate CO2/epoxide. Therefore, amine functionalized metal loaded mesoporous materials are suitable for accomplishing CO2 absorption, activation and subsequent direct conversion of the captured CO2 to useful compounds, avoiding the desorption step. The activation of CO2 and catalytic reaction mechanisms for synthesis of cyclic carbonates are studied by in situ FTIR, NMR, visual observation and other techniques，which will help the design and synthesis of dual functional materials for CO2 absorption/activation and conversion. We believe these findings can pave the way for the development of green process towards low energy and cost effective practical CO2 capture and transformation.

随着资源短缺和环境恶化，将CO2吸附或转化成高附加值的有机化工产品成为化学领域的研究热点。目前CO2吸附和转化是分开进行的，如果将CO2吸附、活化、转化有效结合起来，实现"一体化"策略，能够避免能耗高的脱附过程，简化操作步骤，节省能源，在有效利用资源和缓解温室气体引起的环境问题方面将发挥重要的作用。目前对能同时吸附CO2并活化转化的双功能材料研究极少，针对这一问题，本课题拟利用有机胺功能化金属掺杂的介孔材料的组成、结构具有可控性和多样性的特点，采用不同的合成方法，合成系列有机胺功能化金属掺杂的介孔材料，考察对CO2的吸附性能和直接的活化催化转化性能，实现低压温和条件下将CO2吸附后无需脱附直接催化转化制备环状碳酸酯。在此基础上采用原位红外、核磁、辅助其他手段对吸附活化的CO2中间体结构和催化反应的可能机理进行深入探讨，为定向设计对CO2同时具有高吸附-高活化转化性能的材料提供理论指导。

随着资源短缺以及环境恶化，将二氧化碳吸附、转化成高附加值的有机化工产品成为化学领域的研究热点。目前CO2吸附、转化分开进行，如果进一步将CO2吸附、活化和化学转化有效结合起来，实现“一体化”策略，能够避免能耗高的脱附过程，简化操作步骤，节省能源，在有效利用资源和缓解温室气体引起的环境问题方面发挥重要作用。针对目前开展的同时对CO2吸附、活化转化的双功能材料的研究稀少的问题，本课题我们拟利用有机胺功能化金属掺杂的介孔材料的组成、结构等可控性和多样性的特点，采用不同的合成方法，合成系列有机胺功能化金属掺杂的介孔材料，考察了其对CO2的吸附性能和活化催化转化性能。采用原位红外结合理论计算探讨了有机胺功能化金属掺杂的介孔材料对CO2的催化反应的可能机理。进一步我们拓展了有机胺功能化金属掺杂的介孔材料，成功开发了几种离子液体、非金属基尿素衍生基介孔有机硅材料，并探讨了他们对CO2吸附性和CO2的催化转化性能，及吸附-催化转化“一体化”的性能。这些双功能材料的开发及吸附、催化机理的探讨对CO2的减排及有效利用提供了重要的理论指导。在项目执行期内发表在Green Chem., J. Catal., ChemSusChem,Cat. Sci. Technol., ACS Sustainable Chemistry & Engineering, Applied Catalysis A, Dalton Transactions等SCI论文43篇，其中发表在Green Chemistry,2016,18,2851-2863的论文为高被引论文。同时培养高素质研究生12名，包括博士研究生4名，硕士研究生8名项目执行期内，4人获得研究生国家奖学金，1人获得校优博，1人获得国家宝钢奖，研究生团队获得国家“创新创业大赛”三等奖等一系列奖项,项目负责人被评为2016年皇家化学会RSC “Top 1% 高被引中国学者”。