非贵金属催化CO2/H2作为合成气替代品参与烯烃氢甲酰化反应的研究

CO2 is one of the greenhouse gases associated with climate change. With CO2 as an abundant, ubiquitous, and inexpensive C1 building block, environmental problems caused by excessive CO2 emission could be solved and a plethora of value-added chemicals, energy-related products, and materials could be produced. On the other hand, hydroformylation is an industrial process for the production of aldehydes from alkenes in the presence of syngas (CO/H2), and its production capacity has reached over ten million tons. However, CO suffers from high toxicity and is mainly produced by unsustainable fossil fuels. In this regard, using the combination of CO2 and H2 as syngas surrogate becomes an alternative and promising route to aldehyde/alcohol from alkene if a green and sustainable route is desired. Herein, we would like to design and develop a series of multifunctional Co-based catalysts, which would combine hydrogenation of CO2 to CO via reverse water gas shift and hydroformylation of alkenes in the presence of H2 and in situ CO under relatively mild condition. Furthermore, on the basis of catalyst structure, characterization and catalytic performance evaluation coupled with theoretical calculation, the mechanism and route for hydroformylation using CO2 will be elucidated. We hope this project will shed light on hydroformylation of alkenes with CO2/H2 and afford a variety of novel value-added chemicals with CO2/H2 as syngas surrogate.

CO2是最主要的温室气体，如果能将CO2这种丰富、廉价的C1构筑单元利用起来，不仅能解决过多CO2排放导致的环境问题，还能够获得高附加值的化学品。另一方面，氢甲酰化从烯烃与合成气(CO和H2)出发获得多一个碳原子的醛，通过氢甲酰化生成各种化学品的世界年产量超过一千万吨。然而，CO高毒且易燃，而且目前CO来自于传统的化石燃料。以CO2/H2作为合成气的替代品参与氢甲酰化在可持续化学上具有重要的价值。在此，我们将设计和合成一系列多功能的Co基催化剂，耦合逆水煤气变换和传统氢甲酰化的活性位点，把CO2氢化到CO，原位产生的CO随后与体系中的H2和烯烃反应生成氢甲酰化产物。而且，我们还将在催化剂结构、性能的表征和催化反应性能评价的基础上，结合理论计算，阐明多位点催化CO2参与氢甲酰化的反应机理和路径。本项目的开展将为实现CO2/H2作为合成气替代品合成多种新型高附加值化学品奠定基础。

“碳达峰、碳中和”目标下，将CO2这种丰富、价廉的C1资源进行化学利用，不仅能实现CO2减排，还可以获得高附加值化学品。其中，联合CO2/H2充当关键构筑单元以制备高值化学品对传统产业的转型升级具有重要作用，助推经济社会的可持续发展，。.本项目在使用CO2/H2作为合成气替代品的烯烃氢甲酰化方面取得了显著进展。首先，设计多功能纳米钴基催化剂，实现了CO2/H2参与的还原氢甲酰化，获得醛、醇等高值化学品。其次，针对纳米催化剂欠佳的区域选择性，发展了高效的分子催化剂，实现了CO2/H2参与烯烃氢甲酰化良好的区域选择性，产物的正异比最高达到93:7。除此之外，拓展了所制备纳米钴基催化剂的应用，其对传统氢甲酰化表现出良好的催化效果，甚至与一些纳米铑基催化剂的催化性能相当。.总结来说，本项目研究对于联合CO2/H2充当关键构筑单元以制备高值化学品，具有重要意义和应用前景。