Hefei National Laboratory for Physical Sciences at the Microscale,University of Science and Technology of China
School ofChemistry and Chemical Engineering,Anhui University of Technology

利用绿色H2将CO2转化为高附加值化学品是CO2资源化利用的重要方向,在提高能源利用效率的同时可有效缓解CO2过度排放所造成的生态和环境问题。近年来,热催化CO2加氢发展迅速,生产出多种可再生化学品。与甲烷和一氧化碳等气相产物相比,所得的甲醇、汽油和航空煤油等液体产物由于具有高能量密度和易储存运输的优势而更受青睐,引起学术界和工业界的广泛关注。然而,由于CO2分子的化学惰性及C—C键偶联的高能垒,CO2的活化和向液体产物的选择性转化极具挑战性,目前仍存在CO2单程转化率低、CO等副产物选择性高和催化剂易失活等关键问题。基于此,系统总结了CO2加氢制备液体产物的研究进展。首先从反应路径角度对CO2加氢制液体产物的机理进行介绍。重点阐述了高效催化剂的设计策略,系统归纳了催化剂尺寸、暴露晶面、缺陷位点、碱金属助剂、过渡金属助剂、载体、表面基团和亲疏水性等对催化活性、选择性和稳定性的影响。此外,还从不同尺度介绍了CO2加氢制备液体产物中催化剂多功能活性位点的构筑和调控机制。最后,在此基础上对CO2催化加氢制液体产物的应用前景进行总结与展望,催化剂的精细设计、工艺条件的探索、反应器的优化以及原子分子层面的催化机理研究等将大大推动CO2加氢制液体产物技术的实用化进程。

The conversion of CO2 into high value-added chemicals with green hydrogen is of great significance in the resource utilizationof CO2,which effectively alleviates the ecological and environmental problems caused by excessive CO2 emissions while improving energyefficiency. Recently,thermal-catalytic CO2 hydrogenation have developed rapidly to produce a variety of renewable chemicals. Comparedwith gaseous product (such as CH4 and CO),the resulting liquid products,such as methanol,gasoline,and aviation kerosene,arepreferred due to their advantages of high energy density as well as easy storage and transportation,and have received extensive attentionfrom both academia and industry. However,considering the chemical inertness of CO2 molecules and the high energy barrier of C—Cbond coupling,the activation of CO2 and the selective conversion to liquid products are extremely challenging. Key issues such as lowconversion per pass of CO2,high selectivity of by-products such as CO,and easy deactivation of catalysts are still present. Herein,recentadvancements of CO2 hydrogenation to liquid products are systematically summarized. The mechanism of CO2 hydrogenation to liquidproducts is introduced from the viewpoint of reaction pathway. Moreover,the design strategies of efficient catalysts are elaborated indetail. The effects of size,exposed facets,defect sites,alkali metal promoters,transition metal promoters,supports,surface groups,andhydrophilicity on the catalytic activity, selectivity, and stability are systematically summarized. In addition, the mechanisms ofconstructing and regulating the multifunctional active sites of catalysts in CO2 hydrogenation to liquid products are also introduced fromdifferent scales. Future perspectives for the further development of CO2 catalytic hydrogenation to liquid products are finally proposed.The fine design of catalysts,exploration of process conditions,optimization of reactors,and research on catalytic mechanism at the atomicand molecular levels will greatly promote the practical process of CO2 hydrogenation to liquid products technology.

国家杰出青年科学基金资助项目(21925204);中国科学院稳定支持基础研究领域青年团队计划资助项目(YSBR-051)

辛月,曾杰.CO2加氢制液体产物高效催化剂的设计及催化机理研究[J].洁净煤技术,2024,30(12):1−21.

XIN Yue,ZENG Jie. Design of efficient catalysts and research of catalytic mechanisms for CO2 hydrogenation to liquid products[J].Clean Coal Technology,2024,30(12):1−21.