Acta Phys. -Chim. Sin. ›› 2021, Vol. 37 ›› Issue (5): 2007052.doi: 10.3866/PKU.WHXB202007052

Special Issue: CO2 Reduction

• REVIEW • Previous Articles     Next Articles

Recent Progress in Homogeneous Reductive Carbonylation of Carbon Dioxide with Hydrogen

Xuehua Zhang1,2, Yanwei Cao2, Qiongyao Chen2, Chaoren Shen2, Lin He2,3,*()   

  1. 1 School of Chemistry and Environmental Engineering, Yancheng Teachers University, Yancheng 224007, Jiangsu Province, China
    2 State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China
    3 Dalian National Laboratory for Clean Energy, CAS, Dalian 116023, Liaoning Province, China
  • Received:2020-07-20 Accepted:2020-08-03 Published:2020-08-06
  • Contact: Lin He E-mail:helin@licp.cas.cn
  • About author:Lin He, Email: helin@licp.cas.cn. Tel.: +86-512-88180906
  • Supported by:
    the National Natural Science Foundation of China(21802151);Foundation research project of Jiangsu Province, China(BK20180249);the Dalian National Laboratory For Clean Energy (DNL) Cooperation Fund, the CAS(DNL 201919);the Natural Science Foundation of the Jiangsu Higher Education Institutions of China(18KJB150033)

Abstract:

The efficient utilization of the greenhouse gas CO2 as a C1 feedstock can effectively reduce its emission and create economic value. Hence, the efficient chemical conversion of CO2 has been receiving intense attention. Due to the extremely low energy level of the CO2 molecule, the high energy barrier is the primary challenge for the chemical conversion of CO2. The chemical conversion of CO2 is mainly carried out through non-reductive transformation in industrial. Yet, the new route of chemical synthesis based on CO2 reductive transformation is an interesting topic to expand its resource utilization. In this context, homogeneous reductive carbonylation is a hot topic for the utilization of CO2 via reductive transformation. In this process, the metal hydride intermediate derived from the activation of the hydrogen source is crucial to the CO2 reduction. Hydrogen, a clean source with high atom economy, can be used as a reducing agent for the reductive conversion of inert CO2 through carbonylation, to construct C―O, C―N, and C―C bonds and to synthesize aldehyde/alcohol, carboxylic acid, ester, amide, and other chemicals. These expand the scope of CO2 high-value utilization and show great potential application in terms of resource utilization and environmental protection. This CO2 utilization process is thought to involve cascading catalytic reactions of CO2 reduction and carbonylation. The catalytic systems require the corresponding catalysts to efficiently promote each step and effectively inhibit undesired side reactions. Recently, considerable progress has been made in the homogeneous reductive carbonylation of CO2 with H2. However, this kind of reaction is mostly of the cascade type, and hence, requires harsh conditions and noble metal catalysts. The chemoselectivity is low because of the multiple competing reactions. In addition, due to the steric hindrance and electronic effects of the substrate, there are limitations on the types of substrates that can be employed. With the development of new characterization techniques and theoretical calculations, some progress has been made in revealing the reaction mechanism and in the activation of the carbon-oxygen bonds of CO2. Therefore, there is an urgent need to develop a more efficient catalytic system that requires mild conditions for reductive carbonylation. In this review, we provide an overview of the groundbreaking studies and the recent breakthroughs that have demonstrated the potential of metal catalysts to utilize the combination of CO2 and H2 as a C1 synthon, including olefin carbonylation, amine carbonylation, and alcohol/ether carbonylation, while highlighting the effect of different types of metal catalysts on the reaction. We conclude with a perspective on the future prospects of the homogeneous reductive carbonylation of CO2 with H2, providing readers a snapshot of this rapidly evolving field.

Key words: Carbon dioxide, Hydrogen, Reduction, Homogeneous catalysis, Carbonylation

MSC2000: 

  • O643