物理化学学报 >> 2021, Vol. 37 >> Issue (5): 2007052.doi: 10.3866/PKU.WHXB202007052

所属专题: CO2还原

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均相催化CO2/H2还原羰基化合成高值化学品研究进展

张雪华1,2, 曹彦伟2, 陈琼遥2, 沈超仁2, 何林2,3,*()   

  1. 1 盐城师范学院化学与环境工程学院,江苏 盐城 224007
    2 中国科学院兰州化学物理研究所,羰基合成与选择性氧化重点实验室,兰州 730000
    3 中国科学院洁净能源创新研究院,辽宁 大连 116023
  • 收稿日期:2020-07-20 录用日期:2020-08-03 发布日期:2020-08-06
  • 通讯作者: 何林 E-mail:helin@licp.cas.cn
  • 作者简介:何林,1982年生。2012年于复旦大学化学系获博士学位。2013–2016年在德国莱布尼茨催化所从事博士后研究。现任中国科学院兰州化学物理研究所研究员。主要研究方向集中在均多相催化体系创制用于C1资源高值化方面
  • 基金资助:
    国家自然科学基金(21802151);江苏省自然科学基金(BK20180249);中国科学院洁净能源创新研究院合作基金(DNL 201919);江苏省高等学校自然科学研究项目(18KJB150033)

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)

摘要:

高效利用温室气体CO2资源作为催化合成的C1原料既能有效减少它向大气的排放,又同时创造经济价值。其中基于CO2还原性转化的化学品合成新路线是拓展其资源化利用的热点。如能以清洁、高原子经济性的H2作为还原剂实现惰性CO2还原性转化,通过羰基化构筑C―O、C―N和C―C键,合成醛/醇、羧酸、酯、酰胺等化学品,将极大扩展由CO2高值化利用的范围与种类。近年来,均相催化CO2/H2还原羰基化制备化学品取得长足的进展,但该反应目前仍存在常用贵金属催化剂反应条件苛刻、目标产物选择性低以及底物适用性差等问题,制约了其的发展和应用。因此,设计开发更加高效的催化体系使反应能在相对温和的条件下得以实现仍然是一较大挑战。本文综述近年来均相催化CO2、H2参与的烯烃羰基化、胺羰基化、醇/醚羰基化以及其它羰基化反应研究及发展现状,重点探讨了不同种类的金属催化剂对反应过程的影响。最后对未来可能的发展方向进行了探讨和展望。

关键词: 二氧化碳, 氢气, 还原, 均相催化, 羰基化

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