English

Research Progress Regarding Transition Metal-Catalyzed Carbonylations with CO₂/H₂

• Hua Kaimin ^1,2, ,
• Liu Xiaofang ^1, ,
• Wei Baiyin ^1,3, ,
• Zhang Shunan ^1,2, ,
• Wang Hui ^{1, ,} ,
• Sun Yuhan ^{1,3,4, ,}

• 1.

  CAS Key Laboratory of Low-Carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201203, China

• 2.

  University of the Chinese Academy of Sciences, Beijing 100049, China

• 3.

  School of Physical Science and Technology, ShanghaiTech University, Shanghai 201203, China

• 4.

  Shanghai Institute of Clean Technology, Shanghai 201620, China

Corresponding author: Email: wanghh@sari.ac.cn (W.H.); Tel.: +86-21-20328002 (W.H); Email: sunyh@sari.ac.cn (S.Y.); Tel.: +86-21-20325009 (S.Y.)

• Received Date: 29 September 2020
  Accepted Date: 20 October 2020
  Revised Date: 20 October 2020
  Available Online: 15 May 2021
• Fund Project:

  This work was supported by the National Natural Science Foundation of China (21776296, 21905291), the National Key Research and Development Program of China (2017YFB0602203), Strategic Priority Research Program of the Chinese Academy of Sciences (XDA21090201), Key Research Program of Chinese Academy of Sciences (ZDRW-ZS-2018-1-3), and the Shanghai Sailing Program, China (19YF1453000)

Abstract: Ever-increasing energy demands due to rapid industrialization and urban population growth have drastically reduced petroleum reserves and increased greenhouse-gas production, and the latter has consequently contributed to climate change and environmental damage. Therefore, it is highly desirable to produce fuels and chemicals from non-petroleum feedstocks and to reduce the atmospheric concentrations of greenhouse gases. One solution has involved using carbon dioxide (CO₂), a main greenhouse gas, as a C1 feedstock for producing industrial fuels and chemicals. However, this requires high energy input from reductants or reactants with relatively high free energy (e.g., H₂ gas) because CO₂ is a highly oxidized, thermodynamically stable form of carbon. H₂ can be generated through water photolysis, making it an ideal reductant for hydrogenating CO₂ to CO. In situ generation of CO such as this has been developed for various carbonylation reactions that produce high value-added chemicals and avoid deriving CO from fossil fuels. This is beneficial because CO is toxic, and when extracted from fossil fuels it requires tedious separation and transportation. This combination of CO₂ and H₂ allows for functional molecules to be synthesized as entries into the chemical industry value chain and would generate a carbon footprint much lower than that of conventional petrochemical pathways. Based on this, CO₂/H₂ carbonylations using homogeneous transition metal-based catalysts have attracted increasing attention. Through this process, alkenes have been converted to alcohols, carboxylic acids, amines, and aldehydes. Heterogeneous catalysis has also provided an innovative approach for the carbonylation of alkenes with CO₂/H₂. Based on these alkene carbonylations, the scope of CO₂/H₂ carbonylations has been expanded to include aryl halides, methanol, and methanol derivatives, which give the corresponding aryl aldehyde, acetic acid, and ethanol products. These carbonylations revealed indirect CO₂-HCOOH-CO pathways and direct CO₂ insertion pathways. The use of this process is ever-increasing and has expanded the scope of CO₂ utilization to produce novel, high value-added or bulk chemicals, and has promoted sustainable chemistry. This review summarizes the recent advances in transition-metal-catalyzed carbonylations with CO₂/H₂ and discusses the perspectives and challenges of further research.

Key words:
• Carbon dioxide hydrogenation
•  /  Carbonylation
•  /  Transition metal catalysis
•  /  Alcohols
•  /  Aldehydes
•  /  Carboxylic acids
•  /  Ethanol
•  /  Acetic acid

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