English

Co(Ⅱ)-Based Molecular Complexes for Photochemical CO₂ Reduction

• Jihong Zhang ,
• Dichang Zhong ^, ,
• Tongbu Lu ^,

• Institute for New Energy Materials & Low Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin 300384, China

Corresponding author: Email: dczhong@email.tjut.edu.cn (D.Z.); Email: lutongbu@tjut.edu.cn (T.L.); Tel.: +86-22-60214545 (T.L.)

• Received Date: 22 August 2020
  Accepted Date: 22 September 2020
  Revised Date: 21 September 2020
  Available Online: 15 May 2021
• Fund Project:

  the National Natural Science Foundation of China 

  the National Natural Science Foundation of China 

  the National Natural Science Foundation of China 

  the National Natural Science Foundation of China 

  111 Project of China 

  the Science & Technology Development Fund of Tianjin Education Commission for Higher Education, China 

Abstract: Nowadays, more than 85% of the energy is generated by fossil fuels. The excessive utilization of finite fossil fuels has resulted in the crises of energy shortage and global warming caused by greenhouse gas emissions. Researchers have conceived several means for trying to solve these problems, among which the sunlight-driven CO₂ reduction is viewed as a sustainable process that utilizes CO₂ as the raw material to produce chemical fuels, including CO, formate, and CH₄; this method not only realizes the conversion and storage of intermittent solar energy, but also decreases the CO₂ concentration in the atmosphere and alleviates global warming. However, photochemical CO₂ reduction usually undergoes a sluggish process due to the inertness of CO₂. Moreover, the selectivity of the CO₂ reduction reaction is also challenged by the hydrogen evolution reaction, which exhibits faster reaction kinetics. In this context, the rational design and synthesis of efficient and selective catalysts for photochemical CO₂ reduction are major challenges. Recently, non-noble metal Co(Ⅱ) complexes as molecular catalysts have shown excellent catalytic performances in photocatalytic CO₂ reduction. During the past several decades, significant progress has been achieved in improving the applicability of Co(Ⅱ) complexes for photocatalytic CO₂ reduction. In this review, we systematically report the latest research progress on the use of Co(Ⅱ) complexes in photocatalytic CO₂ reduction. To describe the progress of this research, we characterized the Co(Ⅱ)-based molecular catalysts into four categories according to ligand types, namely: (1) macrocyclic ligands, (2) polypyridine ligands, (3) porphyrin and porphyrin-like ligands, and (4) nonplanar N₄ ligands. The progress of the research on the heterogeneity of Co(Ⅱ) molecular complexes used for photochemical CO₂ reduction was also introduced and discussed. Furthermore, the effects of catalyst structures on catalytic efficiency, selectivity, and stability were particularly summarized and discussed, with the aim of revealing and building the relationship between catalyst structures and catalytic performances to guide the future design and synthesis of Co(Ⅱ) molecular complexes with excellent catalytic performance. Finally, the current challenges and problems in photocatalytic CO₂ reduction were summarized, and several suggestions for designing efficient Co(Ⅱ)-based molecular catalysts for photocatalytic CO₂ reduction were put forward. The trends for the future development of Co(Ⅱ) complex molecular catalysts were also investigated with regard to photocatalytic CO₂ reduction.

Key words:
• Co(Ⅱ) complexes
•  /  Carbon dioxide reduction
•  /  Photocatalysis
•  /  Molecular catalysis
•  /  Homogeneous catalysis

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