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Homogeneously Catalyzed Electroreduction of Carbon Dioxide—Methods, Mechanisms, and Catalysts

2018/01/10 by Robert Francke, Benjamin Schille, Michael Roemelt · 1 citation
Energy · Chemical Engineering · Chemistry · #CO2 Reduction Techniques and Catalysts #Ionic liquids properties and applications #Carbon dioxide utilization in catalysis #Chemistry #Catalysis #Nanotechnology #Cooperativity #Biochemical engineering #Homogeneous #Combinatorial chemistry #Organic chemistry #Materials science #Thermodynamics

paper · doi:10.1021/acs.chemrev.7b00459

openalex publication_date 2018/01/10 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/30

Abstract

The utilization of CO 2 via electrochemical reduction constitutes a promising approach toward production of value-added chemicals or fuels using intermittent renewable energy sources. For this purpose, molecular electrocatalysts are frequently studied and the recent progress both in tuning of the catalytic properties and in mechanistic understanding is truly remarkable. While in earlier years research efforts were focused on complexes with rare metal centers such as Re, Ru, and Pd, the focus has recently shifted toward earth-abundant transition metals such as Mn, Fe, Co, and Ni. By application of appropriate ligands, these metals have been rendered more than competitive for CO 2 reduction compared to the heavier homologues. In addition, the important roles of the second and outer coordination spheres in the catalytic processes have become apparent, and metal–ligand cooperativity has recently become a well-established tool for further tuning of the catalytic behavior. Surprising advances have also been made with very simple organocatalysts, although the mechanisms behind their reactivity are not yet entirely understood. Herein, the developments of the last three decades in electrocatalytic CO 2 reduction with homogeneous catalysts are reviewed. A discussion of the underlying mechanistic principles is included along with a treatment of the experimental and computational techniques for mechanistic studies and catalyst benchmarking. Important catalyst families are discussed in detail with regard to mechanistic aspects, and recent advances in the field are highlighted.

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