Electrocatalytic Reduction of CO₂ to CO by Molecular Cobalt–Polypyridine Diamine Complexes

Abstract

Cobalt complexes have previously been reported to exhibit high faradaic efficiency in reducing CO2 to CO. Herein, we synthesized capsule-like cobalt–polypyridine diamine complexes [Co(L1)](BF4)2 (1) and [Co(L2) (CH3CN)](BF4)2 (2) as catalysts for the electrocatalytic reduction of CO2. Under catalytic conditions, complexes 1 and 2 demonstrated the electrocatalytic reduction of CO2 to CO in the presence or absence of CH3OH as a proton source. Experimental and computational studies revealed that complexes 1 and 2 undergo two consecutive reversible one-electron reductions on the cobalt core, followed by the addition of CO2 to form a metallocarboxylate intermediate [CoII(L)–CO22−]0. This crucial reaction intermediate, which governs the catalytic cycle, was successfully detected using high resolution mass spectrometry (HRMS). In situ Fourier-transform infrared spectrometer (FTIR) analysis showed that methanol can enhance the rate of carbon–oxygen bond cleavage of the metallocarboxylate intermediate. DFT studies on [CoII(L)–CO22−]0 have suggested that the doubly reduced species attacks CO2 on the C atom through the dz2 orbital, while the interaction with CO2 is further stabilized by the π interaction between the metal dxz or dxz orbital with p orbitals on the O atoms. Further reductions generate a metal carbonyl intermediate [CoI(L)–CO]+, which ultimately releases CO.

Keywords

• cobalt
• molecular catalyst
• electrocatalysis
• CO₂ reduction