Through-Space Charge Interaction Substituent Effects in Molecular Catalysis Leading to the Design of the Most Efficient Catalyst of CO2-to-CO Electrochemical Conversion.

The starting point of this study of through-space substituent effects on the catalysis of the electrochemical CO2-to-CO conversion by iron(0) tetraphenylporphyrins is the linear free energy correlation between through-structure electronic effects and the iron(I/0) standard potential that we established separately. The introduction of four positively charged trimethylanilinium groups at the para positions of the tetraphenylporphyrin (TPP) phenyls results in an important positive deviation from the correlation and a parallel improvement of the catalytic Tafel plot. The assignment of this catalysis boosting effect to the Coulombic interaction of these positive charges with the negative charge borne by the initial Fe0-CO2 adduct is confirmed by the negative deviation observed when the four positive charges are replaced by four negative charges borne by sulfonate groups also installed in the para positions of the TPP phenyls. The climax of this strategy of catalysis boosting by means of Coulombic stabilization of the initial Fe0-CO2 adduct is reached when four positively charged trimethylanilinium groups are introduced at the ortho positions of the TPP phenyls. The addition of a large concentration of a weak acid-phenol-helps by cleaving one of the C-O bonds of CO2. The efficiency of the resulting catalyst is unprecedented, as can be judged by the catalytic Tafel plot benchmarking with all presently available catalysts of the electrochemical CO2-to-CO conversion. The maximal turnover frequency (TOF) is as high as 106 s-1 and is reached at an overpotential of only 220 mV; the extrapolated TOF at zero overpotential is larger than 300 s-1. This catalyst leads to a highly selective formation of CO (practically 100%) in spite of the presence of a high concentration of phenol, which could have favored H2 evolution. It is also very stable, showing no significant alteration after more than 80 h of electrolysis.