Electrochemical reduction of CO₂ to CO and HCOO^- using metal-cyclam complex catalysts: predicting selectivity and...

Sustainable fuel production from CO₂ through electrocatalytic reduction is promising but challenging due to high overpotential and poor product selectivity. Herein, we computed the reaction free energies of electrocatalytic reduction of CO₂ to CO and HCOO^- using the density functional theory method and screened transition metal(M)-cyclam(L) complexes as molecular catalysts for CO₂ reduction. Our results showed that pK_a of the proton adduct formed by the protonation of the reduced metal center can be used as a descriptor to select the operating pH of the solution to steer the reaction toward either the CO or hydride cycle. Among the complexes, [LNi]²⁺ and [LPd]²⁺ catalyze the reactions by following the CO cycle and are the CO selective catalysts in the pH ranges 1.81-7.31 and 6.10 and higher, respectively. Among the complexes that catalyze the reactions by following the hydride cycle, [LMo]²⁺ and [LW]³⁺ are HCOO^- selective catalysts and have low limiting potentials of -1.33 V and -1.54 V, respectively. Other complexes, including [LRh]²⁺, [LIr]²⁺, [LW]²⁺, [LCo]²⁺, and [LTc]²⁺ catalyze the reactions resulting in either HCOO^- from CO₂ reduction or H₂ from proton reduction; however, HCOO^- formation is always thermodynamically more favorable. Notably, [LMo]²⁺, [LW]³⁺, [LW]²⁺ and [LCo]²⁺ have limiting potentials less negative than -1.6 V and are based on Earth-abundant elements, making them attractive for practical application.