Three-Way Control on Product Selectivity in Electrocatalytic CO 2 Reduction Reaction Using a Single Molecular Co-NHC Catalyst.

For a long time, molecular electrocatalysts have been developed to reduce CO 2 efficiently to value-added products such as CO and HCO 2 H, along with H 2 ; however, selectivity remained as a major issue. Recent work toward addressing this issue showed that several different catalysts could be used to achieve product selectivity. It is desirable that instead of using different catalysts for specific products, a single catalyst should be able to produce the target products by subtle tuning of the reaction conditions. Toward this objective, herein we presented the organometallic Co electrocatalyst Co- NHC U and successfully utilized it in the electrochemical CO 2 reduction reaction (CO 2 RR) to produce CO, H 2 , and HCO 2 H with notable selectivity. The reduction of CO 2 selectively produced CO with 81 ± 2% Faradaic efficiency (FE) in the presence of 5% H 2 O as a proton source. The selectivity was changed toward H 2 with 80 ± 3% FE when 1.5 M triethylamine was added as an additive in the presence of 10% H 2 O as a proton source. In the presence of 1.0 M morpholine as an external additive, the CO 2 -saturated solution containing 10% trifluoroethanol as a proton source generates 55 ± 5% HCO 2 H as the predominant product, with H 2 as a competitive side product. It was found that the combined effect of the proton source and the additive in association with the nature of the Co- NHC U catalyst changed the selectivity of the products in this reaction.