Enhanced Electrocatalytic Activity of a Zinc Porphyrin for CO2 Reduction: Cooperative Effects of Triazole Units in the Second Coordination Sphere

The control of the second coordination sphere in a coordination complex plays an important role in improving catalytic efficiency. Herein, we report a zinc porphyrin complex ZnPor8T with multiple flexible triazole units comprising the second coordination sphere, as an electrocatalyst for the highly selective electrochemical reduction of carbon dioxide (CO₂) to carbon monoxide (CO). This electrocatalyst converted CO₂ to CO with a Faradaic efficiency of 99 % and a current density of −6.2 mA cm⁻² at −2.4 V vs. Fc/Fc⁺ in N,N-dimethylformamide using water as the proton source. Structure-function relationship studies were carried out on ZnPor8T analogs containing different numbers of triazole units and distinct triazole geometries; these unveiled that the triazole units function cooperatively to stabilize the CO₂-catalyst adduct in order to facilitate intramolecular proton transfer. Our findings demonstrate that incorporating triazole units that function in a cooperative manner is a versatile strategy to enhance the activity of electrocatalytic CO₂ conversion.