Matteo Miola, Simin Li, Xin-Ming Hu, Marcel Ceccato, Annette-E. Surkus, Edmund Welter, Steen U. Pedersen, Henrik Junge, Troels Skrydstrup, Matthias Beller, Kim Daasbjerg

https://doi.org/10.1002/admi.202100067

Electrochemical CO₂ reduction to valuable chemicals represents a green and sustainable approach to close the anthropogenic carbon cycle, but has been impeded by low efficiency and high cost of electrocatalysts. Here, a cost-effective hybrid catalyst consisting of hemin (chloroprotoporphyrin IX iron(III)), a product recovered from bovine blood, adsorbed onto commercial Vulcan carbon is reported. Upon heat treatment, this material shows significantly improved activity and selectivity for CO₂ reduction in water while exhibiting good stability for more than 10 h. The heat treatment leads to consecutive removal of the axial chlorine atom and decomposition of the iron porphyrin ring, restructuring to form atomic Fe sites. The optimized hybrid catalyst obtained at 900 °C shows near-unity selectivity for reduction of CO₂ to CO at a small overpotential of 310 mV. The insight into transformation of adsorbed Fe complexes into single Fe atoms upon heat treatment provides guidance for development of single atom catalysts.