Active Sites of Cobalt Phthalocyanine in Electrocatalytic CO₂ Reduction to Methanol

Many metal coordination compounds catalyze CO₂ electroreduction to CO, but cobalt phthalocyanine hybridized with conductive carbon such as carbon nanotubes is currently the only one that can generate methanol. The underlying structure‐reactivity correlation and reaction mechanism desperately demand elucidation. Here we report the first in situ X‐ray absorption spectroscopy characterization, combined with ex situ spectroscopic and electrocatalytic measurements, to study CoPc‐catalyzed CO₂ reduction to methanol. Molecular dispersion of CoPc on CNT surfaces, as evidenced by the observed electronic interaction between the two, is crucial to fast electron transfer to the active sites and multi‐electron CO₂ reduction.