N-supports for electronic regulation of phthalocyanine cobalt to selective carbon dioxide electroreduction toward methanol

Electrocatalytic carbon dioxide reduction (CO 2 RR) offers a highly promising strategy for achieving carbon-neutral energy cycles by converting CO 2 into high-value chemicals and fuels. While it remains challenging to modulate the electronic environment precisely and systematically around the active sites of catalysts to steer the reaction toward desired products, especially hydrocarbons such as methanol (CH 3 OH). This study reports a strategy that enables highly efficient CO 2 RR to CH 3 OH under neutral conditions by fine-tuning the electronic environment of cobalt center in cobalt phthalocyanine (CoPc) through nitrogen-rich supports. Among them, CoPc/TiN achieved a high Faradaic efficiency of 53.28% for CH 3 OH production at –1.0 V ( vs . reversible hydrogen electrode), with a partial current density of 68.76 mA cm ‒2 . X-ray photoelectron spectroscopy and extended X-ray absorption fine structure analyses reveal that electronic modulation at Co-N sites of CoPc, which can promote *HCO coupling, and it’s a critical step in CH 3 OH formation. Theoretical calculations further demonstrate that nitrogen carriers induce electronic redistribution within the Co center coordination environment. The projected density of states of *HCO on CoPc loaded on (Si)N-MXene)/TiN/C 3 N 4 shown electron deficient characteristics. It promotes the formation of *HCO, thereby facilitating CH 3 OH synthesis. This work provides new mechanistic insights into CO 2 RR for CH 3 OH and opens new avenues for designing efficient catalysts.