Isolation of Highly Reactive Cobalt Phthalocyanine via Electrochemical Activation for Enhanced CO₂ Reduction Reaction

Electrochemical CO₂ -to-CO conversion offers an attractive and efficient route to recycle CO₂ greenhouse gas. Molecular catalysts, like CoPc, are proved to be possible replacement for precious metal-based catalysts. These molecules, a combination of metal center and organic ligand molecule, may evolve into single atom structure for enhanced performance; besides, the manipulation of molecules' behavior also plays an important role in mechanism research. Here, in this work, the structure evolution of CoPc molecules is investigated via electrochemical-induced activation process. After numbers of cyclic voltammetry scanning, CoPc molecular crystals become cracked and crumbled, meanwhile the released CoPc molecules migrate to the conductive substrate. Atomic-scale HAADF-STEM proves the migration of CoPc molecules, which is the main reason for the enhancement in CO₂ -to-CO performance. The as-activated CoPc exhibits a maximum FE_CO of 99% in an H-type cell and affords a long-term durability at 100 mA cm^-2 for 29.3 h in a membrane electrode assembly reactor. Density-functional theory (DFT) calculation also demonstrates a favorable CO₂ activation energy with such an activated CoPc structure. This work provides a different perspective for understanding molecular catalysts as well as a reliable and universal method for practical utilization.