Highly effective electroreduction of carbon dioxide to methanol with molecular catalysts restricted on N–MXene for electronic regulation of CoPc

Molecular catalysts with precisely designed structures and abundant metal-nitrogen active sites have garnered significant attention for their ability to efficiently perform electroreduction of carbon dioxide (ERCD). However, the catalytic efficiency and selectivity are significantly limited by the fixed electronic structure of the metal-nitrogen structure, resulting in low production efficiency of more valuable products. This work presents the electronic regulation of cobalt phthalocyanine (CoPc) through in situ oxidation of N-doped Ti3C2Tx nanosheets (CoPc/o–N–MXene). The resulting material exhibits high activity and tailorable selectivity. The study confirmed a strong interaction between Co-N4 active sites and N–MXene after oxidation, resulting in a "Co–N–MXene" bond. This bond contributes to the transformation of intermediate ∗CO into ∗HCO, leading to a high selectivity of ERCD to methanol. This work provides a perspective on the mechanism of ERCD to methanol and an avenue for the synthesis of effective catalysts.