Coupling Cobalt Phthalocyanine Molecules on 3D Nitrogen‐Doped Vertical Graphene Arrays for Highly Efficient and Robust CO₂ Electroreduction

Abstract Metallic phthalocyanines (MePcs) have shown their potential as catalysts for CO₂ reduction reactions (CO₂RR). However, their low conductivity, easy agglomeration, and poor stability enslave the further progress of their CO₂RR applications. Herein, an integrated heterogeneous molecular catalyst through anchoring CoPc molecules on 3D nitrogen‐doped vertical graphene arrays (NVG) on carbon cloth (CC) is reported. The CoPc‐NVG/CC electrodes exhibit superior performance for reducing CO₂ to CO with a Faradic efficiency of above 97.5% over a wide potential range (99% at an optimal potential), a very high turnover frequency of 35800 h⁻¹, and decent stability. It is revealed that NVG interacts with CoPc to form highly efficient channels for electron transfer from NVG to CoPc, facilitating the Co(II)/Co(I) redox of CO₂ reduction. The strong coupling effect between NVG and CoPc molecules not only endows CoPc with high intrinsic activity for CO₂RR, but also enhances the stability of electrocatalysts under high potentials. This work paves an efficient approach for developing high‐performance heterogeneous catalysts by using rationally designed 3D integrated graphene arrays to host molecular metallic phthalocyanines so as to ameliorate their electronic structures and engineer stable active sites.