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

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.