Implanting Numerous Hydrogen-Bonding Networks in a Cu-Porphyrin-Based Nanosheet to Boost CH₄ Selectivity in...

The exploration of novel systems for the electrochemical CO₂ reduction reaction (CO₂ RR) for the production of hydrocarbons like CH₄ remains a giant challenge. Well-designed electrocatalysts with advantages like proton generation/transferring and intermediate-fixating for efficient CO₂ RR are much preferred yet largely unexplored. In this work, a kind of Cu-porphyrin-based large-scale (≈1.5 μm) and ultrathin nanosheet (≈5 nm) has been successfully applied in electrochemical CO₂ RR. It exhibits a superior FE $$ of 70 % with a high current density (-183.0 mA cm^-2 ) at -1.6 V under rarely reported neutral conditions and maintains FE $$ >51 % over a wide potential range (-1.5 to -1.7 V) in a flow cell. The high performance can be attributed to the construction of numerous hydrogen-bonding networks through the integration of diaminotriazine with Cu-porphyrin, which is beneficial for proton migration and intermediate stabilization, as supported by DFT calculations. This work paves a new way in exploring hydrogen-bonding-based materials as efficient CO₂ RR catalysts.