Targeted Assembly of Hierarchical Ni‐Ru Sites Toward Electrocatalytic Hydrogen Evolution Coupled With Amine Oxidation

ABSTRACT Coupling electrocatalytic hydrogen production with green amine oxidation has garnered significant advantages such as efficient energy consumption and enhanced economic viability. To this point, advanced strategies toward the construction of hybrid catalysts with multiple active components, dual functional activities and optimal synergistic effect have been chasing. Herein, we proposed the targeted assembly of hierarchical sites with single atomic Ni and Ru nanoclusters along fully‐conjugated phthalocyanine frameworks toward the coupling of electrocatalytic hydrogen production and the upgrading amine oxidation reaction, developing the high‐performance bifunctional catalytic system through atomic‐level interface engineering and electronic state modulation. The cooperative active sites demonstrated superior mass activity for HER coupled with the electrooxidation of various type of alternative amines. Specially, the as‐deigned RuNC@CPF‐Ni simultaneously possessed impressive activity for benzylamine oxidation with low overpotential and high Faraday efficiency of 94.6% at 1.47 V (vs. RHE). This work established a paradigm for designing efficient HER‐amine oxidation coupled systems, as well as toward advancing the fundamental understanding of electron modulation and reaction kinetics.