The rational design of multifunctional catalysts that use non-noble metals to facilitate the interconversion between H₂, O₂, and H₂O is an intense area of investigation. Bimetallic nanosystems with highly tunable electronic, structural, and catalytic properties that depend on their composition, structure, and size have attracted considerable attention. Herein, we report the synthesis of bimetallic nickel-copper (NiCu) alloy nanoparticles confined in a sp² carbon framework that exhibits trifunctional catalytic properties toward hydrogen evolution (HER), oxygen reduction (ORR), and oxygen evolution (OER) reactions. The electrocatalytic functions of the NiCu nanoalloys were experimentally and theoretically correlated with the composition-dependent local structural distortion of the bimetallic lattice at the nanoparticle surfaces. Our study demonstrated a downshift of the d-band of the catalysts that adjusts the binding energies of the intermediate catalytic species. XPS analysis revealed that the binding energy for Ni 2p3/2 band of the Ni0.25Cu0.75/C nanoparticles was shifted ∼3 times compared to other bimetallic systems, and this was correlated to the high electrocatalytic activity observed. Interestingly, the bimetallic Ni0.25Cu0.75/C catalyst surpassed the OER performance of RuO₂ benchmark catalyst exhibiting a small onset potential of 1.44 V vs RHE and an overpotential of 400 mV at 10 mA·cm⁻² as well as the electrochemical long-term stability of commercial RuO₂ and Pt catalysts and kept at least 90% of the initial current applied after 20 000 s for the OER/ORR/HER reactions. This study reveals significant insight about the structure-function relationship for non-noble bimetallic nanostructures with multifunctional electrocatalytic properties.
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Ahsan et al. (2020) studied this question.
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