The development of inexpensive and highly robust nanocatalysts (NCs) to boost electrochemical hydrogen evolution reaction (HER) strengthens the implementation of several emerging sustainable-energy technologies. Herein, we proposed a novel nano-architecture consisting of a hierarchical structured Ni@Pd nanocatalyst with Pt-clusters decoration on the surface (denoted by Ni@Pd-Pt) for HER application in acidic (0.5 M H2SO4) and alkaline (0.1 M KOH) mediums. The Ni@Pd-Pt NC is fabricated on a carbon black support via a “self-aligned” heterogeneous nucleation-crystal growth mechanism with 2 wt.% Pt-content. As-prepared Ni@Pd-Pt NC outperforms the standard Pt/C (30 wt.% Pt) catalyst in HER and delivers high-rate catalytic performance with an ultra-low overpotential (11.5 mV) at the cathodic current density of 10 mA∙cm−2 in alkaline medium, which is 161.5 mV and 14.5 mV less compared to Ni@Pd (173 mV) and standard Pt/C (26 mV) catalysts, respectively. Moreover, Ni@Pd-Pt NC achieves an exactly similar Tafel slope (42 mV∙dec−1) to standard Pt/C, which is 114 mV∙dec−1 lesser when compared to Ni@Pd NC. Besides, Ni@Pd-Pt NC exhibits an overpotential value of 37 mV at the current density of 10 mA cm−2 in acidic medium, which is competitive to standard Pt/C catalyst. By utilizing physical characterizations and electrochemical analysis, we demonstrated that such an aggressive HER activity is dominated by the increased selectivity during HER due to the reduced competition between intermediate products on the non-homogeneous NC surface. This phenomenon can be rationalized by electron localization owing to the electronegative difference (χPt > χPd > χNi) and strong lattice mismatch at the Ni@Pd heterogeneous binary interfaces. We believe that the obtained results will significantly provide a facile design strategy to develop next-generation heterogenous NCs for HER and related green-energy applications
Atomic Pt-Clusters Decoration Triggers a High-Rate Performance on Ni@Pd Bimetallic Nanocatalyst for Hydrogen Evolution Reaction in Both Alkaline and Acidic Medium
