<i>In Situ</i> Engineering of Pd Nanosponge Armored with Graphene Dots Using Br^– toward High-Performance and Stable Electrocatalyst for the Hydrogen Evolution Reaction

Abstract

In this study, we report a facile synthetic pathway to three-dimensional (3D) Pd nanosponge-shaped networks wrapped by graphene dots (Pd@G-NSs), which show superior electrocatalytic activity toward the hydrogen evolution reaction (HER) and exhibited excellent long-term stability in acidic media. Pd@G-NSs were synthesized by simply mixing Pd precursors, reducing agent, carbon dots (Cdots), and Br^- ion at 30 °C. Experimental results and density functional theory (DFT) calculations suggested that the Br^- ions played an essential role in accelerating the exfoliation of Cdot, supplying graphene layers, which could wrap the nanosponge-shaped Pd and finally form Pd@G-NS. In the absence of the Br^- ions, only aggregated Pd nanoparticles (NPs) were formed and randomly mixed with Cdots. The resultant Pd@G-NS exhibited a high electrochemically active surface area and accelerated charge transport characteristics, leading to its superior electrocatalytic activity toward the HER in acidic media. The HER overpotential of Pd@G-NS was 32 mV at 10 mA cm^-2, and the Tafel slope was 33 mV dec^-1. Furthermore, the unique Pd@G-NS catalyst showed long-term stability for over 3000 cycles in acidic media as well, owing to the protection of Pd nanosponges by graphene dot wrapping. The overall HER performance of the Pd@G-NS catalyst exceeded that of commercial Pt/C.