Synergistic engineering of palladium-cobalt nanoalloys on graphite sheet for efficient and sustainable hydrogen evolution reaction

The electrochemical hydrogen evolution reaction (HER)—a carbon-free route for hydrogen (H₂) production—is of the utmost importance for H₂-economy. Currently, HER performance is mainly restricted by the lack of promising alternatives to Pt-based electrocatalysts. In this study, we developed bimetallic PdCo alloy thin films with outstanding catalytic properties for the HER under acidic conditions. A simple aerosol-assisted chemical vapor deposition technique designed in-house was used to produce bimetallic alloy thin films on graphite sheets. The thin-film morphological patterns were significantly changed by varying the deposition time from 30 to 90 min. The optimized PdCo catalyst deposited for 30 min had a unique nanostructure with numerous active sites and exhibited faster HER kinetics than its analogs and pure Pd. As-prepared PdCo-30 electrode produced current densities of 10 and 1000 mA cm⁻² at overpotentials of 41 and 161 mV, respectively, along with a Tafel slope of 42 mV/dec, high conductivity (0.28 Ω), and catalytic stability of ∼24 h in 0.5 M H₂SO₄. The excellent HER activity of the PdCo alloy was attributed to the synergy between the noble transition metal and the thin nanostructured layer of the bimetallic catalyst, which promoted formation of extensive electroactive sites on the conductive graphite surface. Density functional theory calculations confirmed the experimental findings. The Gibbs free energy (ΔG_H*) of the PdCo alloy (−0.43 eV) was significantly lower than that of pure Pd (−0.57 eV), confirming the enhancement in HER activity due to the introduction of Co into the Pd lattice.