Au-Nanorods Supporting Pd and Pt Nanocatalysts for the Hydrogen Evolution Reaction: Pd Is Revealed to Be a Better...

Ordered thin films of Au nanorods (NRs) on Ti/Au/Si heterostructure substrates are electrodeposited in thin film aluminum oxide templates and, after template removal, serve as supports for Pd and Pt nanocatalysts. Based on previous work which showed a better electrocatalytic performance for layered Au/Pd nanostructures than monolithic Pd, electrodeposited 20 nm Pd discs on Au-NRs are first investigated in terms of their catalytic activity for the hydrogen evolution reaction (HER) and compared to monolithic 20 nm Pd and Pt discs. To further boost performance, the interfacial interaction area between the Au-NRs supports and the active metals (Pt and Pd) was increased via magnetron sputtering an extremely thin layer of Pt and Pd (20 nm overall sputtered thickness) on the Au-NRs after template removal. In this way, the whole NR surface (top and lateral) was covered with Pt and Pd nanoparticles, ensuring a maximum interfacial contact between the support and the active metal. The HER performance obtained was substantially higher than that of the other nanostructures. A Salient result of the present work, however, is the superior activity obtained for sputtered Pd on Au in comparison to that of sputtered Pt on Au. The results also show that increasing the Au-NR length translates in a strong increase in performance. Density functional theory calculations show that the interfacial electronic interactions between Au and Pd lead to suitable values of hydrogen adsorption energy on all possible sites, thus promoting faster (barrier-free diffusion) hydrogen adsorption and its recombination to H₂. A Volmer-Heyrovsky mechanism for HER is proposed, and a volcano plot is suggested based on the results of the Tafel plots and the calculated hydrogen adsorption energies.