Plasmon-enhanced hydrogen evolution reaction on a Ag-branched-nanowire/Pt nanoparticle/AgCl nanocomposite

Abstract

A plasmon-enhanced photocatalytic system was designed with Ag–Pt–AgCl nanocomposites. Branched nanowires of Ag (AgBNWs) were first synthesized on indium-doped tin oxide-coated glass by electrodeposition. Then, the AgBNWs were dipped into an aqueous solution of Na₂[PtCl₆] at different concentrations from 1 to 5 mM to deposit Pt nanoparticles (PtNPs) on the AgBNWs via galvanic displacement. During the PtNP deposition, eluted Ag⁺ ions reacted with Cl⁻ ions to precipitate AgCl on the AgBNWs. The obtained AgBNW/PtNP/AgCl nanocomposites exhibited plasmonic absorption at approximately 465 nm. The nanocomposites were then examined as photoelectrodes for hydrogen evolution. The hybridization of the PtNPs on the AgBNWs significantly decreased the overpotential for water splitting in the dark, and the large number of PtNPs resulted in a higher efficiency compared to a conventional catalyst. Under blue-light irradiation (479 nm, 100 mW cm⁻²), the overpotential decreased by −110 mV, and the current density increased by 27.8 mA cm⁻². Under red-light irradiation (631 nm, 100 mW cm⁻²), the shift in onset potential was small, which could be attributed to the mismatching of the plasmonic absorption band with the excitation wavelength. The nanocomposite without AgCl (AgBNW/PtNP) was less effective at lowering the overpotential but more effective at improving the onset potential than AgBNW/PtNP/AgCl. These electrochemical behaviors were explained by the synergistic effect of the plasmon-induced photocurrent and charge transfer between Ag, Pt, and AgCl. The nanocomposite retained its photocatalytic activity after 400 cycles; therefore, the AgBNW/PtNP/AgCl nanocomposite could be useful for hydrogen evolution devices.