Platinum monolayer electrocatalyst on gold nanostructures on silicon for photoelectrochemical hydrogen evolution.

Pt monolayer decorated gold nanostructured film on planar p-type silicon is utilized for photoelectrochemical H2 generation in this work. First, gold nanostructured film on silicon was spontaneously produced by galvanic displacement of the reduction of gold ion and the oxidation of silicon in the presence of fluoride anion. Second, underpotential deposition (UPD) of copper under illumination produced Cu monolayer on gold nanostructured film followed by galvanic exchange of less-noble Cu monolayer with more-noble PtCl6(2-). Pt(shell)/Au(core) on p-type silicon showed the similar activity with platinum nanoparticle on silicon for photoelectrochemical hydrogen evolution reaction in spite of low platinum loading. From Tafel analysis, Pt(shell)/Au(core) electrocatalyst shows the higher area-specific activity than platinum nanoparticle on silicon demonstrating the significant role of underlying gold for charge transfer reaction from silicon to H(+) through platinum catalyst.

Enhanced photoelectrochemical hydrogen production from silicon nanowire array photocathode.

Herein we report that silicon nanowires (SiNWs) fabricated via metal-catalyzed electroless etching yielded a photoelectrochemical hydrogen generation performance superior to that of a planar Si, which is attributed to a lower kinetic overpotential due to a higher surface roughness, favorable shift in the flat-band potential, and light-trapping effects of the SiNW surface. The SiNW photocathode yielded a photovoltage of 0.42 V, one of the highest values ever reported for hydrogen generation on p-type Si/electrolyte interfaces.