Synthesis and characterization of a photosensitive interface for hydrogen generation: Chemically modified p-type semiconducting silicon photocathodes.

p-Si photocathodes functionalized first with an N,N'-dialkyl-4,4'-bipyridinium redox reagent, (PQ(2+/+-))(surf), and then with a Pt precursor, PtCl(6) (2-), give significant efficiency (up to 5%) for photoelectrochemical H(2) generation with 632.8-nm light. Naked p-Si photocathodes give nearly zero efficiency, owing to poor H(2) evolution kinetics that are improved by the (PQ(2+/+-))(surf)/Pt modification. The mechanism of H(2) evolution from p-Si/(PQ(2+/+-))(surf)/Pt is first photoexcitation of electrons to the conduction band of Si followed by (PQ(2+))(surf) --> (PQ(+-))(surf) reduction. The dispersion of Pt then catalyzes H(2)O reduction to give H(2) and regeneration of (PQ(2+))(surf). The overall energy conversion efficiency rivals the best direct optical to chemical conversion systems reported to date.