title: H2 Photogeneration Using a Phosphonate-Anchored Ni-PNP Catalyst on a Band-Edge-Modified p-Si(111)|AZO Construct.
abstract: We report the fabrication of a {semiconductor}|{metal oxide}|{molecular catalyst} construct for the photogeneration of dihydrogen (H2) under illumination, including band-edge modulation of the semiconductor electrode depending on the identity of Si(111)-R and the metal oxide. Briefly, a synergistic band-edge modulation is observed upon (i) the introduction of a p-Si|n-AZO heterojunction and (ii) introduction of an organic dimethoxyphenyl (diMeOPh) group at the heterojunction interface; the AZO also serves as a transparent and conductive conduit, which was capped with an ultrathin layer (20 Å) of amorphous TiO2 for stability. A phosphonate-appended PNP ligand and its Ni complex were then adsorbed to the p/n heterojunction for photoelectrochemical H2 generation (figures of merit: Vonset ≈ + 0.03 V vs NHE, Jmax ≈ 8 mA cm(-2) at 60 mM TsOH).
authors.affiliation: Department of Chemistry, University of Texas at Austin , Austin, Texas 78712, United States.
authors.forename: Hark Jin
authors.initials: HJ
authors.lastname: Kim
authors.affiliation: Department of Chemistry, University of Texas at Austin , Austin, Texas 78712, United States.
authors.forename: Junhyeok
authors.initials: J
authors.lastname: Seo
authors.affiliation: Department of Chemistry, University of Texas at Austin , Austin, Texas 78712, United States.
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Rose
keywords: AZO; Ni-PNP; Si(111) semiconductor; TiO2; band-edge modulation; photoelectrochemical H2 evolution