title: Visible light driven benzyl alcohol dehydrogenation in a dye-sensitized photoelectrosynthesis cell.
abstract: Light-driven dehydrogenation of benzyl alcohol (BnOH) to benzaldehyde and hydrogen has been shown to occur in a dye-sensitized photoelectrosynthesis cell (DSPEC). In the DSPEC, the photoanode consists of mesoporous films of TiO2 nanoparticles or of core/shell nanoparticles with tin-doped In2O3 nanoparticle (nanoITO) cores and thin layers of TiO2 deposited by atomic layer deposition (nanoITO/TiO2). Metal oxide surfaces were coderivatized with both a ruthenium polypyridyl chromophore in excess and an oxidation catalyst. Chromophore excitation and electron injection were followed by cross-surface electron-transfer activation of the catalyst to -Ru(IV)═O(2+), which then oxidizes benzyl alcohol to benzaldehyde. The injected electrons are transferred to a Pt electrode for H2 production. The nanoITO/TiO2 core/shell structure causes a decrease of up to 2 orders of magnitude in back electron-transfer rate compared to TiO2. At the optimized shell thickness, sustained absorbed photon to current efficiency of 3.7% was achieved for BnOH dehydrogenation, an enhancement of ~10 compared to TiO2.
authors.affiliation: Department of Chemistry, University of North Carolina at Chapel Hill , CB3290, Chapel Hill, North Carolina 27599, United States.
authors.forename: Wenjing
authors.initials: W
authors.lastname: Song
authors.forename: Aaron K
authors.initials: AK
authors.lastname: Vannucci
authors.forename: Byron H
authors.initials: BH
authors.lastname: Farnum
authors.forename: Alexander M
authors.initials: AM
authors.lastname: Lapides
authors.forename: M Kyle
authors.initials: MK
authors.lastname: Brennaman
authors.forename: Berç
authors.initials: B
authors.lastname: Kalanyan
authors.forename: Leila
authors.initials: L
authors.lastname: Alibabaei
authors.forename: Javier J
authors.initials: JJ
authors.lastname: Concepcion
authors.forename: Mark D
authors.initials: MD
authors.lastname: Losego
authors.forename: Gregory N
authors.initials: GN
authors.lastname: Parsons
authors.forename: Thomas J
authors.initials: TJ
authors.lastname: Meyer