Department of Chemistry, University of North Carolina at Chapel Hill , CB3290, Chapel Hill, North Carolina 27599, United States.
J Am Chem Soc. 2014 Jul 9;136(27):9773-9. doi: 10.1021/ja505022f. Epub 2014 Jun 30.
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.
已证明，在染料敏化光电合成电池（DSPEC）中，苯甲醇（BnOH）在光驱动下脱氢生成苯甲醛和氢气。在 DSPEC 中，光阳极由 TiO2 纳米粒子的介孔薄膜或具有掺锡的 In2O3 纳米粒子（nanoITO）核和原子层沉积（nanoITO/TiO2）沉积的薄层 TiO2 组成。金属氧化物表面与过量的钌多吡啶发色团和氧化催化剂同时进行共衍生化。发色团激发和电子注入后，催化剂通过跨表面电子转移被激活为 -Ru(IV)═O(2+)，然后将苯甲醇氧化为苯甲醛。注入的电子被转移到 Pt 电极以产生 H2。与 TiO2 相比，nanoITO/TiO2 核/壳结构导致反向电子转移速率降低了 2 个数量级。在优化的壳层厚度下，BnOH 脱氢的吸收光子到电流效率达到 3.7%，与 TiO2 相比提高了约 10 倍。
