Bruggeman Didjay F, Bakker Tijmen M A, Mathew Simon, Reek Joost N H
Homogeneous, Supramolecular and Bio-Inspired Catalysis, van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098, XH, Amsterdam, The Netherlands.
Chemistry. 2021 Jan 4;27(1):218-221. doi: 10.1002/chem.202003306. Epub 2020 Nov 26.
This work reports a dye-sensitized photoelectrochemical cell (DSPEC) that couples redox-mediated light-driven oxidative organic transformations to reductive hydrogen (H ) formation. The DSPEC photoanode consists of a mesoporous anatase TiO film on FTO (fluorine-doped tin oxide), sensitized with the thienopyrroledione-based dye AP11, while H was formed at a FTO-Pt cathode. Irradiation of the dye-sensitized photoanode transforms 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) to the oxidized TEMPO (TEMPO ), which acts as a chemical oxidant for the conversion of benzyl alcohol. The TEMPO couple, previously used as redox mediator in DSSC, mediates efficient electron transfer from the organic substrate to the photo-oxidized dye. A DSPEC photoreactor was designed that allows in situ monitoring the reaction progress by infrared spectroscopy and gas chromatography. Sustained light-driven oxidation of benzyl alcohol to benzaldehyde within the DSPEC photoreactor, using of TEMPO as mediator, demonstrated the efficiency of the device, with a photocurrent of 0.4 mA cm , approaching quantitative Faradaic efficiency and exhibiting excellent device stability.
这项工作报道了一种染料敏化光电化学电池（DSPEC），该电池将氧化还原介导的光驱动有机氧化转化与还原态氢（H）的形成相结合。DSPEC光阳极由FTO（氟掺杂氧化锡）上的介孔锐钛矿TiO薄膜组成，用基于噻吩并吡咯二酮的染料AP11敏化，而H在FTO-Pt阴极上形成。染料敏化光阳极的光照将2,2,6,6-四甲基哌啶1-氧基（TEMPO）转化为氧化态的TEMPO（TEMPO），其作为苯甲醇转化的化学氧化剂。TEMPO对，以前在DSSC中用作氧化还原介质，介导了从有机底物到光氧化染料的有效电子转移。设计了一种DSPEC光反应器，该反应器允许通过红外光谱和气相色谱原位监测反应进程。使用TEMPO作为介质，在DSPEC光反应器内将苯甲醇持续光驱动氧化为苯甲醛，证明了该装置的效率，光电流为0.4 mA cm，接近定量法拉第效率并表现出优异的装置稳定性。
