Rastgar Shokoufeh, Wittstock Gunther
Institute of Chemistry, School of Mathematics and Science, Carl von Ossietzky Universität Oldenburg, 26111, Oldenburg, Germany.
Angew Chem Int Ed Engl. 2024 Sep 23;63(39):e202319074. doi: 10.1002/anie.202319074. Epub 2024 Aug 20.
The influence of the ion transfer on photoinduced electron transfer (ET) reactions was studied on the surface of hyperbranched semiconducting BiVO particles spontaneously adsorbed at the liquid-liquid (L/L) interface between an aqueous LiCl solution and bis(triphenylphosphoranylidene) ammonium tetrakis(pentaflurophenyl)borate (BATB) in 1,2-dichlorethane. The organic electrolyte was supplemented with Co(bpy) to accept photoexcited electrons from BiVO under formation of the corresponding Co(II) complex. The L/L interface was stabilized at the orifice of a micropipette (MP) and allowed to record ion transfer cyclic voltammetry (ITCV) by applying a Galvani potential difference between two reference electrodes in the electrolyte solutions with intermittent illumination by visible light (λ>420 nm). The photogenerated holes caused oxidation of water to O. Co(II) and O were detected at constant at an amperometric microelectrode (ME) facing the orifice of the MP in either the organic or the aqueous electrolyte. The overall current exhibits a photocurrent only in the -range, in which the IT of PF is kinetically limited. The amperometric detection of photogenerated products followed the same pattern as the photocurrent in the total current.
在水相LiCl溶液与1,2 - 二氯乙烷中的双（三苯基磷亚基）铵四（五氟苯基）硼酸盐（BATB）之间的液 - 液（L/L）界面上，自发吸附的超支化半导体BiVO颗粒表面研究了离子转移对光致电子转移（ET）反应的影响。有机电解质中添加了Co(bpy)，以便在形成相应的Co(II)络合物的情况下从BiVO接受光激发电子。L/L界面在微量移液器（MP）的孔口处稳定，并通过在可见光（λ>420 nm）间歇照射下，在电解质溶液中的两个参比电极之间施加伽伐尼电位差，记录离子转移循环伏安法（ITCV）。光生空穴导致水氧化为O。在面向MP孔口的有机或水相电解质中的安培微电极（ME）上，在恒定条件下检测到Co(II)和O。总电流仅在PF的IT受到动力学限制的范围内表现出光电流。光生产物的安培检测遵循与总电流中的光电流相同的模式。
