Coupled Electron- and Ion-Transfer Processes at a Liquid/Liquid Interface Decorated with Photoactive Nanomaterials.

The influence of the ion transfer on photoinduced electron transfer (ET) reactions was studied on the surface of hyperbranched semiconducting BiVO 4 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) 3 ](PF 6 ) 3 to accept photoexcited electrons from BiVO 4 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 Δ o w ϕ ${{\rm{\Delta }}_o^w \varphi }$ 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 2 . Co(II) and O 2 were detected at constant Δ o w ϕ ${{\rm{\Delta }}_o^w \varphi }$ 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 Δ o w ϕ ${{\rm{\Delta }}_o^w \varphi }$ -range, in which the IT of PF 6 - is kinetically limited. The amperometric detection of photogenerated products followed the same pattern as the photocurrent in the total current.