Liquid|Liquid Interfacial Photoelectrochemistry of Chromoionophore I Immobilised in 4-(3-Phenylpropyl)Pyridine Microdroplets
Liquid|Liquid Interfacial Photoelectrochemistry of Chromoionophore I Immobilised in 4-(3-Phenylpropyl)Pyridine Microdroplets
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DOI：
10.1002/celc.201300090
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发表时间：
2014-02
期刊：
影响因子：
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通讯作者：
T. R. Bartlett;Safeer Ahmed;F. Tuna;D. Collison;G. Blanchard;F. Marken
中科院分区：
文献类型：
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作者：
T. R. Bartlett;Safeer Ahmed;F. Tuna;D. Collison;G. Blanchard;F. Marken
研究了色离子载体I（ETH 5294）溶于4-（3-苯基丙基）吡啶（PPP）中，以微滴阵列形式（通过乙腈溶液蒸发沉积）沉积在直径为5 mm的基底平面热解石墨（BPPG）电极上的光电化学过程.稳定的双相暗伏安响应（两个电子/两个质子）中观察到的磷酸盐缓冲溶液（从pH 2至12）与开关的反应性在pH 5由于一个双相质子化步骤。在pH 2的光电化学活性进一步研究了光瞬态电流法。质子化的色离子载体I被证明是光敏组分（由EPR数据支持）和液体中的“空穴传输”|液体界面的含水草酸盐被证明。这种界面空穴转移过程可以被疏水阴离子（PF 6 −）“关闭”，它们与阳离子液体竞争。|液体PPP表面结合位点。光捕获和液体半导体性能的影响进行了讨论。
Photoelectrochemical processes are investigated for chromoionophore I (ETH 5294) dissolved in 4-(3-phenylpropyl)pyridine (PPP) and deposited in the form of a microdroplet array (through evaporation deposition from a solution in acetonitrile) onto a 5 mm diameter basal plane pyrolytic graphite (BPPG) electrode. Stable biphasic dark voltammetric responses (two electron/two proton) are observed in phosphate buffer solution (from pH 2 to 12) with a switch in reactivity at pH 5 due to a biphasic protonation step. The photoelectrochemical activity at pH 2 is investigated further by phototransient amperometry. The protonated chromoionophore I is shown to be the photoactive component (supported by EPR data) and “hole transfer” at the liquid|liquid interface to aqueous oxalate is demonstrated. This interfacial hole-transfer process can be “switched off” by hydrophobic anions (PF6−), which compete for cationic liquid|liquid PPP surface binding sites. Implications for light harvesting and liquid semiconductor properties are discussed.