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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Kinetics of Electron Transfer and Oxygen Evolution in the Reaction of [Ru(bpy)3]3+ with Colloidal Iridium Oxide
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Kinetics of Electron Transfer and Oxygen Evolution in the Reaction of [Ru(bpy)3]3+ with Colloidal Iridium Oxide

机译：[Ru（bpy）3] 3+与胶态氧化铱反应的电子转移动力学和氧析出

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摘要

The kinetics of electron transfer and oxygen evolution at citrate-stabilized IrO_xcentre notH_2O colloids were studied by time-resolved UV-visible spectrosopy and by steady-state photolysis of [Ru(bpy)_3]~(2+) (bpy=2,2'-bipyridyl) and persulfate in a hexafluorosilicate/bicarbonate buffer.Time-resolved studies of the reaction of [Ru(bpy)_3]~(3+) with these colloids show an initial fast electron transfer,corresponding to oxidation of Ir(III) to Ir(IV).Further oxidation of surface Ir atoms occurs concomitantly with oxygen evolution with a second-order rate constant of 1.3 x 10~6 M~(-1) s~(-1).Both the time-resolved reduction of [Ru(bpy)_3]~(3+) by IrO_xcentre notH_2O and the photocatalytic oxygen evolution under non-light-limited photolysis conditions have a H/D kinetic isotope effect (KIE) of 1.0.This contrasts with significantly higher KIE values for oxygen evolution from molecular cis,cis-[(bpy)_2Ru-(OH_2)]_2O]~(4+) and [(terpy)(H_2O)Mn~(III)(O)_2(OH_2)terpy)]~(3+) water oxidation catalysts.This is consistent with the conclusion that,under the conditions of most photocatalytic experiments (approx10~(-4) M [Ru(bpy)_3]~(2+) concentration),electron transfer from the colloid to the oxidized sensitizer rather than formation of a surface-bound hydroperoxy species is the rate-determining step in photocatalytic oxygen evolution.
机译：通过时间分辨紫外可见光谱和[Ru（bpy）_3]〜（2+）（bpy = 2,2 [Ru（bpy）_3]〜（3+）与这些胶体反应的时间分辨研究显示了初始快速电子转移，与Ir（III）的氧化相对应。'--联吡啶基）和过硫酸盐在六氟硅酸盐/碳酸氢盐缓冲液中。到Ir（IV）。表面Ir原子的进一步氧化与氧的释放同时发生，其二级速率常数为1.3 x 10〜6 M〜（-1）s〜（-1）。 IrO_xcentre notH_2O引起的[Ru（bpy）_3]〜（3+）的变化和非光限制光解条件下的光催化氧释放具有1.0的H / D动力学同位素效应（KIE）。分子顺式[，（bpy）_2Ru-（OH_2）] _ 2O]〜（4+）和[（叔）（H_2O）Mn〜（III）（O）_2（OH_2）氧]的析氧（3+）水氧化催化剂这与以下结论一致：在大多数光催化实验的条件下（约10〜（-4）M [Ru（bpy）_3]〜（2+）浓度），电子从胶体转移到氧化敏化剂形成表面结合的氢过氧物质是光催化氧放出的速率决定步骤。

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