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首页> 外文期刊>The journal of physical chemistry, B. Condensed matter, materials, surfaces, interfaces & biophysical >Hydroxylamine Electrochemistry at Low-Index Single-Crystal Platinum Electrodes in Acidic Media
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Hydroxylamine Electrochemistry at Low-Index Single-Crystal Platinum Electrodes in Acidic Media

机译：酸性介质中低指数单晶铂电极上的羟胺电化学

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The electrochemistry of hydroxylamine at low-index single-crystal platinum electrodes in acidic media has been studied by voltammetry and in-situ FTIRRAS.Hydroxylamine (HAM) reactivity at platinum is largely controlled by interaction of the other components of the solution or products of the HAM partial oxidation with the electrode surface.Reduction of HAM is a structure-sensitive reaction,at least through the structure sensitivity of the hydrogen adsorption on platinum.No formation of gaseous products was detected in the potential region corresponding to the H_upd region on Pt(lll) and Pt(ll0).Voltammetric and spectroscopic data point to adsorbed nitric oxide (NO) as the main stable intermediate of the HAM oxidation.Being electrochemically stable in a wide potential region between ca.0.5 and 0.8 V,adsorbed NO acts as a poison for further oxidation of HAM.The HAM oxidation to NO appears to be a structure-insensitive process,though somewhat affected by the anion coadsorption.The Tafel slope analysis suggests the second electron transfer to be the rate-determining step in HAM oxidation to adsorbed NO.The mechanism of the HAM oxidation to NOads proposed here is consistent with the mechanism of the NO_(ads) reduction we have proposed elsewhere.Voltammetric data for all three low-index surfaces indicates the possibility of the HAM reduction and oxidation (at moderate potentials) to occur simultaneously.This fact may be tentatively explained by the existence of an intermediate,which appears both in the reduction and oxidation process.Accordingly,the reduction of HAM would be activated by a dehydrogenation step.
机译：通过伏安法和原位FTIRRAS研究了低折射率单晶铂电极在酸性介质中羟胺的电化学反应。在溶液中的其他组分或产物的相互作用很大程度上控制了羟胺（HAM）在铂上的反应性。 HAM在电极表面发生部分氧化.HAM的还原是结构敏感的反应，至少通过氢在铂上的吸附对结构敏感。在对应于Pt（H_upd）的电位区域中未检测到气态产物的形成伏安和光谱数据表明吸附的一氧化氮（NO）是HAM氧化的主要稳定中间体。在约0.5至0.8 V的宽电位区域内电化学稳定时，吸附的NO充当HAM氧化为NO的过程似乎对结构不敏感，尽管它会受到阴离子共吸附的影响。Tafels斜率分析表明第二次电子转移是HAM氧化成吸附NO的决定速率的步骤。本文提出的HAM氧化成NOads的机理与我们在其他地方提出的NO_（ads）还原的机理是一致的。对于所有三个低折射率表面，表明HAM还原和氧化（在中等电势下）同时发生的可能性。这一事实可以用存在于还原和氧化过程中的中间体来临时解释。 HAM的还原将通过脱氢步骤来激活。

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