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首页> 外文期刊>Electrocatalysis >Dynamics of the Interaction of Formic Acid with a Polycrystalline Pt Film Electrode: a Time-Resolved ATR-FTIR Spectroscopy Study at Low Potentials and Temperatures
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Dynamics of the Interaction of Formic Acid with a Polycrystalline Pt Film Electrode: a Time-Resolved ATR-FTIR Spectroscopy Study at Low Potentials and Temperatures

机译：多晶PT薄膜电极甲酸相互作用的动态：低电位和温度下的时间分辨ATR-FTIR光谱研究

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摘要

Aiming at more insights into the interaction of formic acid with a Pt electrode, we have studied the dynamics of formic acid interaction with a polycrystalline Pt film electrode in the potential range around the onset of the reaction, from 0.0 to 0.4 V (reversible hydrogen electrode (RHE)), by a combination of electrochemical and in situ IR spectroscopy transient measurements. The measurements were performed under well-defined mass transport conditions; IR spectra were acquired in an attenuated total reflection (ATR) configuration with a time resolution of up to 25 ms (rapid scan mode). To slow down the reaction kinetics and thus stabilize short-living adsorbed intermediates, measurements were performed at ambient and low reaction temperatures (3 degrees C). Kinetic H/D isotope effects, introduced by using deuterated formic acid, were explored to learn more about the contribution of C-H bond splitting in the rate-determining step in formic acid dehydration (COad formation). Rapid scan ATR-FTIRS measurements show no measurable time delay between the appearance of the bands related to adsorbed bridge-bonded formate species and adsorbed CO at higher potentials (> 0.1 V) and no detectable formate signals at low potentials (<= 0.1 V), although COad is still formed even at 0.0 V. Adsorption of HCOOH species at low potentials (0.0-0.1 V-RHE) is indicated by a band developing at around 1720 cm(-1), which is isotope shifted upon deuteration of the C-H bond. Consequences of these and other observations, including the observation of a bell-shaped potential dependence of the initial rate for COad formation in the potential range 0.0-0.4 V or distinct kinetic H/D isotope effects in the rate constants for COad formation, on the mechanistic understanding of the formic acid-Pt interaction are discussed.
机译：旨在更有见解与PT电极的甲酸相互作用，我们研究了在反应开始围绕反应的潜在范围内的甲酸相互作用的动态，0.0至0.4V（可逆氢电极（RHE）），通过电化学和原位IR光谱瞬态测量的组合。测量在明确定义的大规模运输条件下进行;在衰减的全反射（ATR）配置中获得IR光谱，其时间分辨率高达25ms（快速扫描模式）。为了减慢反应动力学，从而稳定短生物吸附的中间体，在环境温度和低反应温度（3℃）下进行测量。通过使用氘代甲酸引入的动力学H / D同位素效应，以了解有关C-H键分裂在甲酸脱水（CoAD形成）中的速率确定步骤中的贡献的更多信息。快速扫描ATR-FTIRS测量显示，在较高电位（> 0.1V）的吸附桥粘结的甲酸盐物质和吸附CO相关的条带的外观之间没有可测量的时间延迟，并且在低电位下没有可检测的甲酸盐信号（<= 0.1V）尽管甚至在0.0V时仍然形成CoAD仍然形成。在低电位（0.0-0.1V-rhe）下的HCOOH物种的吸附是由约1720cm（-1）的带显影，其是同位素在CH的氘移到键。这些和其他观察结果的后果，包括观察钟形势依赖性在0.0-0.4V的潜在范围内的同志形成或不同的动力学H / D同位素效应中的同志常数，在Coad形成的情况下讨论了对甲酸-PT相互作用的机械理解。

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