Operando ATR-IR spectroscopy applied to investigate the mechanisms of alternative anodic reactions

电化学反应是高度复杂的过程，需要大量的努力才能深入了解发生在电极上的反应机理。对于多电子转移反应，如醇或氨氧化反应和醇的氧化羰基化反应，尤其如此。为此，建立了一个operando衰减全反射（ATR）红外光谱电池，该电池配备了钻孔电极和其他下游分析技术，如HPLC和GC-MS，用于监测电解质中的反应物。为了获得反应条件下电极表面吸附物的更多信息，电极需要接近ATR-IR装置内反射单元（IRE）处的倏逝波。计划将电催化剂沉积在嵌入式微电极中，该微电极将通过x-y-z系统和力传感器定位在IRE上。为了进一步扩大光谱电化学电池的应用范围，计划用掺杂硼的金刚石包覆钽代替作为电极材料的玻碳，研究有机转化中作为氧化剂的过氧化物的形成。

Electrochemical reactions are highly complex processes requiring extensive efforts to achieve in-depth understanding of the reaction mechanisms occurring at electrodes. This is particularly the case for multi-electron transfer reactions such as alcohol or ammonia oxidation reactions and the oxidative carbonylation reaction of alcohols. For this reason, an operando attenuated total reflection (ATR) infrared spectroscopy cell equipped with a borehole electrode and additional downstream analytical techniques such as HPLC and GC-MS was established for monitoring the reactants in the electrolyte. To gain more information about adsorbates on the electrode surface under reaction conditions, the electrode needs to be approached closely to the evanescent wave at the internal reflection element (IRE) of the ATR-IR set-up. It is planned to deposit the electrocatalysts in recessed microelectrodes, which will be positioned at the IRE by a x-y-z system and a force sensor. To further extend the application range of the spectroelectrochemical cell, glassy carbon used as electrode material is planned to be replaced by tantalum coated with boron-doped diamond to study the formation of peroxides applied as oxidizing agents in organic transformations.