Operando Thin-Layer ATR-FTIR Spectroelectrochemical Radial Flow Cell with Tilt Correction and Borehole Electrode.

A novel spectroelectrochemical ATR-FTIR thin-film cell was designed and applied to elucidate the intermediates during electrocatalytic alcohol oxidation. In the novel cell design, the working electrode is positioned coplanar above the internal reflection element (IRE) to ensure uniform electrolyte film thickness at reaction conditions. The depletion of the reactant (i.e., ethanol or ethylene glycol in the case of electrocatalytic alcohol oxidation) is decreased by a specifically designed flow-through glassy carbon borehole electrode embedded in PEEK. The electrolyte can be pumped through the disk-shaped gap between the ring working electrode and the IRE into the borehole via an external peristaltic pump. To ensure a radially uniform electrolyte flow, the working electrode and the internal reflection element need to be aligned in parallel at a well-controlled distance, which was achieved by a three-microelectrode-assisted tilt correction. Tilt correction of this four-electrode ensemble and the IRE was performed by three step-motor-driven micrometer screws that allow adjustment of the electrode orientation. The effect of electrolyte pumping through the borehole electrode was analyzed by performing anodic ethanol oxidation using nickel boride as electrocatalyst. The applicability, reliability, and functionality of the cell was further assessed by oxidizing ethylene glycol and determining the reaction products as a function of the electrolyte flow rate. It is found to be essential to induce forced electrolyte convection into the thin electrolyte layer to achieve well-defined steady-state conditions, as mass transport by diffusion is by far insufficient, resulting in reactant depletion, product accumulation, and local pH changes.