Time-resolved X-ray absorption spectroelectrochemistry of redox active species in solution

Electrochemistry and electrocatalysis have been receiving increased attention recently due to their crucial contribution to electrical-to-chemical conversion systems. We describe here the development and operation of a new spectroelectrochemical transmission cell for time-resolved X-ray absorption spectroscopy of solutions. X-ray absorption spectra were recorded on the ROCK beamline of SOLEIL under constant and scanning potentials. Spectra were recorded at a frequency of 2 Hz during a cyclic voltammetry experiment performed on a 20 mM solution of Fe^IIICl₃·6H₂O at 20 mV s⁻¹ scanning speed. Spectra with good signal-to-noise ratios were obtained when averaging ten spectra over 5 s, corresponding to a 100 mV potential range. A 90% conversion rate from Fe(III) to Fe(II) was spectroscopically demonstrated in cyclic voltammetry mode.