A fluorescence XAFS measurement instrument in the soft X-ray region toward observation under operando conditions.

X-ray absorption fine structure (XAFS) measurements are widely used for the analysis of electronic structure. Generally, XAFS in the soft X-ray region is measured under vacuum, but chemical structures under vacuum are typically different from those under operando conditions, where chemical species exhibit their function. Here, we developed an XAFS measurement instrument, as a step toward operando fluorescent, which yields XAFS measurement using synchrotron radiation in the soft X-ray region. We applied this method to analyze the local electronic structure of the sulfur atoms in L-cysteine in different pH solutions. In water at pH 7, the hydrogen atom does not dissociate from the thiol (-SH) group in L-cysteine, which forms a structure surrounded by and interacting with water molecules. The XAFS spectrum of L-cysteine in solution was altered by changing the pH. At pH 9, the hydrogen atom dissociated and a thiolate anion was formed. Although the -SH group was oxidized to SO4 (2-) when L-cysteine was adsorbed on a metal surface and dried, no oxidation was observed in solution. This may be because the water molecules were densely packed and protected the -SH group from oxidation. Our results show that this instrument aimed toward operando fluorescence XAFS measurements in the soft X-ray region is useful for structural analysis of sulfur atoms in organic molecules in air and in solution. The instrument will be applied to the structural analysis of materials containing elements that have absorption edges in soft X-ray region, such as phosphorus and alkali metals (potassium and cesium). It will be also particularly useful for the analysis of samples that are difficult to handle under vacuum and materials that have specific functions in solution.