In Situ EXAFS Study of Mo–P Bond Dynamics in Molybdenum Phosphide during CO ₂ Reduction and Hydrogen Evolution

Transition Metal Phosphides (TMPs) are widely studied as catalysts in reactions like hydrogen evolution, oxygen reduction, and hydrodesulfurization. TMPs have demonstrated remarkable efficiency in accelerating reactions by providing active sites for adsorption and facilitating the transformation of reaction intermediates, a feature that has increased the interest of TMPs in the electrochemical carbon dioxide reduction reaction (eCO2RR). Despite their growing use, the potential-dependent structural behavior of TMPs under operating electrochemical conditions remains insufficiently understood. This work investigates the dynamics of the Mo–P bond during eCO2RR and hydrogen evolution reaction (HER) using in situ extended X-ray absorption spectroscopy (EXAFS) studies at the Mo–K edge. Structural characterization of the synthesized MoP nanoparticles was performed by powder X-ray diffraction (XRD) and transmission electron microscopy (TEM). Results of the overall electrochemical activity of MoP are presented through linear sweep voltammetry (LSV) experiments in the potential range of 0 to −1.5 V versus Ag/AgCl and chronoamperometry (CA). Liquid products were analyzed by 1H NMR spectroscopy. The synthesized catalyst showed increasing activity with the highest Faradaic efficiency of 11.75% for C2+ products at −1.3 V vs Ag/AgCl. In situ EXAFS revealed a change in the average Mo–P bond distance during eCO2RR, whereas no such change was observed during the hydrogen evolution reaction (HER). This finding suggests that phosphorus, particularly through modulation of the Mo–P bond length, plays an important role in the eCO2RR and demonstrates how in situ EXAFS can track local structural perturbations in MoP catalysts during electrochemical operation, providing complementary structural insight that correlates with electrochemical behavior.