Platinum single-site catalysts (SSCs) are a promising technology for the production of hydrogen from clean energy sources. They have high activity and maximal platinum-atom utilisation. However, the bonding environment of platinum during operation is poorly understood. In this work, we use operando, synchrotron-X-ray absorption spectroscopy to study the platinum bonding in SSCs. First, we synthesise an atomically dispersed platinum complex with aniline and chloride ligands onto graphene and characterise it with ex-situ electron microscopy, X-ray diffractometry, X-ray photoelectron spectroscopy, X-ray absorption near edge structure spectroscopy (XANES), and extended X-ray absorption fine structure spectroscopy (EXAFS). Then, by operando EXAFS and XANES, we show that as a negatively biased potential is applied, the Pt-N bonds break first followed by the Pt-Cl bonds. The platinum is reduced from platinum(II) to metallic platinum(0) by the onset of the hydrogen-evolution reaction at 0 V. Furthermore, we observe an increase in Pt-Pt bonding, indicating the formation of platinum agglomerates. Together, these results indicate that while aniline is used to prepare platinum SSCs, the single-site complexes are decomposed and platinum agglomerates at operating potentials. This work is an important contribution to the understanding of the bonding environment and the evolution of the molecular structure of platinum complexes in SSCs.
Mechanisms of Hydrogen Evolution Reaction in Two-Dimensional Nitride MXenes Using In Situ X-Ray Absorption Spectroelectrochemistry