Highly Dispersed Pt Clusters on F-Doped Tin(IV) Oxide Aerogel Matrix: An Ultra-Robust Hybrid Catalyst for Enhanced Hydrogen Evolution.

Dispersing the minuscule mass loading without hampering the high catalytic activity and long-term stability of a noble metal catalyst results in its ultimate efficacy for the electrochemical hydrogen evolution reaction (HER). Despite being the most efficient HER catalyst, the use of Pt is curtailed due to its scarcity and tendency to leach out in the harsh electrochemical reaction environment. In this study, we combined F-doped tin(IV) oxide (F-SnO) aerogel with Pt catalyst to prevent metallic corrosion and to achieve abundant Pt active sites (approximately 5 nm clusters) with large specific surface area (321 cm·g). With nanoscopic Pt loading inside the SnO aerogel matrix, the as-synthesized hybrid F-SnO@Pt possesses a large specific surface area and high porosity and, thus, exhibits efficient experimental and intrinsic HER activity (a low overpotential of 42 mV at 10 mA·cm in 0.5 M sulfuric acid), a 22-times larger turnover frequency (11.2 H·s) than that of Pt/C at 50 mV, and excellent robustness over 10,000 cyclic voltammetry cycles. The existing metal support interaction and strong intermolecular forces between Pt and F-SnO account for the catalytic superiority and persistence against corrosion of F-SnO@Pt compared to commercially used Pt/C. Density functional theory analysis suggests that hybridization between the Pt and F-SnO orbitals enhances intermediate hydrogen atom (H*) adsorption at their interface, which improves the reaction kinetics.