Transient Thermal Engineering of Pt@rGO Nanocatalysts via Oxygen Anchoring and Chlorine Coordination for Efficient Hydrogen Generation

The accelerating transition to clean hydrogen energy demands highly efficient and stable platinum-based electrocatalyst for the hydrogen evolution reaction (HER). However, achieving uniform low-Pt-loading catalysts remains challenging due to weak interfacial interactions and inadequate dispersion control. Herein, we developed a synergistic interfacial coordination engineering strategy through integrating freeze-drying with transient non-equilibrium Joule heating, enabling the ultrafast synthesis of uniformly dispersed 1.84 ± 0.58 nm Pt nanoclusters on the reduced graphene oxide (i.e., Pt@rGO-T) within 20 s. Structural characterizations and theoretical calculations reveal that oxygen anchoring sites and chlorine coordination cooperatively strengthen the electron–metal–support interaction and modulate the Pt d-band center, thereby tuning the H* adsorption free energy toward a more favorable, near-thermoneutral range. Notably, this interfacial configuration may promote interfacial modulation and possible H* migration between Pt nanoclusters and the rGO support. As a result, the Pt@rGO-T delivers low overpotentials of 29.6 and 73.0 mV at 10 and 100 mA cm −2 , respectively, along with a high mass activity of 6.23 A mg −1 and excellent durability over 200 h. This transient thermal engineering strategy offers a generalizable pathway for the rational design of interfaces and coordination environments in advanced noble metal-based electrocatalysts.