Ultrafine PtRu Alloy Nanoparticles with Tunable Electron Structure by Alloy Effect for Efficient Hydrogen Production Through Seawater Electrolysis

Abstract Platinum (Pt)‐based materials are considered as the most efficient electrocatalysts for the hydrogen evolution reaction (HER), however, reducing the Pt dosage while maintaining a high catalytic efficiency remains a great challenge. In this study, an advanced HER electrocatalyst is designed based on ultrafine 2.64 nm platinum‐ruthenium (PtRu) alloy nanoparticles anchored on porous carbon nanofibers (PCNFs). The experimental and theoretical calculation results show that the synergistic effect between Pt and Ru can not only promote the high dispersion of alloy nanoparticles on PCNFs in the microstructure but also regulate the coordination environment of Pt and Ru in the electronic environment. These combined effects enhance water adsorption, reduce the energy barrier of hydrolysis, and provide a suitable d‐band center for the HER. Consequently, the prepared PtRu/PCNF electrocatalyst exhibits excellent catalytic activity with low Pt and Ru loadings in alkaline and alkaline seawater. The overpotentials at 10 mA cm −2 are 23.1 and 19.5 mV, respectively, with Tafel slopes of 23.5 and 20.7 dec −1 , outperforming commercial Pt/C (20 wt%). This study presents a new type of electrocatalyst for hydrogen production via water and seawater electrolysis.