Titanium dioxide heterojunction support design induced robust platinum catalytic hydrogen evolution over wide pH range

The development of efficient hydrogen evolution reaction (HER) electrocatalysts is critical for water splitting. Herein, rutile/anatase titanium dioxide heterojunction supported platinum nanoparticles (Pt-NPs) design with interfacial effect was developed as efficient HER catalyst (Pt@R/A-TiO2) over wide pH range. The R/A-TiO2 support design induces aggregated Pt-NPs on the heterojunction interface. In-situ Raman and in-situ infrared investigations over wide pH range reveal that there exists a strong hydrogen spillover from Pt-NPs to R/A-TiO2 support and fast proton transfer HER kinetics on Pt@R/A-TiO2. Theoretical calculations demonstrate that the R/A-TiO2 heterojunction modulates more electrons transferred from TiO2 support to Pt-NPs, and this electron-rich Pt-NPs weakens H adsorption, thus enhancing the hydrogen spillover effect and improving the HER performance of Pt@R/A-TiO2. In acidic/alkaline/neutral media, Pt@R/A-TiO2 demonstrates excellent HER activity and stability. Especially in acidic media, Pt@R/A-TiO2 exhibits high mass activity of 12.57 A mgPt−1 at an overpotential of 100 mV, which is nearly 11 times higher than Pt/C, and outperforms the recently reported Pt-based catalysts as well. This work advances the design of efficient and stable HER catalysts over wide pH range.