Anchoring highly surface-exposed Pt single atoms on Ni3S2/Co9S8 with abundant S vacancies triggers d-orbital electron rearrangements for boosted seawater hydrogen evolution

Improving the Pt atoms utilization efficiency on self-supported electrodes is crucial for industrial seawater hydrogen production, but effective strategies are still lacking. Herein, we reported a novel strategy to anchor highly surface-exposed Pt single atoms on Ni3S2/Co9S8 with abundant S vacancies (Pt–Ni3S2/Co9S8–Sv) as a self-supported electrode. Physical characterizations and theoretical calculations confirm that the strong Pt–S electron bridges with the coordinating role of surface S vacancies triggers the d-orbital electron rearrangements and regulates the local electron structures between the Co/Ni and Pt sites. Notably, the Pt–Ni3S2/Co9S8–Sv electrode displays an ultralow overpotential of 18 mV at 10 mA cm−2 in alkaline seawater. More importantly, our Pt–Ni3S2/Co9S8–Sv electrode assembled into an alkaline electrolysis cell can work continuously for 50 h under alkaline seawater @ 60 °C. This work provides a promising strategy for designing highly surface-exposed single-atomic catalyst for large-scale hydrogen evolution through seawater electrolysis. [Display omitted] •Highly surface-exposed Pt SAs on Ni3S2/Co9S8 with abundant S vacancies trigger d-orbital electron rearrangements.•The coordinating role of surface S vacancies regulate local electron structures between the Co/Ni and Pt sites.•Pt–Ni3S2/Co9S8–Sv exhibits the boosted seawater hydrogen evolution.•Self-supported electrode achieves the ultrahigh Pt atoms utilization efficiency.•Pt–Ni3S2/Co9S8–Sv assembled into industrial AEC can work continuously under actual seawater conditions.