▎ 摘　　要

Earth-abundant nickel is a typical non-noble-metal cocatalyst used for photocatalytic hydrogen evolution (PHE). Ni nanoparticles, however, tend to aggregate during the hydrogen production process, significantly lowering their PHE activity. To avoid aggregation, we used single atom form Ni and anchored them on vacancies in nitrogen-doped graphene (Ni-NG) as a cocatalyst for PHE. We demonstrated that Ni-NG is a robust and highly active cocatalyst for PHE from water. With only 0.0013 wt % of Ni loading, the PHE activity of composite Ni-NG/CdS photocatalyst improves by 3.4 times compared to that of NG/CdS, and it does not decay even after 10 rounds of 5-hour running. The quantum efficiency of Ni-NG/CdS for PHE reaches 48.2% at 420 nm, one of the highest efficiencies for non-noble-metal-based cocatalysts reported in the literature. Photoluminescence spectral analyses and electrochemical examinations indicated that Ni-NG coupled to CdS serves not only as an electron storage medium to suppress electronhole recombination but also as an active catalyst for proton reduction reaction. Density functional theory calculations show that the high activity of Ni-NG/CdS composite results from the single Ni atoms trapped in NG vacancies, which significantly reduces the activation energy barrier of the hydrogen evolution reaction. This research may be valuable for developing robust and highly active noble metal free cocatalysts for solar hydrogen production.