▎ 摘　　要

Electro- and photocatalytic hydrogen evolution reaction (e-HER and p-HER) are two promising strategies to produce green hydrogen fuel from water. High intrinsic activity, sufficient active sites, fast charge-transfer capacity, and good optoelectronic properties must be taken into consideration simultaneously in pursuit of an ideal bifunctional catalyst. Here, platinum atomic clusters embedded in defects of TiO2 nanocrystals/graphene nanosheets (Pt-T/G) are reported as a bifunctional catalyst for electro- and photocatalytic hydrogen evolution reaction (e-HER and p-HER). High activity is delivered due to the charge transfer from the other part of the catalyst to the active center (Pt-2-O-4-Ti-x), decreasing the activation energy of the rate-limiting step, which is revealed by synchrotron X-ray absorption spectroscopy, photoelectrochemical measurements, and simulated calculations. In regard to e-HER, it outperforms the commercial 20 wt % Pt/C catalyst by a factor of 17.5 on Pt mass basis, allowing for a 93% reduction in Pt loadings. In regard to p-HER, it achieves photocatalytic efficiency (686.8 mu mol h(-1)) without any attenuation in 9 h.