Photocatalytic hydrogen evolution from glycerol and water over nickel-hybrid cadmium sulfide quantum dots under visible-light irradiation.

Natural photosynthesis offers the concept of storing sunlight in chemical form as hydrogen (H2), using biomass and water. Herein we describe a robust artificial photocatalyst, nickel-hybrid CdS quantum dots (Nih-CdS QDs) made in situ from nickel salts and CdS QDs stabilized by 3-mercaptopropionic acid, for visible-light-driven H2 evolution from glycerol and water. With visible light irradiation for 20 h, 403.2 μmol of H2 was obtained with a high H2 evolution rate of approximately 74.6 μmol h(-1)  mg(-1) and a high turnover number of 38 405 compared to MPA-CdS QDs (mercaptopropionic-acid-stabilized CdS quantum dots). Compared to CdTe QDs and CdSe QDs, the modified CdS QDs show the greatest affinity toward Ni(2+) ions and the highest activity for H2 evolution. X-ray photoelectron spectroscopy (XPS), inductively-coupled plasma atomic emission spectrometry (ICP-AES), and photophysical studies reveal the chemical nature of the Nih-CdS QDs. Electron paramagnetic resonance (EPR) and terephthalate fluorescence measurements clearly demonstrate water splitting to generate ⋅OH radicals. The detection of DMPO-H and DMPO-C radicals adduct in EPR also indicate that ⋅H radicals and ⋅C radicals are the active species in the catalytic cycle.