Extraordinarily efficient photocatalytic hydrogen evolution in water using semiconductor nanorods integrated with crystalline Ni2P cocatalystsElectronic supplementary information (ESI) available: Experimental details including nitrogen adsorption-desorption isotherms, SEM images, HRTEM images, additional XPS data of CdS/Ni2P. See DOI: 10.1039/c5ee01310k

Photocatalytic hydrogen evolution via water splitting is an attractive scientific and technological goal to address the increasing global demand for clean energy and to reduce the climate change impact of CO 2 emission. Although tremendous efforts have been made, hydrogen production by a robust and highly efficient system driven by visible light still remains a significant challenge. Herein we report that nickel phosphide, as a cocatalyst to form a well-designed integrated photocatalyst with one-dimensional semiconductor nanorods, highly improves the efficiency and durability for photogeneration of hydrogen in water. The highest rate for hydrogen production reached ∼1200 μmol h −1 mg −1 based on the photocatalyst. The turnover number (TON) reached ∼3 270 000 in 90 hours with a turnover frequency (TOF) of 36 400 for Ni 2 P, and the apparent quantum yield was ∼41% at 450 nm. The photoinduced charge transfer process was further confirmed by steady-state photoluminescence spectra and time-resolved photoluminescence spectra. Such extraordinary performance of a noble-metal-free artificial photosynthetic hydrogen production system has, to our knowledge, not been reported to date. A hybrid structure constructed by uniformly anchoring crystalline Ni 2 P cocatalyst on 1D CdS nanorods exhibits extraordinarily efficient photocatalytic activity for H 2 evolution in water (rate of 1,200 μmol h −1 mg −1 and TOF of 36,400 h −1 per mol Ni 2 P) under visible light irradiation.