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An orthophosphate semiconductor with photooxidation properties under visible-light irradiation


The search for active semiconductor photocatalysts that directly split water under visible-light irradiation remains one of the most challenging tasks for solar-energy utilization1,2,3,4,5,6. Over the past 30 years, the search for such materials has focused mainly on metal-ion substitution as in In1−xNixTaO4 and (V-,Fe- or Mn-)TiO2 (refs 78), non-metal-ion substitution as in TiO2−xNx and Sm2Ti2O5S2 (refs 910) or solid-solution fabrication as in (Ga1−xZnx)(N1−xOx) and ZnS–CuInS2–AgInS2 (refs 1112). Here we report a new use of Ag3PO4 semiconductor, which can harness visible light to oxidize water as well as decompose organic contaminants in aqueous solution. This suggests its potential as a photofunctional material for both water splitting and waste-water cleaning. More generally, it suggests the incorporation of p block elements and alkali or alkaline earth ions into a simple oxide of narrow bandgap as a strategy to design new photoelectrodes or photocatalysts.

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Figure 1: Crystal structure, particle morphology and optical property of Ag3PO4.
Figure 2: Photooxidation over Ag3PO4 under visible light.
Figure 3: Photoelectrochemistry of Ag3PO4.
Figure 4

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Z.Y. thanks L. Yang and G. Li for their help and stimulating discussions on the experiments and thanks the Japan Society for the Promotion of Science (JSPS) fellowship for financial support. The present research is supported in part by the World Premier International Research Center Initiative on Materials Nanoarchitectonics, MEXT, and the Strategic International Cooperative Program, Japan Science and Technology Agency (JST), Japan. Y.L. and R.L.W. acknowledge financial support from the Australian Research Council (ARC) in the form of ARC Discovery Grants.

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Z.Y. fabricated the samples, designed the study, carried out XRD, SEM, ultraviolet–visible spectra, BET, O2 evolution, quantum yield, organic dyes decomposition, electrochemistry experiments, DFT calculations and related data analysis, and wrote the paper; J.Y. supervised the research work and discussed the results; N.K. carried out the TOC analysis; T.K. offered the BiVO4 samples and carried out the HPLC analysis; S.O. contributed part of the DFT calculations; H.S-W. carried out the 18O isotope analysis; H.Y. directed the electrochemistry experiments; J.C. contributed part of the electrode fabrication; W.L. and Z.L. carried out part of the photocurrent measurement; Y.L. helped with the photoelectrode fabrication; R.L.W. discussed the results and polished the English.

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Correspondence to Jinhua Ye.

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Yi, Z., Ye, J., Kikugawa, N. et al. An orthophosphate semiconductor with photooxidation properties under visible-light irradiation. Nature Mater 9, 559–564 (2010).

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