Photocatalytic and photoelectrochemical water oxidation over metal-doped monoclinic BiVO(4) photoanodes.

ChemSusChem

Department of Chemical Engineering and Division of Advanced Nuclear Engineering, Pohang University of Science and Technology (POSTECH), San 31, Hyoja-dong, Pohang, 790-784, South Korea.

Published: October 2012

The visible-light-induced water oxidation ability of metal-ion-doped BiVO(4) was investigated and of 12 metal ion dopants tested, only W and Mo dramatically enhanced the water photo-oxidation activity of bare BiVO(4); Mo had the highest improvement by a factor of about six. Thus, BiVO(4) and W- or Mo-doped (2 atom %) BiVO(4) photoanodes about 1 μm thick were fabricated onto transparent conducting substrate by a metal-organic decomposition/spin-coating method. Under simulated one sun (air mass 1.5G, 100 mW cm(-2)) and at 1.23 V versus a reversible hydrogen electrode, the highest photocurrent density (J(PH)) of about 2.38 mA cm(-2) was achieved for Mo doping followed by W doping (J(PH) ≈ 1.98 mA cm(-2)), whereas undoped BiVO(4) gave a J(PH) value of about 0.42 mA cm(-2). The photoelectrochemical water oxidation activity of W- and Mo-doped BiVO(4) photoanodes corresponded to the incident photon to current conversion efficiency of about 35 and 40 % respectively. Electrochemical impedance spectroscopy and Mott-Schottky analysis indicated a positive flat band shift of about 30 mV, a carrier concentration 1.6-2 times higher, and a charge-transfer resistance reduced by 3-4-fold for W- or Mo-doped BiVO(4) relative to undoped BiVO(4). Electronic structure calculations revealed that both W and Mo were shallow donors and Mo doping generated superior conductivity to W doping. The photo-oxidation activity of water on BiVO(4) photoanodes (undoped

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http://dx.doi.org/10.1002/cssc.201200254DOI Listing

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