Journal
CHEMSUSCHEM
Volume 5, Issue 10, Pages 1926-1934Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cssc.201200254
Keywords
doping; electrochemistry; oxidation; photochemistry; water splitting
Funding
- Hydrogen R&D Center, National Research Foundation of Korea (NRF)
- Ministry of Education Science and Technology [2012-017247]
- Korea Center for Artificial Photosynthesis (KCAP) [NRF-2009-C1AAA001-2009-0093879]
- BK 21 program [R31-30005]
- WCU [R31-30005]
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The visible-light-induced water oxidation ability of metal-ion-doped BiVO4 was investigated and of 12 metal ion dopants tested, only W and Mo dramatically enhanced the water photo-oxidation activity of bare BiVO4; Mo had the highest improvement by a factor of about six. Thus, BiVO4 and W- or Mo-doped (2 atom?%) BiVO4 photoanodes about 1 mu m thick were fabricated onto transparent conducting substrate by a metalorganic 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 (JPH) of about 2.38 mA?cm-2 was achieved for Mo doping followed by W doping (JPH approximate to 1.98 mA?cm-2), whereas undoped BiVO4 gave a JPH value of about 0.42 mA?cm-2. The photoelectrochemical water oxidation activity of W- and Mo-doped BiVO4 photoanodes corresponded to the incident photon to current conversion efficiency of about 35 and 40?% respectively. Electrochemical impedance spectroscopy and MottSchottky analysis indicated a positive flat band shift of about 30 mV, a carrier concentration 1.62 times higher, and a charge-transfer resistance reduced by 34-fold for W- or Mo-doped BiVO4 relative to undoped BiVO4. 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 BiVO4 photoanodes (undoped
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