期刊
CHEMPLUSCHEM
卷 81, 期 10, 页码 1116-1122出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cplu.201600288
关键词
artificial photosynthesis; interfacial charge transfer; TiO2 photoanodes; water oxidation; water splitting
资金
- JST PRESTO program
- JSPS KAKENHI [24107003, 24350028]
- JSPS
- Grants-in-Aid for Scientific Research [24107003, 16K04885] Funding Source: KAKEN
Polychromium-oxo-deposited TiO2 ((CrxOy)-O-III/TiO2) electrodes were fabricated by a simple electrochemical technique by using different TiO2 basal electrodes (anatase, rutile, and mixed polymorphic phases P25) as earth-abundant photoanodes for visible-light-driven water oxidation. The high-resolution transmission electron microscopy (HR-TEM) observation illustrated that an (CrxOy)-O-III layer with approximately 2-3nm thickness was formed on the surface of the crystalline TiO2 particles. Upon visible-light irradiation of the electrodes, the photoanodic current based on water oxidation was generated at the (CrxOy)-O-III/TiO2 electrodes. However, the wavelength (below 620nm) for photocurrent generation at (CrxOy)-O-III/TiO2-rutile was longer than that (below 560nm) at (CrxOy)-O-III/TiO2-P25 by 60nm, which is in agreement with the difference (0.2eV) in the conduction band (CB) edge energy between rutile and anatase TiO2. This gives a quantitative account for the photocurrent generation based on interfacial charge transfer (IFCT) from Cr3d of the deposited (CrxOy)-O-III layer to the TiO2 CB. The photocurrent generated for (CrxOy)-O-III/TiO2-rutile was higher than that for (CrxOy)-O-III/TiO2-anatase, which is ascribed to 1)more effective (CrxOy)-O-III deposition on the rutile particles, 2)a larger electrolyte/(CrxOy)-O-III interface for water oxidation as a result of smaller rutile particles (ca. 30-40nm) compared with larger P25 particles (ca. 40-80nm), and 3)more effective use of visible light owing to the low energy IFCT transition of rutile.
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