Spectral dependencies of the quantum yield of photochemical processes on the surface of nano-/microparticulates of wide-band-gap metal oxides. 1. Theoretical approach

Journal of Physical Chemistry B

Volumn 103, Issue 8, 1999, Pages 1316-1324

  Emeline, Alexei V ^a,b   Ryabchuk, Vladimir K ^b   Serpone, Nick ^a  

^a Gina Cody School of Engineering and Computer Science   (Canada)

^b ST PETERSBURG STATE UNIVERSITY   (Russian Federation)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000053616     PISSN: 15206106     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp984661i     Document Type: Article

References (54)

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45. -4 cm (i.e., 10-1000 nm) the band bending can be neglected in most cases, especially for insulators. In the general case, one would need to consider both diffusion and drift of carriers, which would add a term to the continuity equation (eq 7) to describe the motion of carriers caused by the near-surface electric field. This renders a solution to eq 7 to be a more complex problem, something we are presently working on. In the present instance, initial conditions were established which correspond to the case when the near-surface electric field is negligible (see text).
46. It should be emphasized that eq 16 affords an analysis of both (i) the spectral dependence of the quantum yield of reaction, Φ, on the surface of the photocatalyst specimen of a given size d when the absorption coefficient α changes with the wavelength of the incident light, and separately (ii) the dependence of Φ on d/2L when Φ increases with decreasing d/2L for a given value of the absorption coefficient α. When the size of the photocatalyst specimen is in the quantum-size regime, that is, as d gets very small to nanometer dimensions, Φ should decrease as d/2L decreases. However, in the quantum-size regime, the absorption coefficient α at a given wavelength also changes: it decreases near the absorption threshold, whereas at shorter wavelengths the changes may be different owing to variations in the probabilities of electronic transitions between the valence and conduction bands. This infers that, in general, even the shape of the absorption spectrum may be different in this regime. Hence, changes in the absorption spectrum (α(d)) caused by the quantum-size effect also need to be considered in the estimation of changes in the quantum yield of reaction, Φ. In the present case, the focus is on an analysis of the spectral dependence of Φ for a given specimen for a constant value of d/2L (see item (i) above).
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51. Absorption of light by a solid is said to be intrinsic when light absorption leads to electronic transitions between states of the regular lattice (bulk and surface), hence to transitions between the valence and conduction bands to generate delocalized excitons and/or free electrons and holes. Absorption is said to be extrinsic when light is absorbed by lattice defects, impurities, and irregularities among others. It is worth noting that some confusion may arise with respect to light absorption by surface states, regardless of whether they are regular or irregular. In some cases light absorption by surface states is said to be extrinsic because the surface is always a defect relative to the bulk of the lattice. In the case treated herein, we refer to light absorption by the regular surface as intrinsic surface absorption and light absorption by surface defects as extrinsic surface absorption.
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