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Impact of Aggregate Size and Structure on the Photocatalytic Properties of TiO2 and ZnO Nanoparticles

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Department of Civil and Environmental Engineering, Pratt School of Engineering, Duke University, Durham, North Carolina 27708, United States
*Phone: 919-660-5292; fax: 919-660-5219; e-mail: [email protected]
Cite this: Environ. Sci. Technol. 2012, 46, 13, 6934–6941
Publication Date (Web):January 5, 2012
https://doi.org/10.1021/es202009h
Copyright © 2012 American Chemical Society
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    Aggregation of photocatalytic semiconductors was determined to reduce the generation of free hydroxyl radicals in aqueous suspensions in a fashion dependent on aggregate size and structure. Static light scattering measurements were used to follow temporal changes in the fractal dimension of aggregating TiO2 and ZnO nanoparticles. At length scales comparable to nanoparticle size, the structure of aggregated TiO2 nanoparticles was independent of particle stability and the associated aggregation rate, consistent with the fused nature of TiO2 primary particles in the initial suspension. In contrast, ZnO aggregates were characterized by smaller fractal dimensions when ionic strength, and the resulting aggregation rate, were increased. The photocatalytic activity of ZnO and TiO2 in generating free hydroxyl radicals varied with aggregate structure and size, consistent with theory that predicts reduced reactivity as aggregates become larger and more dense.

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    Changes in Rh over time for TiO2 (Figure S1a) and ZnO (Figure S1b) after the addition of NaCl; changes in EPM as function of NaCl concentrations (Figure S1c); log(I) vs log(q) over time for aggregating TiO2 and ZnO nanoparticles (Figure S2a–e); multiple scattering verification (Figure S3); impact of aggregate size on hydroxyl radical generation in TiO2 (Figure S4a) and ZnO (Figure S4b) suspensions; change in photoabsorbance over time (Figure S5a–e); excitation spectra of UV bulb (Figure S6); model parameter values (Table S1); estimated light intensity for each wavelength (Table S2). This material is available free of charge via the Internet at http://pubs.acs.org.

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