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Morphological Dependence of the Thermal and Photochemical Reactions of Acetaldehyde on Anatase TiO2 Nanocrystals

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Size and shape selected anatase TiO2 (A-TiO2) nanocrystals that had either a truncated bipyramidal morphology exposing predominantly (101) facets, or a platelet morphology exposing a high fraction of (001) facets and ranging in size from 10 to 25 nm were used to study the influence of crystallite shape and size on the thermal and photocatalytic reactions of acetaldehyde on TiO2 using temperature-programmed desorption in ultra-high vacuum. The primary thermal reaction pathways on the bipyramidal and platelet nanocrystals were aldol condensation to produce crotonaldehyde and reductive coupling to butene. The platelet morphology, however, exhibited higher thermal activity, which was attributed to the higher fraction of exposed (001) facets. For both morphologies crystallite size was found to be important with smaller nanocrystals favoring butene and larger ones favoring crotonaldehyde. The dependence of the selectivity on crystallite size can be attributed to the populations of planar and edge sites exposed by the nanocrystals. The photocatalytic activity of the nanocrystals was also found to vary with size and shape with the platelets having higher activity for acetaldehyde photo-oxidation than the bipyramidal morphology. For both morphologies, photoactivity also increased as the size of the nanocrystals increased.

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Funding for this study was provided by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Grant No. DEFG02-04ER15605.

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Correspondence to Paul A. Pepin or John M. Vohs.

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Pepin, P.A., Diroll, B.T., Murray, C.B. et al. Morphological Dependence of the Thermal and Photochemical Reactions of Acetaldehyde on Anatase TiO2 Nanocrystals. Top Catal 61, 365–378 (2018).

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  • Anatase
  • TiO2
  • TPD
  • UHV
  • Acetaldehyde
  • Photo-oxidation