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The decomposition of ethanol, one of the most important biomass platform molecules, was investigated under green conditions, ambient temperature, atmospheric pressure and air for the synthesis of acetal in the presence of TiO2 activated under UV-A radiation. The impact of ethanol concentration, of the nature of TiO2 (rutile, anatase or mixture), of the photo-deposition of Pt under air or argon were all factors under investigation. Whatever the conditions and the nature of catalyst used, acetaldehyde was initially formed before reacting with ethanol to form acetal, a promising fuel additive. However, the subsequent generation of acetal differs depending on the conditions and the nature of catalyst. In the absence of a noble metal, rutile TiO2 leads to an increase in acetal formation at equivalent acetaldehyde formation. This behavior is discussed considering the acidic and basic properties of rutile and anatase phases together with H+ generated under UV. In the presence of Pt, under air or Ar, the acetal formation begins at a lower concentration of acetaldehyde due to the in-situ photo-deposition of Pt. However, whereas acetal formation is similar for Pt/anatase and Pt/rutile phase under air, under Ar, less acetal is generated on Pt/rutile in agreement with the production of more H2. [ABSTRACT FROM AUTHOR]