NEW PHOTOCATALYTIC APPLICATIONS Roberto Andreozzia; Ilaria Di Sommab; Raffaele Marottaa; Suellen Satyroa; Danilo Spasianoa a Dipartimento di Ingegneria Chimica, dei Materiali e della produzione industriale; Università di Napoli ‘Federico II’; P.le V. Tecchio, 80, 80125, Napoles, Italy b Istituto di Ricerche sulla Combustione (CNR); P.le V. Tecchio, 80, 80125, Napoles, Italy The photocatalytic process can be represented as in the diagram, where A is an electron acceptor (oxidant species) and D is the electron donor (species to be oxidized). The process begins with the absorption of UV radiation by the catalyst and with the formation of an “electron-hole” pair: ππ + − π»ππΆπ ππ½π© + ππͺπ© The high reducing capability of photogenerated electrons allows the reduction of the electron acceptor, that traditionally is represented by dissolved oxygen. In the latter case, the reaction leads to the formation of O2•- radicals: − •− πΆπ + ππͺπ© → πΆπ The positive hole can directly react with dissolved organic substances, water molecules, or OH- ions adsorbed on the catalyst surface. In particular, the last two reactions generate HO• radicals. + − • + + • + π―πΆ + ππ½π© → π―πΆ π―π πΆ + ππ½π© → π―πΆ + π― π« + ππ½π© → π· It is well known that the substitution of oxygen with a species capable of reducing, by trapping the electrons in the conducting band, still enables the oxidation of the organic species present in the solution. Particularly interesting is the case in which oxygen is replaced by a metal ion (Mn+) dissolved in the solution. The latter reduces to a lower oxidation state by capturing the photo-generated electrons on TiO2, whereas the organic species oxidizes, through a direct reaction with the positive holes. In some cases, the reduction of the metal results into its precipitation from the solution thus enabling its separation and recovery. TiO2 Cu(II)aq + BEFORE … TiO2 Cu(0)↓ + Hydrogen production The oxidation of a sacrificial organic species makes possible the continous reduction of cupric ions to zero-valent copper and the formation of hydrogen ions. The latter, in precence of chloride ions, zero-valent copper, and UV solar radiation, reduces to generate hydrogen gas. V. Lanese, D. Spasiano, R. Marotta, I. Di Somma, L. Lisi, S. Cimmino, R. Andreozzi; International Journal of Hydrogen Energy, 2013; DOI: 10.1016/j.ijhydene.2013.05.101 Selective oxidation processes The use of cupric ions instead of oxygen as electron acceptor allows a more selective oxidation of an alcohol (such as benzyl alcohol) into the respective aldehyde, the formation of OH radicals being reduced. Since it is possible to recover the precipitate copper and reoxidize it by air bubbling, its role -considering the whole process - is that of a catalyst. R. Marotta, D. Spasiano, I. Di Somma, R. Andreozzi and V. Caprio; Chemical Engineering Journal, 2012, 209, 69–78. + + D Organic Species + D Oxidized Organic Species AFTER IRRADIATION Treatment of water from soil remediation The oxidation of a sacrificial organic species makes possible the reduction of metal ions which, in some cases (as, for example, cupric ions) may precipitate, thus allowing its recovery from the solution.