Photocatalytic hydrogen formation from ammonia and methyl amine in an aqueous suspension of metal-loaded titanium(IV) oxide particles

Photocatalytic hydrogen (H-2) formation from ammonia and methyl amine in aqueous suspensions of metal-loaded titanium(IV) oxide (TiO2) particles was examined under various conditions. Ammonia was decomposed to H-2 and nitrogen (N-2) with a stoichiometric ratio (3:1, 2NH(3) -> 3H(2) + N-2) under a deaerated condition, and side reactions such as deep oxidation of ammonia to nitrite and nitrate did not occur. The rate of H-2 formation drastically changed depending on the co-catalyst loaded on TiO2 particles, kinds of TiO2 samples and pH of the suspension. The effect of the co-catalyst became greater with decrease in hydrogen over-voltage, the value of which was obtained when the co-catalyst metal was used as an electrode. Among the co-catalysts used in this study, platinum showed the greatest effect as a co-catalyst. The largest rate of H-2 evolution was obtained when the photocatalytic reaction was carried out at pH 10.7, and addition of an acid or base to the suspension decreased the reaction rate. Photocatalytic reaction of methyl amine in aqueous suspension of platinized TiO2 particles under a deaerated condition yielded H-2 but did not form N-2. The methyl group of methyl amine was mineralized and the amino group remained as ammonium ion without being decomposed to H-2 and N-2, resulting in storage of carbon as hydrogencarbonate (HCO3-) in the suspension. Photocatalytic reaction of methyl amine under the present conditions was totally expressed as CH3NH2 + 3H(2)O -> 3H(2) + NH4+ + HCO3-. (C) 2011 Elsevier B.V. All rights reserved.