Photocatalytic degradation of N-heterocyclic aromatics—effects of number and position of nitrogen atoms in the ring

This study demonstrates the influences of position, number of nitrogen (N) atoms and –C–N– or –N=N– linkage present in the six membered heterocyclic compounds such as pyridine, pyrazine, and pyridazine on their photocatalytic degradation by Au, Ag, and Fe⁺² deposited TiO₂ photocatalyst. The photodegradation rate of these heterocyclic compounds follow the order pyridine > pyrazine > pyridazine due to the different extent of hydroxylation and difference in position and number of N atoms in the aromatic moiety. The Au photodeposition significantly improved the TiO₂ photoactivity as compared to Ag and Fe⁺² loading. The presence of two N atoms in pyrazine and pyridazine as compared to one N atom in pyridine hamper the nucleophilc attack of OH radicals in comparison to easy hydroxylation of pyridine ring. There is 1 N atom, 4C–C, 1C–N and 1C=N bond in pyridine, 2 N atoms in the 1 and 4 positions, 2C–C, 2C–N bonds and 2C=N bonds in pyrazine, and pyridazine ring contains 2 N atoms in the 1 and 2 positions, 3C–C, 1N–N bond and 2C=N bonds. The bond strength/energy decreases gradually as: C=N– (615 KJ/mol)?>?–N=N– (418 KJ/mol)?>?–C–C– (347 KJ/mol)?>?–C–N– (305 KJ/mol)?>?–N–N– (163 KJ/mol). As pyridine has 1C–N, 1C=N, and no N–N bond, it photodegrades easily as compared to 1 N–N and 2C=N bonds of pyridazine of lowest photodecomposition rate. The improved photoactivity of Au–TiO₂ is explained on the basis of its favorable redox potential, work function, and electron-capturing capacity, etc.