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

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Abstract

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.

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Acknowledgments

We are thankful to Department of Science and Technology, India for partial financial support. JK is highly indebted to Nidhi Gupta, Rupinder Kaur, and Inderpreet Singh for their timely help in HPLC analysis.

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Correspondence to Bonamali Pal.

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Responsible editor: Vinod Kumar Gupta

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Kaur, J., Pal, B. Photocatalytic degradation of N-heterocyclic aromatics—effects of number and position of nitrogen atoms in the ring. Environ Sci Pollut Res 20, 3956–3964 (2013). https://doi.org/10.1007/s11356-012-1313-2

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