Surface modification of TiO2 with polyaniline (PANI) conducting polymer has been used to achieve visible light photoresponse, thereby increasing solar photocatalytic activity. In this study, photocatalytic performances of PANI-TiO2 composites with different mole ratios were synthesized by the in situ chemical oxidation polymerization method and tested for the degradation of a model refractory organic matter (RfOM), namely humic acid in an aqueous medium under simulated solar irradiation in a comparative manner. Adsorptive interactions under dark conditions and interactions under irradiation were investigated as contributing factors to photocatalysis. Degradation of RfOM was monitored in terms of UV-vis parameters (Color436, UV365, UV280, and UV254) and fluorescence spectroscopic parameters as well as the mineralization extent by dissolved organic carbon contents. The presence of PANI exerted an enhancement in photocatalytic degradation efficiency compared to pristine TiO2. The synergistic effect was more pronounced in lower PANI ratios whereas higher PANI ratios reflected a retardation effect. Degradation kinetics were assessed by pseudo-first-order kinetic model. For all UV-vis parameters analyzed, highest and lowest rate constants (k) were attained in the presence of PT-14 (2.093 × 10-2 to 2.750 × 10-2 min-1) and PT-81 (5.47 × 10-3 to 8.52 × 10-3 min-1), respectively. Variations in selected absorbance quotients, i.e., A254/A436, A280/A436, and A253/A203, were distinctive and compared with respect to irradiation time and photocatalyst type. Upon use of PT-14, a steady decreasing profile with respect to irradiation time was attained for A253/A203 quotient as 0.76-0.61, followed by a rapid decrease to 0.19 in 120 min. The incorporation effect of PANI into TiO2 composite could be visualized in A280/A365 and A254/A365 quotients exhibiting an almost constant and parallel trend. As a general trend, decrease in the major fluorophoric intensity FIsyn,470 with photocatalysis was observed under extended irradiation conditions; however, an abrupt decline was remarkable in the presence of PT-14 and PT-18. Fluorescence intensity decrease correlated well with spectroscopic evaluation of rate constants. A thorough evaluation of spectroscopic parameters of UV-vis and fluorescence can provide significant information for practical applications in control of RfOM in water treatment.
Keywords: Degradation kinetics; PANI-TiO2 composite; Photocatalysis; Refractory organic matter.
© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.