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The photocatalytically driven removal of eco-persistent 4-chlorophenol from water using ZnO is reported here. Kinetic dependence of transformation rate on operating variables such as initial 4-chlorophenol concentration and photocatalyst doses was investigated. A complete degradation of 4-chlorophenol at 50 mg L(-1) levels was realised in 3h. Analytical profiles on 4-chlorophenol transformation were consistent with the best-line fit of the pseudo zero-order kinetics. The addition of small amounts of inorganic anions as SO(4)(2-), HPO(4)(-), S(2)O(8)(2-) and Cl(-) revealed two anion types: active site blockers and rate enhancers. Fortunately, Cl(-) and SO(4)(2-) commonly encountered in contaminated waters enhanced the rate of 4-chlorophenol degradation. The reaction intermediates and route to 4-chlorophenol mineralisation were elucidated by combined RP-HPLC and GC-MS methods. In addition to previously reported pathway products of 4-chlorophenol photo-oxidation catechol was detected. A radical mechanism involving o-hydroxylation is proposed to account for the formation of catechol.

2,4,6-trichlorophenol is an important water pollutant owing to the severity of its toxicity. The aqueous phase photocatalytic oxidation of 2,4,6-trichlorophenol over ZnO was investigated as a potential method for the abatement of this pollutant. The effects of operating parameters such as initial ZnO doses and substrate concentration on the removal of 2,4,6-trichlorophenol were studied and optimised at 0.75 g L− 1 and 50 mg L− 1, respectively. The photocatalytic system afforded the highest degradation efficiency at neutral pH. The decomposition of 2,4,6trichlorophenol by the photoprocess agreed satisfactorily with pseudo zero-order kinetic model. The effect of the presence of SO42−, S2O82−, HPO42− and Cl− on the 2,4,6trichlorophenol removal rate was for the first time revealed. Some hitherto unreported pathway intermediates of ZnO-assisted 2,4,6-trichlorophenol degradation were recorded using gas chromatography-mass spectrometry (GC-MS) and high performance liquid chromatography (HPLC). A tentative reaction mechanism for the formation of these intermediates was proposed.