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Abstract: We report on the kinetics of photoelectrochemical oxidation of salicylic acid (SA) and salicylaldehyde (SH) on titanium dioxide nanotube arrays. The TiO2 nanotubes were prepared by the electrochemical oxidation of titanium substrates in a nonaqueous electrolyte (DMSO/HF). Scanning electron microscopy (SEM) was employed to examine the morphology of the formed nanotubes. Linear voltammetry was used to study the electrochemical and photoelectrochemical behavior of the synthesized TiO2 nanotube arrays. The photoelectrochemical oxidation of SA and SH on the TiO2 nanotubes was monitored by in situ UV–vis spectroscopy, showing that the kinetics of the photoelectrochemical oxidation of SA and SH follows pseudo first-order and that the rate constant of SH oxidation is 1.5 times larger than that of SA degradation. Quantum chemical calculations based on the DFT method were performed on SA and SH to address the large difference in kinetics. The relatively higher E LUMO − E HOMO makes SA more stable and thus more difficult to be oxidized photoelectrochemically. The impact of temperature and initial concentrations on the kinetics of SA and SH photoelectrochemical degradation was also investigated in the present work. [Copyright &y& Elsevier]