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microcomposite catalyst based on zinc oxide microstructures and silicon was synthesized for heterogeneous catalysis. ZnO microstructures with elements 6 μm in diameter, 15 μm long, were grown on conductive silicon (001) substrates by the vapor phase method. Methyl orange (C14H14N3NaO3S) was selected as an organic dye for testing the photocatalytic and photoelectrocatalytic properties of ZnO microstructures. The sample was placed in an aqueous solution of methyl orange in order to perform a photocatalytic decomposition of the dye. DRT-125 quartz lamp with a radiation power of no more than 26 W was used as the radiation source in the wavelength range from 315 to 400 nm. The sample with the aqueous solution of dye in a standard 3.5 ml quartz quvet was irradiated with the lamp at a distance of 10 cm from it. In order to perform the photoelectrocatalytic decomposition of the dye in the aqueous solution, an electric field of 1.5 V was applied between ZnO/Si and Al electrodes, that were simultaneously irradiated with UV for 5 cycles lasting 20 minutes (100 minutes). The degradation kinetics of the dye was determined by changing its concentration, on the basis of the optical density measurement at the absorption maximum of the dye (465 nm) using a Specord M 40 spectrometer. During the photocatalysis, the concentration of the dye decreased by 41 % in 100 min, and during the photoelectrocatalysis, by 59 % in 100 min. First-order kinetics was used for the kinetic analysis of the catalytic reactions. The reactions rate constants were found to be k = 5.1·10-3 min-1 in the case of the photocatalysis, and k = 8.8 ·10-3 min-1 in the case of the photoelectrocatalysis. The increase in the efficiency of the dye decomposition in the latter case was associated with a more efficient redistribution of charge when voltage (1.5 V) was applied and with a higher amount of hydroxyl radicals on the surface of the catalyst. [ABSTRACT FROM AUTHOR]