The production of chlorine and hypochlorite is of great economical and technological interest due to their largescale use in many kinds of commercial applications. Yet, the current processes are not without problems such as inevitable side reactions and the high cost of production. This work reports the photoelectrocatalytic oxidation of chloride ions to free chlorine as it has been investigated by using titanium dioxide (TiO 2 ) and several metaldoped titanium dioxide (M-TiO 2 ) material electrodes. An average concentration of 800 mg L -1 of free chlorine was obtained in an open-air reactor using a TiO 2 thin-film electrode biased at +1.0 V (SCE) and illuminated by UV light. The M-doped electrodes have performed poorly compared with the pure TiO 2 counterpart. Test solutions containing 0.05 mol L -1 NaCl pH 2.0-4.0 were found to be the best conditions for fast production of free chlorine. A complete investigation of all parameters that influence the global process of chlorine production by the photoelectrocatalytic method such as applied potential, concentration of NaCl, pH solution, and time is presented in detail. In addition, photocurrent vs potential curves and the reaction order are also discussed.
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