Kinetics of temperature-dependent photoinduced redox reactions in a photoelectrochemical cell

The effect of temperature on the electrode kinetics of photovoltage generation in photoelectrochemical (PEC) cells consisting of a phenazine dye-EDTA system, separated from an aqueous solution of an electron acceptor like iodine by a salt bridge has been studied. The phenazine dyes used are phenosafranin, safranin-O, and safranin-T. The maximum photovoltages (V_oc) generated and the sunlight engineering efficiency (SEE) have been found to increase with increasing temperature, but there is a fixed critical temperature for each dye above which the V_oc decreases: 29°C for phenosafranin, 35°C for safranin-T, and 40°C for safranin-O. The photovoltage growth and decay follow the functional forms related to the relaxation times. The rate constants for the forward and backward reactions have been calculated from these relaxation times at different temperatures. The rate of the photoinduced chemical reaction increases with an increase in temperature from 20°C–50°C for all the dyes, with concomitant decrease for the backward reaction. The free energies of electron transfer across the electrode/electrolyte interface have been calculated. The activation energies calculated from the rate constants at different temperatures for phenosafranin-EDTA, safranin-T-EDTA, and safranin-O-EDTA reactions are 5.14, 5.60, and 5.63 kJ mol⁻¹ respectively.