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The dye regeneration in dye-sensitized solar cells (DSSCs) is improved by optimizing the charge separation at the level of the sensitized semiconductor treatment of the mesoporous electrode by TiCl4 that passivates the surface for back electron transfer reactions. The dye-regeneration kinetics is analyzed for DN216- and D358-sensitized porous TiO2 electrodes with and without a TiCl4 treatment by means of scanning electrochemical microscopy (SECM). Different mass transport limitation of the [Co(bpy)3]3+ mediator through the porous electrode is found for the comparison of the structurally similar dyes but cannot be detected for the thin layer introduced by the TiCl4 treatment. Phototransient measurements are conducted directly in the SECM cell without any intermediated sample manipulation. The results from those measurements corroborate the findings from steady state SECM measurements
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