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Dye-sensitized photoelectrochemical cell (DS-PEC) is an especially attractive method to generate hydrogen via visible light driven water splitting.Electrolyte,an essential component of DS-PEC,plays a great role in determining the photoactivities of devices for water splitting.When using phosphate buffer (pH =6.4)as electrolyte,the DS-PEC displayed much higher photoactivity than using 0.1 M Na2SO4 (pH =6.4) as electrolyte.The insight is phosphate anion gathers together to form a negative electrostatic field on TiO2 surface,which increases the resistance in the TiO2/catalyst and electrolyte interface and validly reduces the charge recombination from TiO2 to the oxidized catalyst.