Investigation of charge dynamics in dinuclear cobalt phthalocyanine ammonium sulfonate (PDS) modified Ti-Fe2O3 photoanodes for photoelectrochemical water oxidation

The kinetic competition between water oxidation/electron extraction processes and recombination behaviors is a key consideration in the development of efficient photoanodes for solar-driven water splitting. Investigating the photogenerated charge behaviors could guide the construction of high-efficiency photoanodes. In this study, the charge carrier kinetics involved in photoelectrochemical water oxidation of PDS/Ti-Fe2O3 were analyzed using surface photovoltage (SPV), transient photovoltage (TPV), short-pulse transient photocurrent (TPC) and pho-toelectrochemical impedance spectra (PEIS). The TPC results indicate the interfacial electric field introduced by the PDS loading increases the electron extraction and suppresses the bulk recombination, enhancing the spatial separation of photogenerated charges, which is consistent with the SPV and TPV results. Besides, the surface recombination of the back electron (BER) is also attenuated, which enhances the long-lived holes at the surface of PDS/Ti-Fe2O3 photoanode. Similarly, as obtained by PEIS fitting, the loading of PDS accelerates holes transfer at the photoanode/electrolyte interface, and increases the utilization of long-lived holes. In other word, the recombination behaviors of photogenerated charges are restrained both in the bulk and surface of the photoanode after the deposition of PDS, leading to enhanced PEC performance. These findings highlight the importance of understanding charge carrier dynamics in the design of high-efficient photoanodes.