Energy diagram analysis of photoelectrochemical water splitting process

Photoelectrochemical (PEC) water splitting process is thoroughly revisited based on the energy diagram to elucidate the experimental observations. The TiO2 nanorod structure is studied as the model system for the photoanode of the PEC cell due to its stability in both acidic and basic solutions. The photocurrents with the external bias are examined under the various electrolytes of H2SO4, NaCl, and NaOH. The energy diagrams of the whole PEC system related to the water splitting process are interactively constructed in three-electrode configuration with the vacuum level as the common reference. Electrode potentials and photocurrents measured with the external bias in dark and under light are systematically correlated with the energy diagram of the PEC system. The pH dependent flat-band potential is explained by applying the pH dependent Helmholtz layer potential at the interface. In addition, the distribution of the applied potential in the PEC system during the water splitting process is understood by in-depth understanding of the energy band diagram.