Effect of a Cocatalyst on a Photoanode in Water Splitting: A Study of Scanning Electrochemical Microscopy

With a proper band gap of ∼2.4 eV for solar light absorption and suitable valence band edge position for oxygen evolution, scheelite-monoclinic bismuth vanadate (BiVO₄) has become one of the most attractive photocatalysts for efficient visible-light-driven photoelectrochemical (PEC) water splitting. Several studies have indicated that surface modification of BiVO₄ with a cocatalyst such as NiFe layered double hydroxide (LDH) can significantly increase the PEC water splitting performance of the catalyst. Herein, we experimentally investigated the charge transfer dynamics and charge carrier recombination processes by scanning electrochemical microscopy (SECM) with the feedback mode on the surface of BiVO₄ and BiVO₄/NiFe-LDH as model samples. The ratio of rate constants for photogenerated hole (k_h+⁰) to electron (k_e-⁰) via the photocatalyst of BiVO₄/NiFe-LDH reacting with the redox couple is found to be five times larger than that of BiVO₄ under illumination. In this case, the ratio of the rate constants k_h+⁰/k_e-⁰ stands for the interfacial charge recombination process. This implies the cocatalyst NiFe-LDH suppresses the electron back transfer greatly and finally reduces the surface recombination. Control experiments with cocatalysts CoPi and RuO onto BiVO₄ further verify this conclusion. Therefore, the SECM characterization allows us to make an overall analysis on the function of cocatalysts in the PEC water splitting system.