Photoinduced Absorption Spectroscopy of CoPi on BiVO₄: The Function of CoPi during Water Oxidation

Abstract

This paper employs photoinduced absorption and electrochemical techniques to analyze the charge carrier dynamics that drive photoelectrochemical water oxidation on bismuth vanadate (BiVO 4 ), both with and without cobalt phosphate (CoPi) co‐catalyst. These results are correlated with spectroelectrochemical measurements of Co II oxidation to Co III in a CoPi/FTO (fluorine doped tin oxide) electrode during dark electrocatalytic water oxidation. Electrocatalytic water oxidation exhibits a non‐linear dependence on Co III density, with a sharp onset at 1 × 10 17 Co III cm −2 . These results are compared quantitatively with the degree of CoPi oxidation observed under conditions of photoinduced water oxidation on CoPi–BiVO 4 photoanodes. For the CoPi–BiVO 4 photoanodes studied herein, ≤5% of water oxidation proceeds from CoPi sites, making the BiVO 4 surface the predominant water oxidation site. This study highlights two key factors that limit the ability of CoPi to improve the catalytic performance of BiVO 4 : 1) the kinetics of hole transfer from the BiVO 4 to the CoPi layer are too slow to effectively compete with direct water oxidation from BiVO 4 ; 2) the slow water oxidation kinetics of CoPi result in a large accumulation of Co III states, causing an increase in recombination. Addressing these factors will be essential for improving the performance of CoPi on photoanodes for solar‐driven water oxidation.