Photoinduced absorption spectroscopy (PIAS) study of water and chloride oxidation by a WO3 photoanode in acidic solution

The mechanisms of water and chloride oxidation by a WO3 photoanode are probed by photoinduced absorption spectroscopy (PIAS) coupled with transient photocurrent (TC) measurements. Linear sweep voltammograms (LSVs) and incident photon to current efficiencies (IPCEs) are obtained, in the water oxidation electrolyte (1 M HClO4) and chloride oxidation electrolyte (3.5 M NaCl in 1 M HClO4). Other work shows that the faradaic efficiency of water oxidation to O-2 in 1 M HClO4 is ca. 1.0, and that for chloride oxidation to Cl-2 in 3.5 M NaCl plus 1 M HClO4 is ca. 0.62. The PIAS/TC data reveals a 0.4 order dependency of the rate of water oxidation on the steady state concentration of photogenerated surface holes, [h(s)(+)](ss), and an approximately first order dependency of the rate of chloride oxidation on [h(s)(+)](ss). Associated mechanisms and rate determining steps for water and chloride oxidation at the photoanode surface that account for these reaction orders are proposed.

Automated summary

The mechanisms of water and chloride oxidation by a WO3 photoanode are investigated, revealing the correlation between reaction rates and the concentration of photogenerated surface holes.