Optical and electrochemical effects of H 2 and O 2 bubbles at upward-facing Si photoelectrodes
The effects of the size, contact-angle, and coverage of gas bubbles on solar fuels devices were characterized at cm-scale, upward-facing planar and microwire-array Si photoelectrodes in stagnant electrolytes. Experimental measurements were supported by ray-tracing simulations of surface attached gas bubble films. A dilute, redox-active tracer allowed for the quantification of the mass-transport effects of bubble coverage during photoanodic O 2 (g) evolution at upward-facing photoanodes in 1.0 M KOH(aq.). Measurements of the gas coverage at upward-facing p-Si photocathodes in 0.50 M H 2 SO 4 (aq.) allowed for the nucleation rate and contact angle of H 2 (g) bubbles to be evaluated for systems having various surface free energies. Under simulated solar illumination, the rapid departure of small O 2 (g) bubbles produced stable photocurrents at upward-facing oxygen-evolving Si photoanodes and yielded increased mass-transport velocities relative to a stagnant electrolyte, indicating that bubbles can provide a net benefit to the photoelectrochemical performance of an upward-facing photoanode in solar fuels devices.