Electrodeposited Thin Conformal TiO2 Coating Enabling Stable Operation of BiVO4 Photoanodes in Basic Media

Producing hydrogen via solar water splitting using a photoelectrochemical cell (PEC) persists as one of the most exciting research topics in the field of solar fuels. The construction of efficient PECs requires the integration of multiple components including a photoanode, a photocathode, an oxygen evolution catalyst, and a hydrogen evolution catalyst. Therefore, the compatibility and stability of all of these elements in a given operating condition are crucial. When the stability of a semiconductor electrode used as the photoanode or photocathode is limited in an acidic or basic condition which is optimum for the operation of the other components, a thin protective layer has been deposited on the semiconductor surface to prevent its chemical dissolution. Surface coating of a thin and conformal TiO2 layer has been proven to be successful for protecting photoelectrodes since TiO2 is chemically and electrochemically stable in a wide range of pH conditions under both anodic and cathodic conditions. In order to prevent the semiconductor surface from coming into direct contact with the corrosive electrolyte, complete coverage of the photoelectrode with TiO2 is required. At the same time, the TiO2 layer should be thin enough not to interfere with the charge transport properties of the photoelectrode. As a result, atomic layer deposition (ALD) has been the only successful tool used to date to produce an effective protective layer. However, the slow processing time and economic viability of ALD methods motivated us to develop an inexpensive and facile solution-based synthesis method for the deposition of high quality TiO2 coating layers. In this presentation, we report a new electrochemical method to deposit a thin and conformal TiO2 layer on nanoporous BiVO4 that has an intricate, high surface area morphology. BiVO4 is a promising n-type photoanode material with a relatively low bandgap (2.4~2.5 eV). However, its usage has been limited to neutral and mildly basic conditions (pH 5~9) because it is chemically unstable in strongly acidic and basic conditions. Our method allows for the deposition of a 5~6 nm thick TiO2 layer on BiVO4 within 1 min and the resulting BiVO4/TiO2 electrodes exhibit chemical stability in basic solutions (pH 12~13). Sulfite oxidation measurements of BiVO4 and BiVO4/TiO2 electrodes show that the thin TiO2 protective layer does not significantly reduce the hole transfer to the electrolyte. Finally, we demonstrate the photoelectrochemical stability of the BiVO4/TiO2 electrode for photoelectrochemical water oxidation in basic solutions by coupling the BiVO4/TiO2 electrode with appropriate oxygen evolution catalysts.