Bi-containing n-FeWO_4 Thin Films Provide the Largest Photovoltage and Highest Stability for a sub-2 eV Band Gap Photoanode

Photoelectrocatalysis of the oxygen evolution reaction remains a primary challenge for development of tandem-absorber solar fuel generators due to the lack of a photoanode with broad solar spectrum utilization, a large photovoltage, and stable operation. Bismuth vanadate with a 2.4–2.5 eV band gap has shown the most promise becauses its photoactivity down to 0.4 V vs RHE is sufficiently low to couple to a lower-gap photocathode for fuel synthesis. Through development of photoanodes based on the FeWO_4 structure, in particular, Fe-rich variants with addition of about 6% Bi, we demonstrate the same 0.4 V vs RHE turn-on voltage with a 2 eV band gap metal oxide, enabling a 2-fold increase in the device efficiency limit. Combinatorial exploration of materials composition and processing facilitated synthesis of n-type variants of this typical p-type semiconductor that exhibit much higher photoactivity than previous implementations of FeWO_4 in solar photochemistry. The photoanodes are particularly promising for solar fuel applications given their stable operation in acid and base.