Long-term solar water and CO₂ splitting with photoelectrochemical BiOI-BiVO₄ tandems

Photoelectrochemical (PEC) devices have been developed for direct solar fuel production but the limited stability of submerged light absorbers can hamper their commercial prospects.^1,2 Here, we demonstrate photocathodes with an operational H₂ evolution activity over weeks, by integrating a BiOI light absorber into a robust, oxide-based architecture with a graphite paste conductive encapsulant. In this case, the activity towards proton and CO₂ reduction is mainly limited by catalyst degradation. We also introduce multiple-pixel devices as an innovative design principle for PEC systems, displaying superior photocurrents, onset biases and stability over corresponding conventional single-pixel devices. Accordingly, PEC tandem devices comprising multiple-pixel BiOI photocathodes and BiVO₄ photoanodes can sustain bias-free water splitting for 240 h, while devices with a Cu₉₂In₈ alloy catalyst demonstrate unassisted syngas production from CO₂.