Robust and electronically conductive catalyst attachment has presented a formidable challenge to photoelectrochemical silicon devices. Delicate control of the electronic interface is critical for limiting dark current and maximizing attainable photovoltage. Redox polymers have historically been utilized as tunable mediator layers for heterogeneously catalyzed photoelectrochemical hydrogen evolution devices, however they have served limited role in photoelectrochemical CO<sub>2</sub> reduction systems. We demonstrate a system in which viologen based redox polymers are used as mediator layers for CO2 reduction catalysts on silicon electrodes. This design allows for photoelectrochemical CO2 reduction to CO through both heterogeneous and molecular catalyst attachment.

Photoelectrochemical CO2 reduction on p-silicon via redox polymer mediated catalyst attachment

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