Publication date: 21st July 2025
The photoelectrochemical (PEC) reduction of carbon dioxide (CO₂RR) offers a promising strategy for the reduction of greenhouse gas emissions through the generation of valuable chemical fuels. Herein we introduce a versatile 3D-printed photoelectrochemical reactor for CO2 conversion, operating under continuous flow conditions. The modular and compact 3D-printed PEC flow reactor developed includes a back-illuminated Bismuth Vanadate (BiVO₄) photoanode decorated with an electrodeposited cobalt phosphide (CoP) cocatalyst, a proton-exchange membrane, and a Cu-coated GDE as cathode. The system is coupled in line with both a micro gas chromatograph (micro GC) and a benchtop NMR, enabling real-time analysis of gas and liquid products under operating conditions. The system achieves 4.34 mA cm⁻² for PEC water oxidation at 1.75 V, with areas of more than 1 cm2. Integration with a stable copper nanoparticle-coated gas diffusion electrode (Cu/GDE) enabled the simultaneous water oxidation and CO₂ reduction, further increasing the photocurrent to 5.24 mA cm⁻² and effectively driving CO₂RR under continuous flow, demonstrating enhanced performance and operational stability over 100 hours, selectively producing acetate (C₂) and methanol (C₁) from CO₂, with a total Faradaic efficiency of almost 90%. Acetate production reached a maximum FE of 60%, under optimal operation conditions representing competitive performance in comparison to state-of-the-art systems. This work presents a scalable and efficient platform for sustainable fuel production via integrated PEC-EC conversion.
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