Enhancing photoelectrochemical CO2 reduction with CuBi2O4-cellulose nanofiber hybrid photocathodes

Abstract

The photoelectrochemical (PEC) conversion of carbon dioxide (CO2) into valuable chemicals and fuels offers a promising strategy to address global challenges such as climate change and glacier retreat. However, developing high-performance photocathodes for the CO2 reduction reaction (CO2RR) is challenging, particularly in optimizing the surface morphology and active site distribution of the electrodes. In this study, we propose a CuBi2O4 (CBO)-based photocathode capable of gas-phase CO2RR through hybridization with cellulose nanofiber (CNF). Our results reveal that the CBO-CNF membrane exhibits inherent hydrophilicity and significantly larger active sites compared to a CBO film prepared with a Nafion binder, leading to reduced charge transfer resistance on the photocathode surface. Moreover, the simultaneous hydrothermal synthesis of the CBO-CNF composite precursor solution effectively inhibits the formation of undesirable CuO nanoparticles on the surface, which would otherwise increase charge transport resistance within the photocathode bulk. Consequently, the CBO-CNF membrane demonstrates superior PEC activities for CO2RR, achieving a photocurrent density of - 5.69 mA/cm2 at - 0.4 VRHE and an onset potential of 0.015 VRHE. Furthermore, the incorporation of CNF improves the long-term PEC stability of the photocathode by promoting charge carrier participation in CO2RR rather than undesired self-reduction reaction. This enhanced stability, coupled with the improved PEC performance, highlights the potential of CNF to replace existing polymer binder materials. These results suggest the feasibility of developing a new type of CBO photocathode with a porous membrane structure suitable for gas-phase PEC cells, marking a significant step forward in PEC technology for CO2 conversion.