Quantitative In Situ Monitoring of Cu-Atom Release by Cu₂O Nanocatalysts under Photocatalytic CO₂ Reduction Conditions: New Insights into the Photocorrosion Mechanism

Cu₂O is among the most promising photocatalysts for CO₂ reduction, however its photocorrosion remains a standalone challenge. Herein, we present an in situ study of the release of Cu ions from Cu₂O nanocatalysts under photocatalytic conditions in the presence of HCO₃ as a catalytic substrate in H₂O. The Cu-oxide nanomaterials were produced by Flame Spray Pyrolysis (FSP) technology. Using Electron Paramagnetic Resonance (EPR) spectroscopy in tandem with analytical Anodic Stripping Voltammetry (ASV), we monitored in situ the Cu²⁺ atom release from the Cu₂O nanoparticles in comparison with CuO nanoparticles under photocatalytic conditions. Our quantitative, kinetic data show that light has detrimental effect on the photocorrosion of Cu₂O and ensuing Cu²⁺ ion release in the H₂O solution, up to 15.7% of its mass. EPR reveals that HCO₃ acts as a ligand of the Cu²⁺ ions, promoting the liberation of {HCO₃-Cu} complexes in solution from Cu₂O, up to 27% of its mass. HCO₃ alone exerted a marginal effect. XRD data show that under prolonged irradiation, part of Cu²⁺ ions can reprecipitate on the Cu₂O surface, creating a passivating CuO layer that stabilizes the Cu₂O from further photocorrosion. Including isopropanol as a hole scavenger has a drastic effect on the photocorrosion of Cu₂O nanoparticles and suppresses the release of Cu²⁺ ions to the solution. Methodwise, the present data exemplify that EPR and ASV can be useful tools to help quantitatively understand the solid–solution interface photocorrosion phenomena for Cu₂O.