Synergistic Effects of Organic Ligands and Visible Light on the Reductive Dissolution of CeO Nanoparticles: Mechanisms and Implications for the Transformation in Plant Surroundings.

Cerium oxide (CeO) nanoparticles are one of the most important engineered nanomaterials with demonstrated applications in industry. Although numerous studies have reported the plant uptake of CeO, its fate and transformation pathways and mechanisms in plant-related conditions are still not well understood. This study investigated the stability of CeO in the presence of organic ligands (maleic and citric acid) and light irradiation. For the first time, we found that organic ligands and visible light had a synergistic effect on the reductive dissolution of CeO with up to 30% Ce releases after 3 days, which is the highest release reported so far under environmental conditions. Moreover, the photoinduced dissolution of CeO in the presence of citrate was much higher than that in maleate, which are adsorbed on the surface of CeO through inner-sphere and outer-sphere complexation, respectively. A novel ligand-dependent photodissolution mechanism was proposed and highlighted: upon electron-hole separation under light irradiation, the inner-sphere complexed citrate is more capable of consuming the hole, prolonging the life of electrons for the reduction of Ce(IV) to Ce(III). Finally, reoxidation of Ce(III) by oxygen was observed and discussed. This comprehensive work advances our knowledge of the fate and transformation of CeO in plant surroundings.