Upconversion hollow nanospheres CeF3 co-doped with Yb3+ and Tm3+ for photocatalytic nitrogen fixation

Solar driven nitrogen (N2) fixation to synthesize ammonia is a potential alternative for the traditional Haber-Bosch approach to meeting industrial demand, but is largely hampered by the difficulties in the harvesting of solar energy and activating inert N2. In this work, hollow CeF3 nanospheres co-doped with activator Tm3+ and sensitizer Yb3+ (Yb3+:Tm3+:CeF3) were prepared by microwave hydrothermal method. The product was employed as a catalyst for photo-driven N2 fixation by adjusting the molar ratio of Ce3+:Yb3+:Tm3+. Results show that the porous hollow structure enhances the light-harvesting by physical scattering and reflection. In addition, heteroatom doping generates abundant fluorine vacancies (FV) which provide abundant active sites for adsorption and activation of N2. The sample with molar ratio of CeF3:Yb3+:Tm3+ at 178:20:2 demonstrates the highest utilization of solar energy attributed to the strongest upconversion capability of near-infrared (NIR) light to visible and ultraviolet (UV) light, and the NH4+ concentration achieves the highest value of 15.06 μmol/(gcat∙h) under simulated sunlight while nearly 6.22 μmol/(gcat∙h) under NIR light. Current study offers a promising and sustainable strategy for the fixation of atmospheric N2 using full-spectrum solar energy.