Photocatalytic nitrogen fixation over fluoride/attapulgite nanocomposite: Effect of upconversion and fluorine vacancy

Developing cost-effective photocatalyst which converts nitrogen to ammonia under mild conditions remains a great challenge from both academic and industrial perspective. In this work, we synthesize one dimensional attapulgite (ATP) mineral supported Pr3+:CeF3 nanocomposite by a microwave hydrothermal method. Results indicate that adequate doping of Pr3+ facilitates the conversion of visible light into ultraviolet light which expands the adsorption range of solar energy. The abundant fluorine vacancies which generate from the incorporation of partial metal ions of ATP into the crystal lattice of CeF3 act as active sites promoting the adsorption of N-2 as well as weakening the N = N triple bond in the photocatalysis reaction. The 40 wt% loading of Pr3+:CeF3 exhibits the highest photocatalytic nitrogen fixation performance attributed to the formation of Z-scheme structure which not only improves the separation of photoexcited charge carriers, but also preserve the high redox potential to reduce nitrogen. This work provides a sustainable way for nitrogen fixation using solar energy based on natural mineral and beyond.