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 (F_V) 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/(g_cat∙h) under simulated sunlight while nearly 6.22 μmol/(g_cat∙h) under NIR light. Current study offers a promising and sustainable strategy for the fixation of atmospheric N₂ using full-spectrum solar energy.

太阳能驱动的氮 (N ₂ ) 固定以合成氨是传统 Haber-Bosch 方法满足工业需求的潜在替代方案，但在很大程度上受到太阳能收集和活化惰性 N ₂的困难的阻碍。本工作采用微波水热法制备了共掺杂活化剂Tm ³⁺和敏化剂Yb ³⁺ (Yb ³⁺ :Tm ³⁺ :CeF _{3 )的空心CeF 3纳米球。}通过调节Ce ³⁺ :Yb ³⁺ :Tm ³⁺的摩尔比，将该产物用作光驱动N _{2固定的催化剂}. 结果表明，多孔中空结构通过物理散射和反射增强了光的捕获能力。此外，杂原子掺杂产生大量氟空位（F _{V ），为N 2}的吸附和活化提供了丰富的活性位点。_{CeF 3} :Yb ³⁺ :Tm ³⁺摩尔比为178:20:2 的样品展示了太阳能的最高利用率，这归因于近红外 (NIR) 光到可见光和紫外 (UV) 的最强上转换能力光照下，NH ₄ ⁺浓度在模拟日光下达到最高值15.06 μmol/(g _cat ∙h)，接近6.22 μmol/(g _cat∙h) 在近红外光下。目前的研究为使用全光谱太阳能固定大气中的 N ₂提供了一种有前途且可持续的策略。