Intensifying Upconverted Ultraviolet Emission towards Efficient Reactive Oxygen Species Generation

Multiphoton upconversion that can convert near-infrared irradiation into ultraviolet emission offers many unique opportunities for photocatalysis and phototherapy. However, the high-lying excited states of lanthanide emitters are often quenched by the interior lattice defects and deleterious interactions among different lanthanides, resulting in weak ultraviolet emission. Here, we describe a novel excitation energy lock-in approach to boost ultraviolet upconversion emission in a new class of multilayer core-shell nanoparticles with a gadolinium-rich core domain. Remarkably, we observe more than 70-fold enhancements in Gd³⁺ emission from the designed nanoparticles compared with the conventional nanoparticles. Our mechanistic investigation reveals that the combination of energy migration over the core domain and optically inert NaYF₄ interlayer can effectively confine the excitation energy and thus lead to intense multiphoton ultraviolet emission in upconversion nanostructures. We further achieve a 35.6% increase in photocatalytic reactivity and 26.5% in reactive oxygen species production yield in ZnO-coated upconversion nanocomposites under 808-nm excitation. This study provides a new insight to energy transfer mechanism in lanthanide-doped nanoparticles and offers an exciting avenue for exploring novel near-infrared photocatalysts.