Near-Infrared-Triggered Nitrogen Fixation over Upconversion Nanoparticles Assembled Carbon Nitride Nanotubes with Nitrogen Vacancies

Photocatalytic artificial fixation of N-2 to NH3 occurs over NaYF4:Yb,Tm (NYF) upconversion nanoparticles (NPs) decorated carbon nitride nanotubes with nitrogen vacancies (NYF/NV-CNNTs) in water under near-infrared (NIR) light irradiation. NYF NPs with a particle size of ca. 20 nm were uniformly distributed on the surface of NV-CNNTs. The NYF/NV-CNNTs with 15 wt % NYF exhibited the highest NH3 production yield of 1.72 mmol L-1 g(cat)(-1), corresponding to an apparent quantum efficiency of 0.50% under NIR light illumination, and about three times higher the activity of the bare CNNTs under UV-filtered solar light. N-15 isotope-labeling NMR results confirm that the N source of ammonia originates from the photochemical N-2 reduction. The spectroelectrochemical measurements reveal that NVs can greatly facilitate the photogenerated electron transfer without energy loss, while the presence of NYF NPs shifts both the deep trap state and the edge of conduction band toward a lower potential. Moreover, NYF NPs endow the photocatalyst with a NIR light absorption via the fluorescence resonance energy transfer process, and NVs have the ability to enhance the active sites for a stronger adsorption of N-2 and decrease the surface quenching effect of NYF NPs, which thus can promote the energy migration within the heterojunctions. This work opens the way toward full solar spectrum photocatalysis for sustainable ammonia synthesis under aqueous system.

Automated summary

The photocatalytic artificial fixation of N-2 to NH3 was achieved using NaYF4:Yb,Tm (NYF) upconversion nanoparticles (NPs) decorated carbon nitride nanotubes with nitrogen vacancies (NYF/NV-CNNTs). The mixture containing 15% NYF exhibited the highest NH3 yield under NIR light, with N-15 isotope-labeling NMR results confirming the origin of ammonia. NVs and NYF NPs were found to enhance the photogenerated electron transfer and active sites for N-2 adsorption, respectively.