Metal-Organic Framework Membranes Encapsulating Gold Nanoparticles for Direct Plasmonic Photocatalytic Nitrogen...

Photocatalytic nitrogen fixation reaction can harvest the solar energy to convert the abundant but inert N₂ into NH₃. Here, utilizing metal-organic framework (MOF) membranes as the ideal assembly of nanoreactors to disperse and confine gold nanoparticles (AuNPs), we realize the direct plasmonic photocatalytic nitrogen fixation under ambient conditions. Upon visible irradiation, the hot electrons generated on the AuNPs can be directly injected into the N₂ molecules adsorbed on Au surfaces. Such N₂ molecules can be additionally activated by the strong but evanescently localized surface plasmon resonance field, resulting in a supralinear intensity dependence of the ammonia evolution rate with much higher apparent quantum efficiency and lower apparent activation energy under stronger irradiation. Moreover, the gas-permeable Au@MOF membranes, consisting of numerous interconnected nanoreactors, can ensure the dispersity and stability of AuNPs, further facilitate the mass transfer of N₂ molecules and (hydrated) protons, and boost the plasmonic photocatalytic reactions at the designed gas-membrane-solution interface. As a result, an ammonia evolution rate of 18.9 mmol g_Au^-1 h^-1 was achieved under visible light (>400 nm, 100 mW cm^-2) with an apparent quantum efficiency of 1.54% at 520 nm.