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

摘要

Photocatalytic nitrogen fixation reaction can harvest the solar energy to convert the abundant but inert N_2 into NH_3. 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 N_2 molecules adsorbed on Au surfaces. Such N_2 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 N_2 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.