Abstract
Plasmonic Au nanocrystals (NCs) are incorporated into covalent organic frameworks (COFs) with precisely modulated distributions to improve the efficiency of electron-hole separation and optimize the charge-carrier utilization. Specifically, through balancing the rate of dynamic covalent reactions and assembly of NCs, sparsely dispersed Au NCs (AuSP/COFs) or the close packed ones (AuCP/COFs) in COFs are fabricated, in which the contributions of electron acceptors/cocatalysts on the catalytic properties of Au/COFs composites are addressed by EPR, PL, and electrochemical measurements. Au3SP/COFs shows the best photocatalytic performances in photodegradation of RhB (remove >95 % in 120 min, kw=1.8 min−1 g−1) and dehalogenation of phenacyl bromide (conversion >99 %, selectivity of acetophenone ∼92.8 %) under visible light irradiation, which are associated with accelerated electron transfer, increased available Au/COFs Schottky junctions and boosted interfacial reaction kinetics. Overall, this work contributes to the fundamental understanding of the how spatial distributions of NCs in COFs affect the photocatalytic performances.
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