Generation of sub-5 nm AuNPs in the special space of the loop-cluster corona of a polymer vesicle: preparation and its unique catalytic performance in the reduction of 4-nitrophenol

Abstract

The hybrid vesicle AuNP@LCCV, in which a large number of AuNPs with an average size of about 2.8 nm were densely and uniformly distributed in an isolated state throughout the corona of the unusual polymer vesicle, was prepared via in situ reduction of Au³⁺ ions, which were encapsulated in advance in the unique polymer vesicle (LCCV) consisting of a hydrophobic membrane of poly(2-phenyl-2-oxazoline) and a hydrophilic loop-cluster corona of polyethyleneimine. The vesicle was formed via self-assembly from a comb-like block copolymer in which a polystyrenic main chain was grafted densely with diblock polyethyleneimine-b-poly(2-phenyl-2-oxazoline) and acted as a reactor for the reduction of Au³⁺. The hybrid vesicle AuNP@LCCV showed powerful catalytic ability in the reduction of nitrophenols (NPs). Interestingly, the reduction reactions of NPs showed a remarkably long induction time, which could be shortened dramatically from 60 min to 1-2 min by greatly increasing the concentration of NaBH₄. It is revealed that the oxygen adsorbed on the AuNPs significantly inhibited the reduction, causing the induction time. Once the oxygen is chemically cleaned from the surface of the AuNPs, the reduction of 4-NP proceeds gradually for a while and then completes suddenly. The reduction mechanism accompanying the oxygen-dependent induction time is proposed from the view of the strong oxygen affinity of the catalyst AuNP@LCCV.