Comprehensive Study on the Controlled Plasmon-Enhanced Photocatalytic Activity of Hybrid Au/ZnO Systems Mediated by Thermoresponsive Polymer Linkers.

Hybrid semiconductor/noble metal nanostructures coupled with responsive polymers were used to probe unique plasmon-mediated photocatalytic properties associated with swelling-shrinking transitions in polymer chains triggered by specific external stimuli. Poly(N-isopropylacrylamide) (PNIPAM) brushes were anchored on Au films by atom transfer radical polymerization and ZnO nanoparticles were immobilized on the PNIPAM layer to explore controlled photocatalytic activity. The plasmon-enhanced photocatalytic activity was dictated by two critical parameters, that is, grafting density and molecular weight of PNIPAM involved in Au film-PNIPAM-ZnO. The effect of the areal density of PNIPAM chains on the temperature-responsive UV light photocatalytic activities showed mutually antagonistic trends at two different temperatures. The performance at high density was higher above a lower critical solution temperature (LCST), that is, under contracted configuration, while the sample with low density showed higher activity below LCST, that is, extended configuration. Among all the cases explored, the UV light activity was highest for the sample with thin PNIPAM layer and high density above LCST. The visible light activity was induced only for thin PNIPAM layer and high density, and it was higher above LCST. The efficiency of photocatalytic decomposition of phenol pollutant was dramatically enhanced from 10% to 55% upon the increase in temperature under visible light illumination.