Magnetic Silver Nanoparticles Stabilized by Superhydrophilic Polymer Brushes with Exceptional Kinetics and Catalysis

Stimuli-responsive catalysts with exceptional kinetics and complete recoverability for efficient recyclability are essential in, for example, converting pollutants and hazardous organic compounds into less harmful chemicals. Here, we used a novel approach to stabilize silver nanoparticles (NPs) through magneto/hydro-responsive anionic polymer brushes that consist of poly (acrylic acid) (PAA) moieties at the amine functional groups of chitosan. Two types of responsive catalyst systems with variable silver loading (wt.%) of high and low (PAAgCHI/Fe3O4/Ag (H, L)) were prepared. The catalytic activity was evaluated by monitoring the reduction of organic dye compounds, 4-nitrophenol and methyl orange in the presence of NaBH4. The high dispersity and hydrophilic nature of the catalyst provided exceptional kinetics for dye reduction that surpassed previously reported nanocatalysts for organic dye reduction. Dynamic light scattering (DLS) measurements were carried out to study the colloidal stability of the nanocatalysts. The hybrid materials not only showed enhanced colloidal stability due to electrostatic repulsion among adjacent polymer brushes but also offered more rapid kinetics when compared with as-prepared Ag nanoparticles (AgNPs), which results from super-hydrophilicity and easy accumulation/diffusion of dye species within polymer brushes. Such remarkable kinetics, biodegradability, biocompatibility, low cost and facile magnetic recoverability of the Ag nanocatalysts reported here contribute to their ranking among the top catalyst systems reported in the literature. It was observed that the apparent catalytic rate constant for the reduction of methyl orange dye was enhanced, PAAgCHI/Fe3O4/Ag (H) ca. 35-fold and PAAgCHI/Fe3O4/Ag (L) ca. 23-fold, when compared against the as prepared AgNPs. Finally, the regeneration and recyclability of the nanocatalyst systems were studied over 15 consecutive cycles. It was demonstrated that the nanomaterials display excellent recyclability without a notable loss in catalytic activity.