Controlling the distribution of nanoparticles in hydrogels via interfacial synthesis

In this article, a dual-solvent method is presented which allows for precise control over the distribution of nanoparticles (NPs) in hydrogels. The technique is based on the interfacial reaction between a reducing agent (herein THPC) initially solubilized in the hydrogel phase, and an organometallic precursor (herein Au(PPh₃)Cl) solubilized in the surrounding organic liquid phase. When the organic phase is completely immiscible with water, the interfacial reaction yields a fragile monolayer film of NPs at the hydrogel surface. Then, the addition of a co-solvent (miscible with both aqueous and organic phases) allows precise tuning over the distribution of NPs, from a fine and well-anchored layer at the interface, to the whole gel volume. As a result, it is possible to independently control the size and concentration of NPs, and their distribution. The impact of such control is demonstrated with the reduction of p-nitrophenol to p-aminophenol catalyzed by gold nanoparticles (AuNPs). When AuNPs are mostly localized at the gel surface, the apparent reaction rate is more than 10× superior compared to AuNPs distributed in the whole gel - at comparable particle content and size. This approach is straightforward, decisive and compatible with broad arrays of NPs and hydrogel chemistries, and solvent combinations.