In-situ and ex-situ chitosan-silver nanoparticle composite: comparison of storage/release and catalytic properties

In this work storage of silver nanoparticles (Ag NPs) in chitosan gel and its subsequent release for catalytic reduction processes is investigated. The generation of small sized metal nanoparticles which acts as catalyst is prerequisite to progress of a catalytic reaction. We show that Ag NPs extracted from chitosan gel are less than 5 nm so very effective in catalysis. Chitosan-Ag nanocomposite gels were prepared from two different approaches. The first approach involves in-situ incorporation of Ag nanoparticles into the reaction mixture while preparing the chitosan hydrogel and termed as chitosan-Ag-in-situ (CH-Ag-I) nanocomposite gel. And, in second approach already prepared chitosan hydrogel was placed in Ag NPs solutions, resulting in adsorption of Ag NPs and thus forming chitosan-Ag-ex-situ (CH-Ag-E) nanocomposite gel. The prepared gels were characterized by UV-Visible spectroscopy, Fourier transformed infra-red spectroscopy (FTIR), Thermogravimetric analysis (TGA) and Scanning electron microscopy (SEM). Swelling studies showed that the CH-Ag-E exhibits efficient water absorption property compared to that of CH-Ag-I. In addition to efficient swelling properties the CH-Ag-E can also act as store house of Ag NPs that can be used to catalyze the reduction of 4-Nitrophenol (4-NP) to 4-Aminophenol (4-AP) as Ag NPs of this composite can be easily extracted just by treating with sodium borohydride which is not possible in case of CH-Ag-I. The rate of the reaction increases upto 10 fold when CH-Ag-E nanocomposite gel is used as catalyst in comparison to CH-Ag-I. The reduction reaction catalyzed by such Ag NPs follow zero order kinetics and dependent on the size of the Ag NPs loaded in the gel (CH-Ag-E) as well as on the amount of the gel used. We found that smaller is the size of the loaded Ag NPs in CH-Ag-E, more effective it is in catalyzing the reduction reaction. The CH-Ag-E gel also showed reusability with efficient catalysis.