Hydrothermal synthesis of metal nanoparticles@hydrogels and statistical evaluation of reaction conditions' effects on nanoparticle morphologies

We report a facile green hydrothermal synthesis (HTS) of monoliths of hydrogels decorated with noble metal nanoparticles (NPs). The one-pot approach requires solely water, a polysaccharide able to form a hydrogel, and a salt precursor (Mx+-containing) for the metal NPs. The polysaccharide fulfills three roles: (i) it acts as the reducing agent of Mx+ to M0 under hydrothermal conditions, (ii) it stabilizes NPs surfaces, and (iii) it forms a hydrogel scaffold in which the metal NPs are embedded. The NPs’ localization in the hydrogel can be controlled through the gelation mechanism. Specifically, the NPs can either be located on and slightly under the surface of the hydrogel monoliths or in the volume. The former is found when a hydrogel monolith is crosslinked prior to HTS. The latter is observed when the HTS reaction mixture contains a polysaccharide dissolved in H2O, which forms a hydrogel upon cooling. Furthermore, we studied the influence of HTS conditions on NP shapes. To find significant levers towards morphological control, a set of HTS experiments featuring broad ranges of reaction conditions was performed. Subsequently, we employed statistical analyses with multivariate regression fits to evaluate synthesis parameter effects. Thereby, we can link the synthesis parameters of temperature, time, precursor concentration, heating rate, choice of metallic precursor, and type of biopolymer, to morphology descriptors such as diameter, circularity, and polydispersity index. The presented approach is in fine compatible with broad arrays of NPs and can in principle be modified for different chemistries, thereby providing a tool for quantitatively assessing morphological impacts of reaction parameters.