Research into chemical reactions confined to the nano-dimensions has the potential to discover unique means for controlling chemical reactivity. This study is the first attempt to explore the effects of nanoconfinement on the kinetics and mechanism of a broad range of reaction types. The reactions include solid-state and liquid-state intra- and inter- molecular reactions of several dicyanamide salts. FTIR, NMR, pXRD and DSC were employed to analyze the thermally induced reactions of sodium, potassium, ammonium and guanidinium dicyanamide salts in both the bulk and confined to organically modified nanoporous silica. Nanoconfinement did not cause an apparent change in the reaction mechanism but drastically changed the reaction kinetics. This research correlates the change in kinetics to the phase of the reactant and the type of reaction, i.e. solid versus liquid and intermolecular versus intramolecular. This work is especially telling since we are altering the reaction by only changing the cation present between two alkali metals and ammonium based ions. We propose that the increased ordering of solid over liquid is more important for intermolecular than intramolecular transformations.

Novel insights into nanoconfined reactions: Thermally induced transformations of dicyanamide salts

248th National Meeting (2014)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.