Investigations of Nanoparticle Suspensions of Prussian Blue and Its Copper Analogue: Amine Functionalization and Electrochemical Studies.

Prussian blue (PB) and its analogues are promising materials for electrochemical energy storage, yet their use in flow-type devices is limited by their lack of redox responsiveness as colloidal suspensions. We have investigated the redox chemistry amine functionalization of PB along with its Cu analogue (CuPBA). No redox response of colloidal PB was observed and suspensions of CuPBA formed films on electrode surfaces with and without applied potentials; the films were redox-active but the material that remained suspended in solution did not participate in redox chemistry. Propylamine (pa), ethylenediamine (en), or tetramethylethylenediamine (TMEDA) were added in an attempt to maintain well dispersed suspensions through nanoparticle surface functionalization. Propylamine modifications resulted in a loss of the CuPBA network and subsequent precipitation of insoluble materials. Coordination of ethylenediamine prompted the formation of Cu and Fe monomers ([Cu(en)2]m+/[Fe(CN)6]n-]) that remained soluble in aqueous electrolytes. In the absence of supporting electrolytes, these monomers formed a one-dimensional (1D) polymeric structure (Cu2Fe-1D). TMEDA modification preserved the CuPBA extended structure with only modest precipitate formation over 30 min. The redox responsiveness of these suspensions depended on conditions; in 1 M KCl, no redox chemistry was observed for the CuPBA. In pH 4 potassium hydrogen phthalate buffer, a signal was observed that was attributed to the Fe centers of CuPBA. Under these conditions, the material precipitated in ∼15 min and the signal was lost. Although the Fe centers in these networks are redox-active, additional work is needed to realize longer-term redox activity and stability. Ligand modifications can alter the properties of these networks but within a given ligand class, e.g., amines, the effects can vary greatly from the deconstruction of the framework to preventing film formation.

Low-Loading Mixed Matrix Materials: Fractal-Like Structure and Peculiarly Enhanced Gas Permeability.

Mixed matrix materials (MMMs) containing metal-organic framework (MOF) nanoparticles are attractive for membrane carbon capture. Particularly, adding <5 mass % MOFs in polymers dramatically increased gas permeability, far surpassing the Maxwell model's prediction. However, no sound mechanisms have been offered to explain this unusual low-loading phenomenon. Herein, we design an ideal series of MMMs containing polyethers (one of the leading polymers for CO2/N2 separation) and discrete metal-organic polyhedra (MOPs) with cage sizes of 2-5 nm. Adding 3 mass % MOP-3 in a polyether increases the CO2 permeability by 100% from 510 to 1000 Barrer at 35 °C because of the increased gas diffusivity. No discernible changes in typical physical properties governing gas transport properties are detected, such as glass transition temperature, fractional free volume, d-spacing, etc. We hypothesize that this behavior is attributed to fractal-like networks formed by highly porous MOPs, and for the first time, we validate this hypothesis using small-angle X-ray scattering analysis.