Adsorption studies of divalent, dinuclear coordination complexes as molecular spacers on SWCNTs.

In order to enhance the electrical energy storage capabilities of nanostructured carbon materials, inter-particle spacer strategies are needed to maintain ion-accessible surface area between the nanoparticles. This paper presents a comparison between different classes of divalent, dinuclear coordination complexes which both show strong adsorption to SWCNTs and have molecular spacer properties that maintain electrochemical activity. We find that a novel, dinuclear zinc hydrazone complex binds as an ion-pair at very high loading while not inducing significant aggregation as compared to our previously studies of dinuclear ruthenium complexes. These conclusions are supported by conductivity and dispersion stability data. Moreover, since zinc is an earth abundant metal, these complexes can be used as components in sustainable energy storage materials. Binding kinetics and binding equilibrium data are presented. Modeling of the adsorption isotherm is best fit with the BET model. Kinetics data support an independent binding model. Preliminary capacitance and membrane resistance data are consistent with the complexes acting as molecular spacers between the SWCNTs in a condensed thin film.

Aggregation kinetics of single-walled carbon nanotubes investigated using mechanically wrapped multinuclear complexes: probing the tube-tube repulsive barrier.

The rational design of supraparticle assemblies requires a detailed understanding of directed assembly processes. The stability of dispersions of nanoscale materials, like single-walled carbon nanotubes (SWCNTs), is still not fully understood, nor are the mechanisms of aggregation and assembly. A detailed balance of attractive van der Waals type interactions with various repulsive barrier mechanisms is needed to control the assembly of industrially viable and functional hybrid-nanoscale supraparticles. We report a detailed study of SWCNT dispersion stability and aggregation kinetics as a function of the nature of the coagulant used in various solvent systems. We explore three classes of coagulants that vary in charge, size, shape, solvation energy, and the ability to bind to the SWCNTs. We use these kinetic data to assess the tube-solvent-coagulant-tube interactions. We compare the relative contributions from two types of repulsive barriers. We find that tube-mediated structured solvent around the SWCNTs does not sufficiently describe our measured kinetic data. A DLVO type, electrical double layer repulsion is used to rationalize our observations. The data presented in this paper require a more detailed theoretical understanding of the physico-chemical environment near nanoparticle surfaces such as aggregating SWCNTs.

Binding of rigid dendritic ruthenium complexes to carbon nanotubes.

Single-walled carbon nanotubes (SWNTs) bind strongly to rigid ruthenium metallodendrimers. High valence ions effectively coagulate these nanotubes from stable dispersions in N,N-dimethylforamide. While ruthenium salts and small [Ru(diimine)(3)](2+) complexes also coagulate the nanotubes, they require much higher concentrations and are easily extracted from the nanotubes with acetonitrile. Enantiomerically pure ruthenium metallodendrimer [Lambda(6)Delta(3)Lambda-Ru(10)](20+)[PF(6)(-)](20) is shown to bind strongly and specifically to the SWNTs. Most of the nanotube's ends are functionalized with this large (5.8 nm), optically active, rigid supramolecular complex. We study the binding capacity with UV-vis and atomic absorption spectroscopy. Imaging the functionalized nanotubes with scanning electron microscopy and atomic force microscopy (AFM) yields direct confirmation of end functionalization. Statistical analysis of the AFM images shows the morphology of the functionalized ends is consistent with the nanotubes binding to one of the endo- or exoreceptors around the dendrimer. Implications of these results toward efficient nanomanufacturing of carbon nanotube devices are discussed.