Self‐Assembly Directed Organization of Nanodiamond During Ionic Liquid Crystalline Polymer Formation

Abstract

The UV-initiated free radical polymerization of a lyotropic mesophase prepared by co-assembly of an aqueous mixture of an ionic liquid (IL) monomer, 3-decyl-1-vinylimidazolium chloride, in a dimethyl sulfoxide dispersion of an IL-monomer nanodiamond conjugate yields a well-ordered 2D hexagonally structured network-polymer composite. The IL monomer is covalently bound to carboxylated detonation diamond via ester-linked 3-decyl-1-vinylimidazolium bromide. Successful preparation of the amphiphile-functionalized nanodiamond is determined by ATR/FT-IR, thermogravimetric analysis, and small-angle X-ray scattering (SAXS). Mesophase and composite structure are evaluated by SAXS, revealing a columnar architecture composed of amphiphilic ionic liquid cylinders containing solvent-rich cores. Self-assembly directed site localization of the nanodiamond positions the particles in the alkyl chain continuum upon polymerization. The composite reversibly swells in ethanol allowing structural variation and modulation of the nanoparticle internal packing arrangement. This work demonstrates that through careful molecular design, self-organization and site-directed assembly of nanodiamond into chemically distinct regions of a nanostructured organogel can be achieved.

3D Volumetric Structural Hierarchy Induced by Colloidal Polymerization of a Quantum-Dot Ionic Liquid Monomer Conjugate

“…At higher temperatures, a multicomponent transition is observed between 400 and 500 °C. The losses at 298, 419, 445, and 461 °C compare well to that previously reported on nanodiamond (ND) IL monomer copolymers . The emergence of the higher transitions has been previously noted for nanodiamond poly­(IL) composites and attributed to regions of polymer with enhanced thermal stability due to covalently bound NPs acting to hinder thermal degradation .…”

“…The losses at 298, 419, 445, and 461 °C compare well to that previously reported on nanodiamond (ND) IL monomer copolymers. 31 The emergence of the higher transitions has been previously noted for nanodiamond poly(IL) composites and attributed to regions of polymer with enhanced thermal stability due to covalently bound NPs acting to hinder thermal degradation. 31 Lastly, a feature is found above 500 °C, which may signal the onset of QD decomposition.…”

“…Although the change in solution consistency (from liquid to solid) suggests polymerization of the monomer mixture, the success is further verified by ATR/FT-IR spectroscopy (Figure S5, blue). Specifically, the polymerization was monitored by tracking the loss of the vinyl modes located at 1628 cm –1 (ν­(−CC−)), 1407 cm –1 δ­(=CH 2 ), 1294 cm –1 ρ­(=CH), 1084 cm –1 ρ­(=CH 2 ), and 920 cm –1 (C–H bending modes). , Polymerization/cross-linking was deemed complete as evidenced by the disappearance of these bands. Modes confirming retention of the IL monomer conjugate bound to the QD are at 617 cm –1 (ν­(Cd–S)) and 645 cm –1 (ν­(C–S)) .…”

“…Specifically, the polymerization was monitored by tracking the loss of the vinyl modes located at 1628 cm −1 (ν(−CC−)), 1407 cm −1 δ(=CH 2 ), 1294 cm −1 ρ(=CH), 1084 cm −1 ρ(=CH 2 ), and 920 cm −1 (C−H bending modes). 30,31 Polymerization/cross-linking was deemed complete as evidenced by the disappearance of these bands. Modes confirming retention of the IL monomer conjugate bound to the QD are at 617 cm −1 (ν(Cd−S)) and 32 645 cm −1 (ν(C− S)).…”

Nitrogen-doped carbon-coated nanodiamonds for electrocatalytic applications

“…This could be interesting for application in catalysts since those parameters play important roles in the improvement of catalyst reactivity [41]. The modification of NDs with amphiphilic ILs and PILs has been introduced for forming gels [42], removal of environmental pollutions [43], and dynamic tuning properties [44]. However, the ionic conductivity of ILs and PILs cannot enhance the electrical conductivity of insulating NDs, limiting their application in electro-catalysts.…”