Search

We report here the highly ordered restacking of the layered phosphatoantimonic dielectric materials H 3(1- x ) M 3 x Sb 3 P 2 O 14 , (where M = Li, Na, K, Rb, Cs and 0 ≤ x ≤ 1), from their nanosheets dispersed in colloidal suspension, induced by a simple pH change using alkaline bases. H 3 Sb 3 P 2 O 14 aqueous suspensions are some of the rare examples of colloidal suspensions based on 2D materials exhibiting a lamellar liquid crystalline phase. Because the lamellar period can reach several hundred nanometers, the suspensions show vivid structural colors and because these colors are sensitive to various chemicals, the suspensions can be used as sensors. The structures of the lamellar liquid crystalline phase and the restacked phase have been studied by X-ray scattering (small and wide angle), which has followed the dependence of the lamellar/restacked phase equilibrium on the cation exchange rate, x . The X-ray diffraction pattern of the restacked phase is almost identical to that of the M 3 Sb 3 P 2 O 14 crystalline phase, showing that the restacking is highly accurate and avoids the turbostratic disorder of the nanosheets classically observed in nanosheet stacking of other 2D materials. Strikingly, the restacking process exhibits features highly reminiscent of a first-order phase transition, with the existence of a phase coexistence region where both ∼1 nm (interlayer spacing of the restacked phase) and ∼120 nm lamellar periods can be observed simultaneously. Furthermore, this first-order phase transition is well described theoretically by incorporating a Lennard-Jones-type lamellar interaction potential into an entropy-based statistical physics model of the lamellar phase of nanosheets. Our work shows that the precise cation exchange produced at room temperature by a classical neutralization reaction using alkaline bases leads to a crystal-like restacking of the exfoliated free Sb 3 P 2 O 14 3- nanosheets from suspension, avoiding the turbostratic disorder typical of van der Waals 2D materials, which is detrimental to the controlled deposition of nanosheets into complex integrated electronic, spintronic, photonic or quantum structures.

Bottom-up strategies for the production of well-defined nanostructures often rely on the self-assembly of anisotropic colloidal particles (nanowires and nanosheets). These building blocks can be obtained by delamination in a solvent of low-dimensionality crystallites. To optimize particle availability, determination of the delamination mechanism and the different organization stages of anisotropic particles in dispersion is essential. We address this fundamental issue by exploiting a recently developed system of fluorohectorite smectite clay mineral that delaminates in water, leading to colloidal dispersions of single-layer, very large (≈20 μm) clay sheets at high dilution. We show that when the clay crystallites are dispersed in water, they swell to form periodic one-dimensional stacks of fluorohectorite sheets with very low volume fraction (<1%) and therefore huge (≈100 nm) periods. Using optical microscopy and synchrotron X-ray scattering, we establish that these colloidal stacks bear strong similarities, yet subtle differences, with a smectic liquid-crystalline phase. Despite the high dilution, the colloidal stacks of sheets, called colloidal accordions, are extremely robust mechanically and can persist for years. Moreover, when subjected to AC electric fields, they rotate as solid bodies, which demonstrates their outstanding internal cohesion. Furthermore, our theoretical model captures the dependence of the stacking period on the dispersion concentration and ionic strength and explains, invoking the Donnan effect, why the colloidal accordions are kinetically stable over years and impervious to shear and Brownian motion. Because our model is not system specific, we expect that similar colloidal accordions frequently appear as an intermediate state during the delamination process of two-dimensional crystals in polar solvents.

Aqueous suspensions of nanosheets are readily obtained by exfoliating low-dimensional mineral compounds like H 3 Sb 3 P 2 O 14 . The nanosheets self-organize, at low concentration, into a periodic stack of membranes, i.e. a lamellar liquid-crystalline phase. Due to the dilution, this stack has a large period of a few hundred nanometres, it behaves as a 1-dimensional photonic material and displays structural colours. We experimentally investigated the dependence of the period on the nanosheet concentration. We theoretically showed that it cannot be explained by the usual DLVO interaction between uniform lamellae but that the particulate nature of nanosheet-laden membranes must be considered. Moreover, we observed that adding small amounts of 100 kDa poly(ethylene oxide) (PEO) decreases the period and allows tuning the colour throughout the visible range. PEO adsorbs on the nanosheets, inducing a strong reduction of the nanosheet charge. This is probably due to the Lewis-base character of the EO units of PEO that become protonated at the low pH of the system, an interpretation supported by theoretical modeling. Oddly enough, adding small amounts of 1 MDa PEO has the opposite effect of increasing the period, suggesting the presence of an additional intermembrane repulsion not yet identified. From an applied perspective, our work shows how the colours of these 1-dimensional photonic materials can easily be tuned not only by varying the nanosheet concentration (which might entail a phase transition) but also by adding PEO. From a theoretical perspective, our approach represents a necessary step towards establishing the phase diagram of aqueous suspensions of charged nanosheets.

Imparting liquid-crystal (LC) materials with the plasmonic properties of metal nanoparticles is actively pursued for applications. We achieved this goal by synthetizing gold nanoparticles onto clay nanosheets, leading to nematic nanocomposite suspensions. Optical observations and structural analysis show the growth of the gold nanoparticles without altering the LC properties of the nanosheets. These colloids display plasmonic structural colours and they can be aligned by an electric field, which is relevant for fundamental and materials chemistry of colloidal LC.

Complex aqueous mixtures comprised of swelling clays and hydrosoluble polymers naturally occur in soils and play a major role in pedogenesis. They are also very often used for formulating oil-well drilling fluids, paints, and personal-care products. The suspensions of some natural clays, thanks to their large nanoparticle aspect ratio, spontaneously form nematic liquid-crystalline phases where the particles align parallel to each other, which affects their flow properties. We observed that adding small amounts of hydrosoluble polymers to these clay suspensions destabilizes the nematic phase with respect to the isotropic (disordered) phase. The polymers that we used (poly(ethylene oxide) and dextran) were too small to adopt particle-bridging conformations and small-angle X-ray scattering experiments showed that the structure of the nematic phase is not altered by polymer doping. However, the adsorption isotherm shows that the macromolecules adsorb onto the clay nanosheets, effectively coating them with a polymer layer. Our extension of Onsager's theory for polymer-coated platelets properly captures the experimental phase diagram and shows how the nematic phase destabilization can be due to the polymer adsorbing more on the platelet faces than at the rim. Because the flow properties of the nematic phase are very different from those of the isotropic phase, the presence or absence of the former phase is an important factor to be determined and considered to explain the rheological behavior of these complex systems.