Intercalation of CO2 Selected by Type of Interlayer Cation in Dried Synthetic Hectorite.

Clay minerals are abundant in caprock formations for anthropogenic storage sites for CO2, and they are potential capture materials for CO2 postcombustion sequestration. We investigate the response to CO2 exposure of dried fluorohectorite clay intercalated with Li+, Na+, Cs+, Ca2+, and Ba2+. By in situ powder X-ray diffraction, we demonstrate that fluorohectorite with Na+, Cs+, Ca2+, or Ba2+ does not swell in response to CO2 and that Li-fluorohectorite does swell. A linear uptake response is observed for Li-fluorohectorite by gravimetric adsorption, and we relate the adsorption to tightly bound residual water, which exposes adsorption sites within the interlayer. The experimental results are supported by DFT calculations.

Bright, noniridescent structural coloration from clay mineral nanosheet suspensions.

Structural colors originate by constructive interference following reflection and scattering of light from nanostructures with periodicity comparable to visible light wavelengths. Bright and noniridescent structural colorations are highly desirable. Here, we demonstrate that bright noniridescence structural coloration can be easily and rapidly achieved from suspended two-dimensional nanosheets of a clay mineral. We show that brightness is enormously improved by using double clay nanosheets, thus optimizing the clay refractive index that otherwise hampers structural coloration from such systems. Intralayer distances, and thus the structural colors, can be precisely and reproducibly controlled by clay concentration and ionic strength independently, and noniridescence is readily and effortlessly obtained in this system. Embedding such clay-designed nanosheets in recyclable solid matrices could provide tunable vivid coloration and mechanical strength and stability at the same time, thus opening a previously unknown venue for sustainable structural coloration.

CO2 Adsorption Enhanced by Tuning the Layer Charge in a Clay Mineral.

Due to the compact two-dimensional interlayer pore space and the high density of interlayer molecular adsorption sites, clay minerals are competitive adsorption materials for carbon dioxide capture. We demonstrate that with a decreasing interlayer surface charge in a clay mineral, the adsorption capacity for CO2 increases, while the pressure threshold for adsorption and swelling in response to CO2 decreases. Synthetic nickel-exchanged fluorohectorite was investigated with three different layer charges varying from 0.3 to 0.7 per formula unit of Si4O10F2. We associate the mechanism for the higher CO2 adsorption with more accessible space and adsorption sites for CO2 within the interlayers. The low onset pressure for the lower-charge clay is attributed to weaker cohesion due to the attractive electrostatic forces between the layers. The excess adsorption capacity of the clay is measured to be 8.6, 6.5, and 4.5 wt % for the lowest, intermediate, and highest layer charges, respectively. Upon release of CO2, the highest-layer charge clay retains significantly more CO2. This pressure hysteresis is related to the same cohesion mechanism, where CO2 is first released from the edges of the particles thereby closing exit paths and trapping the molecules in the center of the clay particles.

Water Dynamics in Composite Aqueous Suspensions of Cellulose Nanocrystals and a Clay Mineral Studied through Magnetic Resonance Relaxometry.

1H spin-lattice relaxation time (T1) measurements were performed to probe the dynamic behavior of water in aqueous suspensions of cellulose nanocrystals (CNCs) and a layered smectite clay mineral with different degrees of concentration. 1H-T1 experiments were carried out over a wide frequency domain, ranging from a few kilohertz to 500 MHz, with the aid of conventional and fast field cycling nuclear magnetic resonance (NMR) techniques. The experimental relaxometry data illustrate differences between the dynamic behavior of bulk water and that confined in the vicinity of CNC-clay surfaces. Clay alone in moderate concentration was found to enforce almost no effect on the water dynamics, whereas introducing CNCs to the system presented a significantly enhanced relaxivity. The modeling of the relaxation dispersions allowed the determination of dynamical processes and variables explaining the dynamic behavior of water in CNC-clay suspensions. It turned out that reorientations mediated by translational displacements are a leading NMR relaxation mechanism for water interacting with the surfaces of CNC-clay particles in the low-frequency domain. In the high-frequency regime, however, the inner-sphere paramagnetic relaxation mechanism dominates, which is caused by the interaction of water protons with dissolved Fe ions.

Controlled sample environment for studying solid-gas interactions by in situ powder X-ray diffraction.

A sample cell for powder X-ray diffraction studies with in situ applied pressure and control of temperature is demonstrated. The cell is based on a previously reported design and consists of a glass or quartz capillary glued into a Swagelok weld gland; this configuration can hold up to 100 bar (1 bar = 100 kPa). The cell is placed in contact with a copper plate for control of temperature between -30 and 200°C. This is achieved by Peltier elements, heat cartridges and a refrigerated circulating bath. This work mainly focuses on the temperature control system. Commissioning tests were performed in a custom-made small/wide-angle X-ray diffractometer at the Norwegian University of Science and Technology. The system is easily portable to synchrotron facilities.

Unmodified Clay Nanosheets at the Air-Water Interface.

Quasi-two-dimensional (2D) nanolayers, such as graphene oxide or clay layers, adhere to gas-liquid or liquid-liquid interfaces. Particularly, clays are of wide general interest in this context because of their extensive and crucial use as Pickering emulsion stabilizers, as well as for their ability to provide colloidosome capsules. So far, clays could only be localized at oil-water or air-saline-water interfaces in aggregated states, while our results now show that clay nanosheets without any modification can be located at air-deionized-water interfaces. The clay mineral used in the present work is synthetic fluorohectorite with a very high aspect ratio and superior quality in homogeneity and charge distribution compared to other clay minerals. This clay mineral is more suitable for achieving unmodified clay anchoring to fluid interfaces compared to other clay minerals used in previous works. In this context, we studied clay nanosheet organization at the air-water interface by combining different experimental methods: Langmuir-Blodgett trough studies, scanning electron microscopy (SEM) studies of film deposits, grazing-incidence X-ray off-specular scattering (GIXOS), and Brewster angle microscopy (BAM). Clay films formed at the air-water interface could be transferred to solid substrates by the Langmuir-Schaefer method. The BAM results indicate a dynamic equilibrium between clay sheets on the interface and in the subphase. Because of this dynamic equilibrium, the Langmuir monolayer surface pressure does not change significantly when pure clay sheets are spread on the liquid surface. However, also, GIXOS results confirm that there are clay nanosheets at the air-water interface. In addition, we find that clay sheets modified by a branched polymer are much more likely to be confined to the interface.

Clay nanolayer encapsulation, evolving from origins of life to future technologies.

Clays are the siblings of graphite and graphene/graphene-oxide. There are two basic ways of using clays for encapsulation of sub-micron entities such as molecules, droplets, or nanoparticles, which is either by encapsulation in the interlayer space of clay nanolayered stacked particles ("the graphite way"), or by using exfoliated clay nanolayers to wrap entities in packages ("the graphene way"). Clays maybe the prerequisites for life on earth and can also be linked to the natural formation of other two-dimensional materials such as naturally occurring graphite and its allotropes. Here we discuss state-of-the-art in the area of clay-based encapsulation and point to some future scientific directions and technological possibilities that could emerge from research in this area.

A nano-silicate material with exceptional capacity for CO2 capture and storage at room temperature.

In order to mitigate climate change driven by the observed high levels of carbon dioxide (CO2) in the atmosphere, many micro and nano-porous materials are being investigated for CO2 selectivity, capture and storage (CCS) purposes, including zeolites, metal organic frameworks (MOFs), functionalized polymers, activated carbons and nano-silicate clay minerals. Key properties include availability, non-toxicity, low cost, stability, energy of adsorption/desorption, sorbent regeneration, sorption kinetics and CO2 storage capacity. Here, we address the crucial point of the volumetric capture and storage capacity for CO2 in a low cost material which is natural, non-toxic, and stable. We show that the nano-silicate Nickel Fluorohectorite is able to capture 0.79 metric tons of CO2 per m3 of host material - one of the highest capacities ever achieved - and we compare volumetric and gravimetric capacity of the best CO2 sorbent materials reported to date. Our results suggest that the high capture capacity of this fluorohectorite clay is strongly coupled to the type and valence of the interlayer cation (here Ni2+) and the high charge density, which is almost twice that of montmorillonite, resulting in the highest reported CO2 uptake among clay minerals.

Sample cell for studying liquid interfaces with an in situ electric field using X-ray reflectivity and application to clay particles at oil-oil interfaces.

Commissioning results of a liquid sample cell for X-ray reflectivity studies with an in situ applied electrical field are presented. The cell consists of a Plexiglas container with lateral Kapton windows for air-liquid and liquid-liquid interface studies, and was constructed with grooves to accept plate electrodes on the walls parallel to the direction of the beam. Both copper and ITO plate electrodes have been used, the latter being useful for simultaneous optical studies. Commissioning tests were made at the I07 beamline of the Diamond Light Source.

A simple way for targeted delivery of an antibiotic: In vitro evaluation of a nanoclay-based composite.

The sodium-modified form of fluorohectorite nanoclay (NaFh) is introduced as a potential drug carrier, demonstrating its ability for the controlled release of the broad-spectrum antibiotic Ciprofloxacin through in vitro tests. The new clay-drug composite is designed to target the local infections in the large intestine, where it delivers most of the incorporated drug thanks to its pH-sensitive behavior. The composite has been conceived to avoid the use of coating technology and to decrease the side-effects commonly associated to the burst-release of the ciprofloxacin at the stomach level. NaFh was obtained from lithium-fluorohectorite by ion exchange, and its lack of toxicity was demonstrated by in vivo studies. Ciprofloxacin hydrochloride (Cipro) was encapsulated into the clay at different values of the pH, drug initial concentration, temperature and time. Systematic studies by X-ray diffraction (XRD), infrared and visible spectrophotometry (FT-IR and UV-vis), and thermal analysis (TGA) indicated that the NaFh host exhibits a high encapsulation efficiency for Cipro, which reaches a 90% of the initial Cipro in solution at 65 oC, with initial concentration of drug in solution of 1.36 x 10-2 mol L-1 at acid pH. XRD revealed that a true intercalation of Cipro takes place between clay layers. TG showed an increased thermal stability of the drug when intercalated into the clay, as compared to the "free" Cipro. IR suggested a strong clay-Cipro interaction via ketone group, as well as the establishment of hydrogen bonds between the two materials. In vitro drug release tests revealed that NaFh is a potentially efficient carrier to deliver Cipro in the large intestine, where the release process is mediated by more than just one mechanism.

Mechanics of Pickering Drops Probed by Electric Field-Induced Stress.

Fluid drops coated with particles, so-called Pickering drops, play an important role in emulsion and capsule applications. In this context, knowledge of mechanical properties and stability of Pickering drops are essential. Here we prepare Pickering drops via electric field-driven self-assembly. We use direct current (DC) electric fields to induce mechanical stress on these drops, as a possible alternative to the use of, for example, fluid flow fields. Drop deformation is monitored as a function of the applied electric field strength. The deformation of pure silicone oil drops is enhanced when covered by insulating polyethylene (PE) particles, whereas drops covered by conductive clay particles can also change shape from oblate to prolate. We attribute these results to changes in the electric conductivity of the drop interface after adding particles, and have developed a fluid shell description to estimate the conductivity of Pickering particle layers that are assumed to be non-jammed and fluid-like. Retraction experiments in the absence of electric fields are also performed. Particle-covered drops retract slower than particle-free drops, caused by increased viscous dissipation due to the presence of the Pickering particle layer.

Electroformation of Janus and patchy capsules.

Janus and patchy particles have designed heterogeneous surfaces that consist of two or several patches with different materials properties. These particles are emerging as building blocks for a new class of soft matter and functional materials. Here we introduce a route for forming heterogeneous capsules by producing highly ordered jammed colloidal shells of various shapes with domains of controlled size and composition. These structures combine the functionalities offered by Janus or patchy particles, and those given by permeable shells such as colloidosomes. The simple assembly route involves the synergetic action of electro-hydrodynamic flow and electro-coalescence. We demonstrate that the method is robust and straightforwardly extendable to production of multi-patchy capsules. This forms a starting point for producing patchy colloidosomes with domains of anisotropic chemical surface properties, permeability or mixed liquid-solid phase domains, which could be exploited to produce functional emulsions, light and hollow supra-colloidosome structures, or scaffolds.

Oxygen-controlled phase segregation in poly(N-isopropylacrylamide)/laponite nanocomposite hydrogels.

The combination of nanoparticles and polymers into nanocomposite gels has been shown to be a promising route to creating soft materials with new or improved properties. In the present work, we have made use of Laponite nanoparticles in combination with a poly(N-isopropylacrylamide) (PNIPAAM) polymer and describe a phenomenon taking place during the polymerization and gelling of this system. The presence of small amounts of oxygen in the process induces two distinctly separated phases, one polymer-rich and one polymer-deficient water-clay phase. Complex interactions among clay, oxygen, and the polymer are found to govern the behavior of these phases. It is also observed that the initial clay concentration can be used to control the volume fraction of the polymer-deficient phase directly. The dynamics of the phase boundary is found to be dependent on water penetration and in general to exhibit non-Fickian behavior. An approach using video recording to monitor hydrogel swelling is also presented, and its advantages are addressed.

Guided self-assembly of nanostructured titanium oxide.

A series of nanostructured titanium oxide particles were synthesized by a simple wet chemical method and characterized by means of small-angle x-ray scattering (SAXS)/wide-angle x-ray scattering (WAXS), atomic force microscope (AFM), scanning electron microscope (SEM), transmission electron microscope (TEM), thermal analysis, and rheometry. Tetrabutyl titanate (TBT) and ethylene glycol (EG) can be combined to form either TiO(x) nanowires or smooth nanorods, and the molar ratio of TBT:EG determines which of these is obtained. Therefore, TiO(x) nanorods with a highly rough surface can be obtained by hydrolysis of TBT with the addition of cetyl-trimethyl-ammonium bromide (CTAB) as surfactant in an EG solution. Furthermore, TiO(x) nanorods with two sharp ends can be obtained by hydrolysis of TBT with the addition of salt (LiCl) in an EG solution. The AFM results show that the TiO(x) nanorods with rough surfaces are formed by the self-assembly of TiO(x) nanospheres. The electrorheological (ER) effect was investigated using a suspension of titanium oxide nanowires or nanorods dispersed in silicone oil. Oil suspensions of titanium oxide nanowires or nanorods exhibit a dramatic reorganization when submitted to a strong DC electric field and the particles aggregate to form chain-like structures along the direction of applied electric field. Two-dimensional SAXS images from chains of anisotropically shaped particles exhibit a marked asymmetry in the SAXS patterns, reflecting the preferential self-assembly of the particles in the field. The suspension of rough TiO(x) nanorods shows stronger ER properties than that of the other nanostructured TiO(x) particles. We find that the particle surface roughness plays an important role in modification of the dielectric properties and in the enhancement of the ER effect.

X-ray studies of carbon dioxide intercalation in Na-fluorohectorite clay at near-ambient conditions.

We show experimentally that gaseous CO(2) intercalates into the interlayer space of the synthetic smectite clay Na-fluorohectorite at conditions not too far from ambient. The mean interlayer repetition distance of the clay when CO(2) is intercalated is found to be 12.5 Å for the conditions -20 °C and 15 bar. The magnitude of the expansion of the interlayer upon intercalation is indistinguishable from that observed in the dehydrated-monohydrated transition for H(2)O, but the possibility of water intercalation is ruled out by a careful analysis of the experimental conditions and repeating the measurements exposing the clay to nitrogen gas. The dynamics of the process is observed to be dependent on the pressure, with a higher intercalation rate at increased pressure. The rate of CO(2) intercalation at the studied conditions is found to be several orders of magnitude slower than the intercalation rate of water or humidity at ambient pressure and temperature.

Intercalated water in synthetic fluorhectorite clay.

(7)Li and (1)H nuclear magnetic resonance together with X-ray diffraction measurements in powdered samples and pseudocrystalline films of synthetic fluorhectorite as a function of relative ambient humidity permit to address several aspects of the structure and dynamics of intercalated water molecules. The role of proton exchange as a possibly dominant mechanism of charge transport in the one-water layer regime of hydration is reexamined. The experimental results in Li-fluorhectorite support the result of molecular simulations which predict, for Li-montmorillonite, the existence of an intermediate regime, between one-water layer and two-water layer states.

Minute synthesis of extremely stable gold nanoparticles.

We describe a rapid environmentally friendly wet-chemical approach to synthesize extremely stable non-toxic, biocompatible, water-soluble monodispersed gold nanoparticles (AuNPs) in one step at room temperature. The particles have been successfully achieved in just a few minutes by merely adding sodium hydroxide (NaOH) acting as an initiator for the reduction of HAuCl(4) in aqueous solution in the presence of polyvinylpyrrolidone (PVP) without the use of any reducing agent. It is also proved to be highly efficient for the preparation of AuNPs with controllable sizes. The AuNPs show remarkable stability in water media with high concentrations of salt, various buffer solutions and physiological conditions in biotechnology and biomedicine. Moreover, the AuNPs are also non-toxic at high concentration (100 microM). Therefore, it provides great opportunities to use these AuNPs for biotechnology and biomedicine. This new approach also involved several green chemistry concepts, such as the selection of environmentally benign reagents and solvents, without energy consumption, and less reaction time.

Fluid imbibition in paper fibers: precursor front.

We employ nuclear magnetic resonance imaging to study water penetration in cylindrical blocks of unsized paper prepared under different molding pressures. From the measured kinetics of the imbibition profiles, we determine the dependence of the effective transport diffusivity upon degree of saturation of the pores by the penetrating fluid. In general, the transport process is found to be non-Fickian and we discuss different methods of data analysis adapted to this situation. The effective transport diffusivity vividly captures the presence of a precursor front, consisting of fluid in partially filled pores, with a much higher effective diffusivity than that of fluid in largely saturated pores.