Intercalation and delamination of two-dimensional solids in many cases is a requisite step for exploiting their unique properties. Herein we report on the intercalation of two-dimensional Ti3C2, Ti3CN and TiNbC-so called MXenes. Intercalation of hydrazine, and its co-intercalation with N,N-dimethylformamide, resulted in increases of the c-lattice parameters of surface functionalized f-Ti3C2, from 19.5 to 25.48 and 26.8 A, respectively. Urea is also intercalated into f-Ti3C2. Molecular dynamics simulations suggest that a hydrazine monolayer intercalates between f-Ti3C2 layers. Hydrazine is also intercalated into f-Ti3CN and f-TiNbC. When dimethyl sulphoxide is intercalated into f-Ti3C2, followed by sonication in water, the f-Ti3C2 is delaminated forming a stable colloidal solution that is in turn filtered to produce MXene 'paper'. The latter shows excellent Li-ion capacity at extremely high charging rates.

/pdf/intercalation-and-delamination-of-layered-carbides-and-n54wqm9e9n.pdf

Intercalation and delamination of layered carbides and carbonitrides

Surface ionization and complexation at the oxide/water interface

The long-term stabilization of soil organic matter (SOM) in tropical and temperate regions is mediated by soil biota (e.g. fungi, bacte- ria, roots and earthworms), soil structure (e.g. aggregation) and their interactions. On average, soil C turnover was twice as fast in tropical com- pared with temperate regions, but no major differences were observed in SOM quality between the two regions. Probably due to the soil mineralogy dominated by 1:1 clay minerals and oxides in tropical regions, we found a higher aggregate stability, but a lower correlation between C contents and aggregate stability in tropical soils. In addition, a smaller amount of C associated with clay and silt particles was observed in tro- pical versus temperate soils. In both tropical and temperate soils, a general increase in C levels (≈ 325 ± 113 kg C·ha -1 ·yr -1 ) was observed under no-tillage compared with conventional tillage. On average, in temperate soils under no-tillage, compared with conventional tillage, CH4 uptake (≈ 0.42 ± 0.10 kg C-CH4·ha -1 ·yr -1

/pdf/soil-organic-matter-biota-and-aggregation-in-temperate-and-4fy8bn1320.pdf

Soil organic matter, biota and aggregation in temperate and tropical soils - Effects of no-tillage

Halloysite clay minerals are ubiquitous in soils and weathered rocks where they occur in a variety of particle shapes and hydration states. Diversity also characterizes their chemical composition, cation exchange capacity and potassium selectivity. This review summarizes the extensive but scattered literature on halloysite, from its natural occurrence, through its crystal structure, chemical and morphological diversity, to its reactivity toward organic compounds, ions and salts, involving the various methods of differentiating halloysite from kaolinite. No unique test seems to be ideal to distinguish these 1:1 clay minerals, especially in soils. The occurrence of 2:1 phyllosilicate contaminants appears, so far, to provide the best explanation for the high charge and potassium selectivity of halloysite. Yet, hydration properties of the mineral probably play a major role in ion sorption. Clear trends seem to relate particle morphology and structural Fe. However, future work is required to understand the possible mechanisms linking chemical, morphological, hydration and charge properties of halloysite.

Halloysite clay minerals — a review

Surface area control of organic carbon accumulation in continental shelf sediments

Adsorption of potential-determining ions at the ferric oxide-aqueous electrolyte interface

The dissolution of synthetic magnetite, maghemite, hematite, goethite, lepidocrocite, and ak- aganeite was faster in HCI than in HCIO4. In the presence of H § the C1- ion increased the dissolution rate, but the 004- ion had no effect, suggesting that the formation of Fe-Cl surface complexes assists dissolution. The effect of temperature on the initial dissolution rate can be described by the Arrhenius equation, with dissolution rates in the order: lepidocrocite > magnetite > akaganeite > maghemite > hematite > goe- thite. Activation energies and frequency factors for these minerals are 20.0, 19.0, 16.0, 20.3, 20.9, 22.5 kcal/ mole and 5.8  1011, 1.8  101~ 7.4  10 7, 5.1  101~ 2.1  101~ 3.0 x 1011 g Fe dissolved/mZ/hr, re- spectively. The complete dissolution of magnetite, maghemite, hematite, and goethite is well described by the cube-root law, whereas that of lepidocrocite is not.

Dissolution of Iron Oxides and Oxyhydroxides in Hydrochloric and Perchloric Acids

The specific adsorption of Hg(II), as Hg2+ and HgCl20, on goethite has been measured as a function of pH The results show that the mercuric ion is not a typical heavy metal cation since its adsorption is considerably less than for other cations at pH values near their respective p*K values Complexing the mercuric ion with chloride to give HgCl20 was found to reduce adsorption to negligible amounts

It is concluded that hydroxo ligands are essential for Hg(II) adsorption and it is probable that two hydroxo bridges are formed between the oxide surface and the adsorbed Hg(II) atom Reduction of the positive charged surface The considerable covalency of the Hg-OH bonds is believed to cause the relatively low affinity of the mercuric ion for the oxide by polarizing the surface-OH-Hg bonds and therefore minimizing the strength of the surface-OH bonds

The complex ions [Co(NH3)6]3+, [Co(NH3)5H2O]3+, and [Co(en)2(H2O)2]3+ were not specifically adsorbed even when the latter two were hydrolyzed to hydroxo species Their inability to adsorb is again attributed to the covalency of the Co(III)-OH bonds of the hydroxo ions which prevents the formation of stable hydroxo bridges between the oxide surface and the Co(III) species

The specific adsorption of inorganic Hg(II) species and Co(III) complex ions on goethite

The development of the ethylene glycol monoethyl ether (EGME) method for measuring the hydratable' surface area of soils and clays is reviewed. We have examined the EGME retention of 18 montmorillonites and compared the surface areas obtained in this way with those obtained using the b-axis parameter and total chemical composition of each clay. The original hypothesis of Dyal and Hendricks (1950), that a monolayer of ethylene glycol (and presumably of EGME) forms on each of the opposing lamellae within a montmorillonite quasi-crystal, is approximately correct. However, the existing evidence for beidellites suggests that this mineral species is intermediate in retention behavior between montmorillonites and vermiculites. For illites and kaolinites the surface areas measured with EGME are significantly greater than those measured with N. However, we have shown that there is much better agreement between the surface areas measured with N and those calculated from the amount of water adsorbed at a relative vapor pressure of about p/p 0 = 0.2, using 0.108 nm 2 as the molecular area of adsorbed water. Accordingly, we recommend that the amount of water adsorbed at p/p 0 = 0.19 (a saturated solution of CaBr 2 at 20°C) be used as a single point determination for the routine examination of large numbers of soil samples as an indication of surface extent. We provide reasons why it is inappropriate to convert the water adsorption value to a surface area. We briefly discuss the significance of surface area measurements in studies of the chemical and physical aspects of soil and clay behavior.

Appraisal of the Ethylene Glycol Monoethyl Ether Method for Measuring Hydratable Surface Area of Clays and Soils

We have used the Poisson−Boltzmann (PB) theory and DLVO double-layer theory together with the hypernetted chain formalism based on the primitive model for electrolyte solutions to examine recently published results for extensive crystalline swelling of Li-montmorillonite as revealed by d(001) spacings over the pressure range 0.05−0.9 MPa and the concentration range 1−10-4 M LiCl. The analysis based on Langmuir's use of elliptical integrals reveals that the theory satisfactorily predicts surface separation over the range 18−120 A and that the DLVO theory, with a 5.5 A Stern layer, indicates Gouy plane potentials ranging from −58 to −224 mV over the concentration range 0.1−10-4 M LiCl and a constant Gouy plane charge of 0.038 C m-2, which is 30% of the crystal lattice charge. The anisotropic hypernetted chain (HNC) analysis, also based on lattice charge, satisfactorily predicts pressure−distance relationships over the range of concentrations. There is no evidence for the operation of the “secondary hydratio...

Application of Double-Layer Theories to the Extensive Crystalline Swelling of Li-Montmorillonite

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