Co-solvent exfoliation and suspension of hexagonal boron nitride.

A simple method is presented for exfoliating and suspending hexagonal boron nitride using a co-solvent approach. A 60 w/w% concentration of tert-butanol in water is very effective at exfoliating boron nitride especially when compared to the individual components alone as indicated by UV-vis and transmission electron microscopy. Molecular weight and surface tension are found to play inverse roles in the exfoliation.

Rapid solid-state synthesis of tantalum, chromium, and molybdenum nitrides.

Solid-state metathesis (exchange) reactions can be used to synthesize many different transition-metal nitrides under ambient conditions including TiN, ZrN, and NbN. Typical metathesis reactions reach temperatures of greater than 1300 degrees C in a fraction of a second to produce these refractory materials in highly crystalline form. Likely due to the large amount of heat produced in these solid-state reactions, some transition-metal nitrides such as TaN, CrN, and gamma-Mo(2)N cannot easily be synthesized under ambient conditions. Here metathesis reactions are demonstrated to produce the cubic nitrides TaN, CrN, and gamma-Mo(2)N when sufficient pressure is applied before the reaction is initiated. By pressing a pellet of TaCl(5) and Li(3)N with an embedded iron wire, crystalline cubic TaN forms under 45 kbar of pressure after a small current is used to initiate the chemical reaction. Crystalline cubic CrN is synthesized from CrCl(3) and Li(3)N initiated under 49 kbar of pressure. Crystalline gamma-Mo(2)N is produced from MoCl(5) and Ca(3)N(2) (since MoCl(5) and Li(3)N self-detonate) initiated under 57 kbar of pressure. The addition of ammonium chloride to these metathesis reactions drastically lowers the pressure requirements for the synthesis of these cubic nitrides. For example, when 3 mol of NH(4)Cl is added to CrCl(3) and Li(3)N, crystalline CrN forms when the reaction is initiated with a resistively heated wire under ambient conditions. Cubic gamma-Mo(2)N also forms at ambient pressure when 3 mol of NH(4)Cl is added to the reactants MoCl(5) and Ca(3)N(2) and ignited with a resistively heated wire. A potential advantage of synthesizing gamma-Mo(2)N under ambient conditions is the possibility of forming high-surface-area materials, which could prove useful for catalysis. Nitrogen adsorption (BET) indicates a surface area of up to 30 m(2)/g using a Langmuir model for gamma-Mo(2)N produced by a metathesis reaction at ambient pressure. The enhanced surface area is confirmed using scanning electron microscopy.

Self-propagating metathesis routes to metastable group 4 phosphides.

Group 4 phosphides, which are typically prepared at high temperatures (> 800 degrees C) over several days, are synthesized in self-propagating metathesis (exchange) reactions in seconds. These reactions produce cubic forms of zirconium phosphide (ZrP) and hafnium phosphide (HfP) which are normally made at temperatures greater than 1425 degrees C and 1600 degrees C, respectively. To test whether the high temperatures reached in the metathesis reactions are responsible for the formation of the cubic phases, inert salts are added to lower the maximum reaction temperatures. The lower temperature reactions still result in cubic phosphides, although smaller crystallites form. Further experiments with phosphorus addition indicate that the phosphorus content is not responsible for cubic phase formation. Templating is ruled out using lattice mismatched KCl and hexagonal ZnS as additives. Therefore, the direct synthesis of the high-temperature cubic phase in metathesis reactions appears to be caused by nucleation of the metastable cubic form that is then trapped by rapid cooling. Heating the cubic phase of either ZrP or HfP to 1000 degrees C for 18 h, or carrying out metathesis reactions in sealed ampules at 1000 degrees C, results only in the hexagonal phase.

Rapid solid-state precursor synthesis of materials.

Precursor reactions based on metathetical (exchange) pathways have been found to be an effective synthetic route for the preparation of a large number of materials. These solid-solid reactions are extremely rapid (typically less than 1 second) and often can be initiated at or near room temperature. They are potentially useful for controlling product particle size and for preparing highquality cationic or anionic solid solutions. The frequently self-propagating and sometimes explosive behavior exhibited by these reactions can be attributed to the large amount of heat they release. As a consequence, thermodynamic considerations can be used to help select the best set of precursors as judged from reaction enthalpies. The factors that influence these reactions are illustrated by a discussion of MoS(2), ZrN, MoSi(2), and GaAs, examples of the many compounds accessible by this synthetic route.

Pressure Dependence of Superconductivity in Single-Phase K3C60.

The superconducting compound K(3)C(60) (with transition temperature T(c) = 19.3 kelvin at ambient pressure), formed as a single phase by reaction of alkali vapor with solids of the icosahedral C(60) molecule (buckminsterfullerene), shows a very large decrease of T(c) with increasing pressure. Susceptibility measurements on sintered pellets showing bulk superconductivity are reported up to 21 kilobars of pressure, where T(c) is already less than 8 kelvin. The results are consistent with a piling up of the density of states at the Fermi level.

Conjugated polymer films for gas separations.

Permeabilities for a series of gases through free-standing films of the conjugated polymer polyaniline are reported. A remarkable selectivity has been achieved for important gas pairs incuding hydrogen-nitrogen, oxygen-nitrogen, and carbon dioxide-methane. The selectivity values of 3590 for H(2)/N(2), 30 for O(2)/N(2), and 336 for CO(2)/CH(4) surpass the highest previously reported values of 313, 16, and 60 for the nonconjugated polymers poly(trifluorochloroethylene), cellulose nitrate, and a fluorinated polyimide, respectively. The process for tailoring gas selectivity of a polyaniline membrane involves first enhancing the permeabilities of gases with small diameters [<3.5 angstroms (A)] by doping and undoping the polymer film with counterions of an appropriate size. High selectivities are then achieved by decreasing the permeabilities of larger gases (>3.5 A diameter) through controlled redoping of the polymer. The permanent morphological changes induced in this conjugated polymer system and others indicate the potential for development of universal membranes for gas separations.