Carbon nanothreads are a new one-dimensional sp carbon nanomaterial. They assemble into hexagonal crystals in a room temperature, nontopochemical solid-state reaction induced by slow compression of benzene to 23 GPa. Here we show that pyridine also reacts under compression to form a well-ordered sp product: CNH carbon nitride nanothreads. Solid pyridine has a different crystal structure from solid benzene, so the nontopochemical formation of low-dimensional crystalline solids by slow compression of small aromatics may be a general phenomenon that enables chemical design of properties. The nitrogen in the carbon nitride nanothreads may improve processability, alters photoluminescence, and is predicted to reduce the bandgap.

Carbon nanothreads are a new type of one-dimensional sp-carbon nanomaterial formed by slow compression and decompression of benzene. We report characterization of the chemical structure of C-enriched nanothreads by advanced quantitative, selective, and two-dimensional solid-state nuclear magnetic resonance (NMR) experiments complemented by infrared (IR) spectroscopy. The width of the NMR spectral peaks suggests that the nanothread reaction products are much more organized than amorphous carbon. In addition, there is no evidence from NMR of a second phase such as amorphous mixed sp/sp-carbon. Spectral editing reveals that almost all carbon atoms are bonded to one hydrogen atom, unlike in amorphous carbon but as is expected for enumerated nanothread structures. Characterization of the local bonding structure confirms the presence of pure fully saturated "degree-6" carbon nanothreads previously deduced on the basis of crystal packing considerations from diffraction and transmission electron microscopy. These fully saturated threads comprise between 20% and 45% of the sample. Furthermore, C-C spin exchange experiments indicate that the length of the fully saturated regions of the threads exceeds 2.5 nm. Two-dimensional C-C NMR spectra showing bonding between chemically nonequivalent sites rule out enumerated single-site thread structures such as polytwistane or tube (3,0) but are consistent with multisite degree-6 nanothreads. Approximately a third of the carbon is in "degree-4" nanothreads with isolated double bonds. The presence of doubly unsaturated degree-2 benzene polymers can be ruled out on the basis of C-C NMR with spin exchange rate constants tuned by rotational resonance and H decoupling. A small fraction of the sample consists of aromatic rings within the threads that link sections with mostly saturated bonding. NMR provides the detailed bonding information necessary to refine solid-state organic synthesis techniques to produce pure degree-6 or degree-4 carbon nanothreads.

The compression of glassy carbon forms a series of lightweight, ultrastrong, hard, elastic, and conductive carbons.

Phase-pure samples of a metastable allotrope of silicon, Si-III or BC8, were synthesized by direct elemental transformation at 14 GPa and ∼900 K and also at significantly reduced pressure in the Na-Si system at 9.5 GPa by quenching from high temperatures ∼1000 K. Pure sintered polycrystalline ingots with dimensions ranging from 0.5 to 2 mm can be easily recovered at ambient conditions. The chemical route also allowed us to decrease the synthetic pressures to as low as 7 GPa, while pressures required for direct phase transition in elemental silicon are significantly higher. In situ control of the synthetic protocol, using synchrotron radiation, allowed us to observe the underlying mechanism of chemical interactions and phase transformations in the Na-Si system. Detailed characterization of Si-III using X-ray diffraction, Raman spectroscopy, (29)Si NMR spectroscopy, and transmission electron microscopy are discussed. These large-volume syntheses at significantly reduced pressures extend the range of possible future bulk characterization methods and applications.

Carbon nanothreads are a new one-dimensional sp 3-bonded nanomaterial of CH stoichiometry synthesized from benzene at high pressure and room temperature by slow solid-state polymerization. The resulting threads assume crystalline packing hundreds of microns across. We show high-resolution electron microscopy (HREM) images of hexagonal arrays of well-aligned thread columns that traverse the 80-100 nm thickness of the prepared sample. Diffuse scattering in electron diffraction reveals that nanothreads are packed with axial and/or azimuthal disregistry between them. Layer lines in diffraction from annealed nanothreads provide the first evidence of translational order along their length, indicating that this solid-state reaction proceeds with some regularity. HREM also reveals bends and defects in nanothread crystals that can contribute to the broadening of their diffraction spots, and electron energy-loss spectroscopy confirms them to be primarily sp 3 hybridized, with less than 27% sp 2 carbon, most likely associated with partially saturated "degree-4" threads.

Aerogels offer a potential alternative to noble metals that could reduce both the cost and environmental impact associated with catalytic converter production. The environmental impact of the production of aerogel catalysts could be further reduced by using a rapid supercritical extraction (RSCE) technique, which reduces the time and solvent waste associated with aerogel preparation. Alumina aerogels, which have shown activity in catalyzing exhaust processing reactions, were prepared using an epoxide-assisted gelation technique with RSCE processing in a contained mold in a hydraulic hot press. Samples were characterized by FTIR, XRD, SEM, EDX, nitrogen adsorption porosimetry and pycnometry. Solvent characterization by GC-MS headspace analysis shows that excess propylene oxide and chloropropanol products of an irreversible epoxide ring-opening reaction are present in the alumina gel following gelation, but can be removed via solvent exchange. Alumina aerogels with surface areas as high as 790 m 2 /g and bulk densities as low as 0.05 g/mL were prepared. Preliminary characterization of these aerogels, utilizing a catalytic test bed and a simulated emissions gas blend, demonstrates that they have moderate ability for removal of hydrocarbons, carbon monoxide and nitrogen oxide.

Tetracyanomethane, C(CN), is a tetrahedral molecule containing a central sp carbon that is coordinated by reactive nitrile groups that could potentially transform to an extended CN network with a significant fraction of sp carbon. High-purity C(CN) was synthesized, and its physiochemical behavior was studied using in situ synchrotron angle-dispersive powder X-ray diffraction (PXRD) and Raman and infrared (IR) spectroscopies in a diamond anvil cell (DAC) up to 21 GPa. The pressure dependence of the fundamental vibrational modes associated with the molecular solid was determined, and some low-frequency Raman modes are reported for the first time. Crystalline molecular C(CN) starts to polymerize above ∼7 GPa and transforms into an interconnected disordered network, which is recoverable to ambient conditions. The results demonstrate feasibility for the pressure-induced polymerization of molecules with premeditated functionality.

Na4Si24 is the precursor to Si24, a recently discovered allotrope of silicon. With a quasidirect band gap near 1.3 eV, Si24 has potential to transform silicon-based optoelectronics including solar energy conversion. However, the lack of large, pure crystals has prevented the characterization of intrinsic properties and has delayed deposition-based metastable growth efforts. Here, we report an optimized synthesis methodology for single-crystalline Na4Si24 with crystals approaching the millimeter-size scale with conditions near 9 GPa and 1123 K. Single-crystal diffraction was used to confirm the open-framework structure, and Na atoms remain highly mobile within the framework channels, as determined by electrical conductivity and electron energy loss spectroscopy (EELS) measurements. An epitaxial relationship between Na4Si24 and diamond cubic silicon (DC-Si), observed through high-resolution transmission electron microscopy (HRTEM), is proposed to facilitate the growth of high-quality Na4Si24 crystals from DC-Si wafers mixed with metallic Na, and could provide a viable path forward for scaling efforts of Na4Si24 and Si24.