Richard G. Blair

Mechanocatalysis for biomass-derived chemicals and fuels

Heterogeneous catalysis cannot be easily applied to solids such as cellulose. However, by mechanically grinding the correct catalyst and reactant, it is possible to induce solid–solid catalysis or mechanocatalysis. This process allows a wide range of solids to be effectively utilized as feedstock for commercially relevant compounds. Here we show a set of structural and physical parameters important for the implementation of catalysts in mechanocatalytic processes and their application in the catalytic depolymerization of cellulose. Using the best catalysts, which possess high surface acidities and layered structures, up to 84% of the available cellulose can be converted to water-soluble compounds in a single pass. This approach offers significant advantages over current methods - less waste, insensitivity to feedstock, multiple product pathways, and scalability. It can be easily integrated into existing biorefineries - converting them into multi-feedstock and multi-product facilities. This will expand the use of non-food polysaccharide sources such as switch grass.

Comparison of shaking versus baking: further understanding the energetics of a mechanochemical reaction

Using a mechanically driven Diels–Alder reaction we were able to characterize the chemical energetics of a SPEX 8000M mixer/mill. Our results demonstrate that the conditions produced by this type of mill are similar to those produced when performing the same reaction at 90 °C in solution. Discrete element models and in situ temperature logging were used to analyse the energetics of this system. These models indicate that the yields obtained using a SPEX 8000M mill are best correlated to the velocity of the media and number of non-zero force collisions.

NANOCOMPOSITES TO ENHANCE ZT IN THERMOELECTRICS

The concept of using “self-assembled” and “force-engineered” nanostructures to enhance the thermoelectric figure of merit relative to bulk homogeneous and composite materials is presented in general terms. Specific application is made to the Si-Ge system for use in power generation at high temperature. The scientific advantages of the nanocomposite approach for the simultaneous increase in the power factor and decrease of the thermal conductivity are emphasized along with the practical advantages of having bulk samples for property measurements and a straightforward path to scale-up materials synthesis and integration of nanostructured materials into thermoelectric cooling and power generation devices.

Mechanochemical synthesis of alkaline earth carbides and intercalation compounds

High-energy ball milling has been successfully employed to produce alkaline earth carbides from the elements. In particular, CaC(2) yields of up to 98% can be realized in as little as 12 h. Similarly, the carbides of Mg (39% yield), Sr (87% yield), and Ba (82% yield) have been prepared. An intermediate in the synthesis of CaC(2) is the newly discovered gold-colored Ca-graphite intercalation compound CaC(6). Sr and Ba also go through initial intercalation phases (SrC(6) and BaC(6)) before ultimately producing the carbides. The magnesium product consisted of Mg(2)C(3) with no MgC(2) observed. The addition of sulfur to CaC(2) forming reactions did not adversely affect the overall synthesis; this suggests that this method may be utilized to sequester sulfur from high-sulfur coal. The preparation of these compounds by high-energy ball milling represents a novel method for producing pure carbides, as well as a convenient route to isotopically enriched ethyne.

Microwave initiated solid-state metathesis routes to Li2SiN2

The fast ion conductor lithium silicon nitride, Li2SiN2, is produced in a metathesis reaction between silicon chloride, SiCl4, and lithium nitride, Li3N, initiated in a conventional microwave oven. Lithium amide, LiNH2, and ammonium chloride, NH4Cl, serve to control the temperature and enhance the yield of Li2SiN2. A reaction mechanism is proposed based on the exothermicity of forming the by-product salt lithium chloride with silicon nitride, Si3N4, as a likely intermediate. By varying the stoichiometry of the reactants the phase LiSi2N3 can also be produced. The Li2SiN2 product is characterized using powder X-ray diffraction, scanning electron microscopy and complex impedance spectroscopy. A pressed pellet of Li2SiN2 has a conductivity of 2.70 × 10−3 S cm−1 at 500 °C.

Heterogeneous Metal-Free Hydrogenation over Defect-Laden Hexagonal Boron Nitride

Catalytic hydrogenation is an important process used for the production of everything from foods to fuels. Current heterogeneous implementations of this process utilize metals as the active species. Until recently, catalytic heterogeneous hydrogenation over a metal-free solid was unknown; implementation of such a system would eliminate the health, environmental, and economic concerns associated with metal-based catalysts. Here, we report good hydrogenation rates and yields for a metal-free heterogeneous hydrogenation catalyst as well as its unique hydrogenation mechanism. Catalytic hydrogenation of olefins was achieved over defect-laden h-BN (dh-BN) in a reactor designed to maximize the defects in h-BN sheets. Good yields (>90%) and turnover frequencies (6 × 10–5–4 × 10–3) were obtained for the hydrogenation of propene, cyclohexene, 1,1-diphenylethene, (E)- and (Z)-1,2-diphenylethene, octadecene, and benzylideneacetophenone. Temperature-programmed desorption of ethene over processed h-BN indicates the formation of a highly defective structure. Solid-state NMR (SSNMR) measurements of dh-BN with high and low propene surface coverages show four different binding modes. The introduction of defects into h-BN creates regions of electronic deficiency and excess. Density functional theory calculations show that both the alkene and hydrogen-bond order are reduced over four specific defects: boron substitution for nitrogen (BN), vacancies (VB and VN), and Stone–Wales defects. SSNMR and binding-energy calculations show that VN are most likely the catalytically active sites. This work shows that catalytic sites can be introduced into a material previously thought to be catalytically inactive through the production of defects.

Synthesis and crystal structure of cubic Ca16Si17N34.

Since the late 1960s, the exact structure of cubic calcium silicon nitride has been a source of debate. This paper offers evidence that the cubic phase CaSiN(2) described in the literature is actually Ca(16)Si(17)N(34). Presented here is a method for synthesizing single crystals of cubic-calcium silicon nitride from calcium nitride and elemental silicon under flowing nitrogen at 1500 °C. The colorless millimeter-sized crystals of Ca(16)Si(17)N(34) with a refractive index (n(25)) = 1.590 were found to be cubic (a = 14.8882 Å) and belong to the space group F43m (216). The synthesis of bulk, powdered cubic-Ca(16)Si(17)N(34) from calcium cyanamide and silicon is also discussed. Ca(16)Si(17)N(34) is a relatively air-stable refractory ceramic. In contrast to the orthorhombic phase of CaSiN(2), in which Ca(2+) sits in octahedral sites, this cubic phase has Ca(2+) in cubic sites that makes it an interesting host for new phosphors and gives rise to unique crystal field splitting.

High temperature Ir segregation in Ir–B ceramics: effect of oxygen presence on stability of IrB2 and other Ir–B phases

The formation of IrB2, IrB1.35, IrB1.1 and IrB monoboride phases in the Ir–B ceramic nanopowder was confirmed during mechanochemical reaction between metallic Ir and elemental B powders. The Ir–B phases were analysed after 90 h of high energy ball milling and after annealing of the powder for 72 h at 1050°C in vacuo. The iridium monoboride (IrB) orthorhombic phase was synthesised experimentally for the first time and identified by powder X-ray diffraction. Additionally, the ReB2 type IrB2 hexagonal phase was also produced for the first time and identified by high resolution transmission electron microscope. Ir segregation along disordered domains of the boron lattice was found to occur during high temperature annealing. These nanodomains may have useful catalytic properties.

Hexagonal OsB2 reduction upon heating in H2 containing environment

Abstract The stability of hexagonal ReB2 type OsB2 powder upon heating under reforming gas was investigated. Pure Os metal particles were detected by powder X-ray diffraction starting at 375°C and complete transformation of OsB2 to metallic Os was observed at 725°C. The mechanisms of precipitation of metallic Os is proposed and changes in the lattice parameters of OsB2 upon heating are analysed in terms of the presence of oxygen or water vapour in the heating chamber. Previous studies suggested that Os atoms possess (0) valence, while B atoms possess both (+3) and (−3) valences in the alternating boron/osmium sheet structure of hexagonal (P63/mmc, No. 194) OsB2; if controllable method for Os removal from the lattice could be found, the opportunity would arise to form two-dimensional (2D) layers consisting of pure B atoms.

High Temperature Thermoelectric Properties of Nano-Bulk Silicon and Silicon Germanium

Point defect scattering via the formation of solid solutions to reduce the lattice thermal conductivity has been an effective method for increasing ZT in state-of-the-art thermoelectric materials such as Si-Ge, Bi 2 Te 3 -Sb 2 Te 3 and PbTe-SnTe. However, increases in ZT are limited by a concurrent decrease in charge carrier mobility values. The search for effective methods for decoupling electronic and thermal transport led to the study of low dimensional thin film and wire structures, in particular because scattering rates for phonons and electrons can be better independently controlled. While promising results have been achieved on several material systems, integration of low dimensional structures into practical power generation devices that need to operate across large temperature differential is extremely challenging. We present achieving similar effects on the bulk scale via high pressure sintering of doped and undoped Si and Si-Ge nanoparticles. The nanoparticles are prepared via techniques that include high energy ball milling of the pure elements. The nanostructure of the materials is confirmed by powder X-ray diffraction, transmission electron microscopy, scanning electron microscopy, and dynamic light scattering. Thermal conductivity measurements on the densified pellets show a drastic 90% reduction in the lattice contribution at room temperature when compared to doped single crystal Si. Additionally, Hall effect measurements show a much more limited degradation in the carrier mobility. The combination of low thermal conductivity and high power factor in heavily doped n-type nanostructured bulk Si leads to an unprecedented increase in ZT at 1275 K by a factor of 3.5 over that of single crystalline samples. Experimental results on both n-type and p-type Si are discussed in terms of the impact of the size distribution of the nanoparticles, doping impurities and nanoparticle synthesis processes.