Synthesis of Al3BC from mechanically milled and spark plasma sintered Al-MgB2 composite materials

The aluminium-rich ternary aluminium borocarbide, Al₃BC was synthesised for the first time by solid-state reactions occurring during heat treatments after mechanical milling (MM) of pure aluminium with 15 or 50 at% MgB₂ powder mixtures in the presence of the process control agent (PCA).

The solid-state reactions in the Al–15 and 50 at% MgB₂ composite materials occurred between the MMed powders and process control agent (PCA) after heating at 773–873 K for 24 h. The products of the solid-state reaction induced Al₃BC, AlB₂, γ-Al₂O₃ and spinel MgAl₂O₄. MM processing time and heating temperatures in the Al–15 and 50 at% MgB₂ composite materials affected the selection of those intermetallic compounds. When MM processing time was increased for a given composition, the formation of the Al₃BC compound started at lower heat treatment temperatures. However, when the amount of MgB₂ was increased in the 4 h MM processing regime, the formation of the Al₃BC compound during heating was suppressed. As a result of the solid-state reactions in MMed powders the hardness was observed to increase after heating at 573–873 K for 24 h.

The fully dense bulk nano-composite materials have been successfully obtained through the combination of the MM and spark plasma sintering (SPS) processes for the 4 h or 8 h MMed powders of the Al–15 at% MgB₂ composite materials sintered under an applied pressure of 49 MPa at 873 K for 1 h.

Facile synthesis of NiCo2O4 nanorod arrays on Cu conductive substrates as superior anode materials for high-rate Li-ion batteries

In this work, we report a mild and cost-effective solution method to directly grow Ni-substituted Co3O4 (ternary NiCo2O4) nanorod arrays on Cu substrates. Electrochemical impedance spectroscopy (EIS) measurements show that the values of the electrolyte resistance Re and charge-transfer resistance Rct of NiCo2O4 are 6.8 and 63.5 Ω, respectively, which are significantly lower than those of binary Co3O4 (10.4 and 122.4 Ω). This EIS characterization strongly confirms that the ternary NiCo2O4 anode has much higher electrical conductivity than that of the binary Co3O4 electrode materials, which should greatly enhance the lithium storage performances. Due to the well-aligned 1D nanorod microstructure and a higher electrical conductivity, these ternary NiCo2O4 nanorod arrays manifest high specific capacity, excellent cycling stability (a high reversible capacity of about 830 mA h g−1 was achieved after 30 cycles at 0.5 C) and high rate capability (787, 695, 512, 254, 127 mA h g−1 at 1 C, 2 C, 6 C 50 C and 110 C, respectively).

Synthesis of ZnO nanowires using ball-milling and annealing method

Nanowires represent a new class of ZnO morphologies with many exiting new properties and applications. The research in the synthesis and characterization of ZnO nanowires has received enormous attention in recent years. However, most synthesis methods using vapor deposition process can only produce small amount of sample, mass production has not been achieved yet. Large-quantity production of ZnO nanowires needs to be realized for large-scale property and application studies. One of the promising approaches to the large scale synthesis is a ball-milling and annealing method. This paper first introduces several common synthesis methods of ZnO nanowires and then summarizes the one dimensional nanomaterials produced by the ball milling and annealing method. Finally, some preliminary results of ZnO nanowire synthesis are presented.

Mechanochemical synthesis of nanoparticles

The results of recent investigation of the mechanochemical synthesis of inorganic nanoparticles are reviewed. It was demonstrated that, by selecting suitable chemical reaction paths, stoichiometry of starting materials and milling conditions, mechanochemical processing can be used to synthesise a wide range of nanocrystalline particles dispersed within a soluble salt matrix. Selective removal of the matrix phase by washing the resulting powder with appropriate solvents can yield nanoparticles of the desired phase. This technique has been shown to have advantages over other methods of producing nanoparticles in terms of low cost, small particle sizes, low agglomeration, narrow size distributions and uniformity of crystal structure and morphology.

Approaches to the synthesis of peptide substituted frameworks

The 1,3 dipolar cycloaddition between carbonyl ylids (generated from cyclobutene epoxides flanked by esters) and norbornyl alkenes – the ACE reaction – offers a facile method for the construction of polynorbornyl molecular frameworks. This reaction has, as described in this dissertation, underpinned the construction of molecular frameworks that have peptides and amino acids attached. Such highly rigid peptide-frameworks are of use in the field of peptidomimetics; the template molecule governs the final positioning of any attached groups such that a precise arrangement of amino acids can be achieved without the need to construct entire proteins. In the course of any ACE reaction the ester flanked cyclobutene epoxide is transformed to a 1,3 dipole, the esters serve to stablise this reactive intermediate and are as a consequence incorporated in the reaction product. Modification of these esters provides pseudo-equatorial points for peptide attachment. These methyl esters were replaced with tert-butyl esters to provide pseudo-axial attachment points that could be selectively addressed. The optimal strategy for peptide-framework construction involved direct condensation of carboxyl protected amino acids to bicyclo[2.2.1]hept-5-ene-2-endo-carboxylic acid as well as condensation of amino acids to cyclobutene epoxides derived from this acid. The ACE reaction of (±) bicycloheptene-2-endo-carboxylic acid derivatives with cyclobutene epoxides synthesised from such racemic acid derivatives provided a mixture of enantiomers and meso compounds. In order to control the position of the attachment points – and hence the final location of the attached peptides – the ACE reaction required chiral starting materials. Accordingly, all peptidoframeworks were derived from the chiral (2S)-(-)-bicycloheptene carboxylic acid. The ACE reaction of this (S)-norbornene with the (S)-epoxide provided a peptide framework in which the attached amino acids were positioned pseudo-axially. Deprotection of the amino acid allowed peptide chain building in the pseudo-axial direction. Using this strategy a framework with an alanine residue and a triglycine peptide was synthesised. By combining this strategy with the ter-butyl ester variant a framework with pseudo-axial alanine and pseudo-equatorial glycine residues was manufactured.

Synthesis of 2-(selenophen-2-yl) pyrroles and their electropolymerization to electrochromic nanofilms

The divergent syntheses of 2-(selenophen-2-yl)pyrroles and their N-vinyl derivatives from available 2-acylselenophenes and acetylenes in a one-pot procedure make these exotic heterocyclic ensembles accessible. Now we face a potentially vast area for exploration with a great diversity of far-reaching consequences including conducting electrochromic polymers with repeating of pyrrole and selenophene units (emerging rivalry for polypyrroles and polyselenophenes), the synthesis of functionalized pyrrole–selenophene assembles for advanced materials, biochemistry and medicine, exciting models for theory of polymer conductivity.

Mild and cost-effective synthesis of iron fluoride-graphene nanocomposites for high-rate Li-ion battery cathodes

Exploring high performance cathode materials is essential to realize the adoption of Li-ion batteries for application in electric vehicles and hybrid electric vehicles. FeF3, as a typical iron-based fluoride, has been attracting considerable interest due to both the high electromotive force value of 2.7 V and the high theoretical capacity of 237 mA h g_1 (1e_ transfer). In this study, we report a facile lowtemperature solution phase approach for synthesis of uniform iron fluoride nanocrystals on reduced graphene sheets stably suspended in ethanol solution. The resulting hybrid of iron fluoride nanocrystals and graphene sheets showed high specific capacity and high rate performance for iron fluoride type cathode materials. High stable specific capacity of about 210 mA h g_1 at a current density of 0.2 C was achieved, which is much higher than that of LiFePO4 cathode material. Notably, these iron fluoride/ nanocomposite cathode materials demonstrated superior rate capability, with discharge capacities of 176, 145 and 113 mA h g_1 at 1, 2 and 5 C, respectively.

Facile synthesis of graphene oxide hybrids bridged by copper ions for increased conductivity

In this article, we report a facile method for preparing graphene oxide (GO) hybrid materials consisting of copper ions (Cu2+) complexed with GO, where Cu2+ acted as bridges connecting GO sheets. The method of film formation is based on cross-linking GO using Cu2+ followed by filtration onto nanoporous supports. This binding can be rationalized due to the chemical interaction between the functional groups on GO and the metal ion. We observed that there was a decrease in charge transfer resistance through electrochemical study. It suggests that the presence of metal ions in GO films could introduce new energy levels along the electron transport pathway and open up possible conduction channels. We also found that the hybrid graphene film assembled with Cu2+ dramatically decreases resistance through flash light reduction.

Synthesis and self-assembly of hybrid amphiphilic block copolymers

This thesis focused on the synthesis and self-assembly of novel block copolymers for the purpose of drug delivery. The block copolymers achieved comprise of a synthetic block and a peptide block and self-assemble into nano sized particles which can act as drug containers.

Comparative study of materials-binding peptide interactions with gold and silver surfaces and nanostructures : A thermodynamic basis for biological selectivity of inorganic materials

Controllable 3D assembly of multicomponent inorganic nanomaterials by precisely positioning two or more types of nanoparticles to modulate their interactions and achieve multifunctionality remains a major challenge. The diverse chemical and structural features of biomolecules can generate the compositionally specific organic/inorganic interactions needed to create such assemblies. Toward this aim, we studied the materials-specific binding of peptides selected based upon affinity for Ag (AgBP1 and AgBP2) and Au (AuBP1 and AuBP2) surfaces, combining experimental binding measurements, advanced molecular simulation, and nanomaterial synthesis. This reveals, for the first time, different modes of binding on the chemically similar Au and Ag surfaces. Molecular simulations showed flatter configurations on Au and a greater variety of 3D adsorbed conformations on Ag, reflecting primarily enthalpically driven binding on Au and entropically driven binding on Ag. This may arise from differences in the interfacial solvent structure. On Au, direct interaction of peptide residues with the metal surface is dominant, while on Ag, solvent-mediated interactions are more important. Experimentally, AgBP1 is found to be selective for Ag over Au, while the other sequences have strong and comparable affinities for both surfaces, despite differences in binding modes. Finally, we show for the first time the impact of these differences on peptide mediated synthesis of nanoparticles, leading to significant variation in particle morphology, size, and aggregation state. Because the degree of contact with the metal surface affects the peptide's ability to cap the nanoparticles and thereby control growth and aggregation, the peptides with the least direct contact (AgBP1 and AgBP2 on Ag) produced relatively polydispersed and aggregated nanoparticles. Overall, we show that thermodynamically different binding modes at metallic interfaces can enable selective binding on very similar inorganic surfaces and can provide control over nanoparticle nucleation and growth. This supports the promise of bionanocombinatoric approaches that rely upon materials recognition.

Synthesis of single-crystalline LiFePO4 with rhombus-like morphology

In this investigation, carbon-coated LiFePO4 cathode materials were synthesized with a facile hydrothermal method. The structure and electrochemical properties of the materials were investigated by X-ray diffraction (XRD), Roman, transmission electron microscopy-energy dispersive spectroscopy (TEM-EDS), and electrochemical impedance spectroscopy (EIS). By adjusting the mixing concentration of starting materials, a single-crystalline LiFePO4 with an anisotropic rhombus morphology (Space Group: Pmnb No. 62) were successfully synthesized. In addition, the carbon coated on the surface of LiFePO4 material prepared has a lower ID/IG (0.80), which indicates an optimized carbon structure with an increased amount of sp2-type carbon. Electrochemical performance test shows that the carbon-coated LiFePO4 cathode materials have an initial discharge capacity of 146 mAh g−1 at 0.2C.