Utilisation of CO2 as "Structure Modifier" of Inorganic Solids.

Utilisation of CO2 as a chemical reagent is challenging, due to the molecule's inherent chemical stability. However, CO2 reacts promptly at high temperature (∼1000 °C) with alkaline-earth oxides to form carbonates and such reactions are used towards capture and re-utilisation. In this work, this concept is extended and CO2 is utilised as a reagent to modify the crystal structure of mixed-metal inorganic solids. Modification of the crystal structure is a "tool" used by materials scientists to tailor the physical property of solids. CO2 gas was reacted with several isostructural mixed-metal oxides Sr2 CuO3 , Sr1.8 Ba0.2 CuO3 and Ba2 PdO3 . These oxides are carefully selected to show anion vacancies in their crystal structure, to act as host sites for CO2 molecules, leading to the formation of carbonate anions, (CO3 )2- . The corresponding oxide carbonates were formed successfully and the favourable formation of SrCO3 as secondary phase was minimised via an innovative, yet simple synthetic procedure involving alternating of CO2 and air. We also derived a simple model to predict the kinetics of the reactions for the cuprates, using first-principles density functional theory and assimilating the reaction to a gas-surface process.

Fluoride doped γ-Fe2O3 nanoparticles with increased MRI relaxivity.

Iron oxide nanoparticles (IONs) are being actively researched and experimented with as contrast agents for Magnetic Resonance Imaging (MRI), as well as image-directed delivery of therapeutics. The efficiency of an MRI contrast agent can be described by its longitudinal and transverse relaxivities, r1 and r2. γ-Fe2O3 nanoparticles - doped with fluoride in a controlled manner and functionalised with citric acid - showed a 3-fold increase in r1 and a 17-fold increase in r2 in a magnetic field of 3 T and almost 6-fold increase in r1 and a 14-fold increase in r2 at 11 T. Following fluorination, PXRD shows that the crystal structure of γ-Fe2O3 is maintained, Mössbauer spectroscopy shows that the oxidation state of the Fe cation is unchanged and HREM shows that the particle size does not vary. However, magnetisation curves show a large increase in the coercive field, pointing towards a large increase in the magnetic anisotropy for the fluorinated nanoparticles compared to the un-doped γ-Fe2O3 nanoparticles. Therefore, a chemically induced increase in magnetic anisotropy appears to be the most relevant parameter responsible for the large increase in relaxivity for γ-Fe2O3 nanoparticles.

Doping of inorganic materials in microreactors - preparation of Zn doped Fe3O4 nanoparticles.

Microreactor systems are now used more and more for the continuous production of metal nanoparticles and metal oxide nanoparticles owing to the controllability of the particle size, an important property in many applications. Here, for the first time, we used microreactors to prepare metal oxide nanoparticles with controlled and varying metal stoichiometry. We prepared and characterised Zn-substituted Fe3O4 nanoparticles with linear increase of Zn content (ZnxFe3-xO4 with 0 ≤ x ≤ 0.48), which causes linear increases in properties such as the saturation magnetization, relative to pure Fe3O4. The methodology is simple and low cost and has great potential to be adapted to the targeted doping of a vast array of other inorganic materials, allowing greater control on the chemical stoichiometry for nanoparticles prepared in microreactors.

Linear antiferromagnetism in Ba2CoS3.

Ba(2)CoS(3) is the first example of an inorganic solid containing one-dimensional corner-sharing [Co(2+)-anion] chains, which leads to one-dimensional cooperative antiferromagnetism.

Direct amine-functionalisation of γ-Fe2O3 nanoparticles.

A novel and simple preparation of amine-modified γ-Fe2O3 nanoparticles is described. The presence of amine groups on the surface, instead of hydroxyl groups, will allow conjugation of biologically active molecules to the iron oxide nanoparticles without the need for a size increasing silica shell. Furthermore, the outer amine-layer increases the temperature of the γ-Fe2O3 to α-Fe2O3 structural transition in a similar way to previously reported cationic substitutions. This may suggest the formation of an oxide-nitride outer layer. Re-dispersion of the amine-modified γ-Fe2O3 nanoparticles led to the preparation of stable ferrofluids.