Timothy John White

Biphasic Pd−Au Alloy Catalyst for Low-Temperature CO Oxidation

Low-temperature CO oxidation over a compositional series of Pd-Au nanoalloy catalysts supported on silica fume was studied. Except for the pure metals, these materials invariably showed biphasic separation into palladium- and gold-rich components. Performance was optimal for a catalyst of bulk composition Pd(4)Au(1), a mixture of Pd(90)Au(10) (72.5 at. %) and Pd(31)Au(69) (27.5 at. %), that was remarkably active at 300 K and more stable than a pure Au catalyst. For bulk materials dominated by Pd (Pd:Au = 16:1; 8:1; 4:1), the palladium-rich alloy fraction frequently adopted hollow sphere or annular morphology, while the gold-rich crystals were often multiply twinned. Quantitative powder X-ray diffraction (XRD) showed that under the synthesis conditions used, the Au solubility limit in Pd crystals was approximately 12 at. %, while Pd was more soluble in Au (approximately 31 at. %). This was consistent with X-ray photoelectron spectroscopy (XPS), which revealed that the surfaces of Pd-rich alloys were enriched in gold relative to the bulk composition. In situ Fourier transform infrared spectra collected during CO oxidation contained a new band at 2114 cm(-1) (attributed to linear CO-Au/Au-Pd bonds) and reduced intensity of a band at 2090 cm(-1) (arising from a linear CO-Pd bond) with escalating Au content, indicating that the Pd sites became increasingly obscured by Au. High-resolution electron micrographs (HRTEM) of the Pd-rich alloys revealed atomic scale surface defects consistent with this interpretation. These results demonstrate that gold-containing biphasic Pd nanoalloys may be highly durable alternatives for a range of catalytic reactions.

Structural derivation and crystal chemistry of apatites

The crystal structures of the [A(1)(2)][A(2)(3)](BO(4))(3)X apatites and the related compounds [A(1)(2)][A(2)(3)](BO(5))(3)X and [A(1)(2)][A(2)(3)](BO(3))(3)X are collated and reviewed. The structural aristotype for this family is Mn(5)Si(3) (D8(8) type, P6(3)/mcm symmetry), whose cation array approximates that of all derivatives and from which related structures arise through the systematic insertion of anions into tetrahedral, triangular or linear interstices. The construction of a hierarchy of space-groups leads to three apatite families whose high-symmetry members are P6(3)/m, Cmcm and P6(3)cm. Alternatively, systematic crystallographic changes in apatite solid-solution series may be practically described as deviations from regular anion nets, with particular focus on the O(1)-A(1)-O(2) twist angle phi projected on (001) of the A(1)O(6) metaprism. For apatites that contain the same A cation, it is shown that phi decreases linearly as a function of increasing average ionic radius of the formula unit. Large deviations from this simple relationship may indicate departures from P6(3)/m symmetry or cation ordering. The inclusion of A(1)O(6) metaprisms in structure drawings is useful for comparing apatites and condensed-apatites such as Sr(5)(BO(3))(3)Br. The most common symmetry for the 74 chemically distinct [A(1)(2)][A(2)(3)](BO(4))(3)X apatites that were surveyed was P6(3)/m (57%), with progressively more complex chemistries adopting P6(3) (21%), P3; (9%), P6 (4.3%), P2(1)/m (4.3%) and P2(1) (4.3%). In chemically complex apatites, charge balance is usually maintained through charge-coupled cation substitutions, or through appropriate mixing of monovalent and divalent X anions or X-site vacancies. More rarely, charge compensation is achieved through insertion/removal of oxygen to produce BO(5) square pyramidal units (as in ReO(5)) or BO(3) triangular coordination (as in AsO(3)). Polysomatism arises through the ordered filling of [001] BO(4) tetrahedral strings to generate the apatite-nasonite family of structures.

Nomenclature of the apatite supergroup minerals

The apatite supergroup includes minerals with a generic chemical formula IX M12 VII M23( IV TO4)3 X( Z ¼ 2); chemically they can be phosphates, arsenates, vanadates, silicates, and sulphates. The maximum space group symmetry is P63/m, but several members of the supergroup have a lower symmetry due to cation ordering and deviations from the ideal topology, which may result in an increase of the number of the independent sites. The apatite supergroup can be formally divided into five groups, based on crystal-chemical arguments: apatite group, hedyphane group, belovite group, britholite group, and ellestadite group. The abundance of distinct ions which may be hosted at the key-sites (M ¼ Ca 2þ , Pb 2þ , Ba 2þ , Sr 2þ , Mn 2þ , Na þ , Ce 3þ , La 3þ ,Y 3þ , Bi 3þ ;T ¼ P 5þ , As 5þ ,V 5þ , Si 4þ ,S 6þ ,B 3þ ;X ¼ F � , (OH) � , Cl � ) result in a large number of compositions which may have the status of distinct mineral species. Naming of apatite supergroup minerals in the past has resulted in nomenclature inconsistencies and problems. Therefore, an ad hoc IMA-CNMNC Subcommittee was established with the aim of rationalizing the nomenclature within the apatite supergroup and making some order among existing and potentially new mineral species. In addition to general recommendations for the handling of chemical (EPMA) data and for the allocation of ions within the various sites, the main recommendations of this subcommittee are the following: 1. Nomenclature changes to existing minerals. The use of adjectival prefixes for anions is to be preferred instead of modified Levinson suffixes; accordingly, six minerals should be renamed as follows: apatite-(CaF) to fluorapatite, apatite-(CaOH) to hydroxylapatite, apatite-(CaCl) to chlorapatite, ellestadite-(F) to fluorellestadite, ellestadite-(OH) to hydroxylellestadite, phospho- hedyphane-(F) to fluorphosphohedyphane. For the apatite group species these changes return the names that have been used in thousands of scientific paper, treatises and museum catalogues over the last 150 years. The new mineral IMA 2008-009, approved without a name, is here named stronadelphite. Apatite-(SrOH) is renamed fluorstrophite. Deloneite-(Ce) is renamed deloneite. The new mineral IMA 2009-005 is approved with the name fluorbritholite-(Y).

Gadolinium oxide ultranarrow nanorods as multimodal contrast agents for optical and magnetic resonance imaging.

We demonstrate a simple synthetic strategy for the fabrication of single-phase rare earth (RE) doped gadolinium oxide (Gd(2)O(3):RE where RE = terbium (Tb), ytterbium (Yb), and erbium (Er)) nanorods (NRs) as multimodal imaging probes. The NRs are ultranarrow and exhibit both emission and magnetic characteristics. The Tb-doped and Yb/Er-codoped Gd(2)O(3) NRs exhibit down- and up-conversion fluorescence respectively, and also exhibit paramagnetism. Importantly, these codoped NRs possess excellent magnetic characteristics, as shown in their longitudinal relaxation time (T1) -weighted image contrast, which is closer to that of commercial Gadovist for magnetic resonance imaging (MRI) applications. This property opens up new avenues in the development of contrast agents.

A combined single crystal neutron/X-ray diffraction and solid-state nuclear magnetic resonance study of the hybrid perovskites CH3NH3PbX3 (X = I, Br and Cl)

The 1H and 13C NMR spectra in methylammonium lead halide perovskites, CH3NH3PbX3 (X = I, Br and Cl) show that the CH3NH3+ units undergo dynamic reorientation, as the organic component tumbles in the perovskite cage. In addition, the differences in the anomalously long relaxation times of the protons associated with the CH3 and not the NH3 groups indicate that only the amine end of the CH3NH3+ group is interacting with the inorganic network. Using this information, we have refined some single crystal X-ray and neutron diffraction data to probe their unusual structures in more detail. Furthermore, impedance spectroscopy has been used to monitor the high-temperature phase transition of CH3NH3PbI3, which confirms a significant increase in conductivity, when it is in its high temperature and higher symmetry structural regime. The optical band-gaps of each halide perovskite were determined using UV-visible spectroscopy and are consistent with previous reports.

Transparent nanohybrids of nanocrystalline TiO2 in PMMA with unique nonlinear optical behavior

PMMA is one of the most versatile polymeric materials for applications in various technological areas including optics and electro-optics. While the current applications of PMMA in optics and electro-optics are limited by their linear optical behavior, we report here in this paper the unique nonlinear optical behavior of nanohybrids consisting of nanocrystalline TiO2 in PMMA. Transparent thin films of TiO2–PMMA nanohybrid on substrates were synthesized by in-situ sol–gel and polymerisation, assisted by spin coating. Using titanium isoproproxide (Ti-iP) as the starting material for nanocrystalline titania, together with methyl methacrylate and 3-(trimethoxysilyl)propyl methacrylate, nanohybrids containing up to 80% Ti-iP in PMMA were successfully realized. The resulting nanohybrid thin films coated on quartz substrates are optically transparent and demonstrate large nonlinear optical behavior, with an ultrafast response of <1.5 ps. The highest two-photon absorption coefficient (β) and nonlinear refractive index (n2) are observed with the nanohybrid thin film of 60 wt% Ti-iP in PMMA, as confirmed by the Z-scan technique.

Controlling the crystallinity and nonlinear optical properties of transparent TiO2–PMMA nanohybrids

Titania–polymer nanohybrid thin films represent a new class of potential materials for optoelectronic applications. While most such nanohybrid thin films lack control in crystallinity, we report in this paper transparent nanohybrids of titania-polymethyl methacrylate (TiO2–PMMA) thin films having a remarkably enhanced nanocrystallinity. Post-treatments with water vapor at relatively low temperatures were applied on these thin films, following in situ sol–gel polymerization. They promoted rearrangement of flexible Ti–O–Ti bonds leading to enhanced crystallization of the TiO2 phase. The degree of TiO2 crystallinity in the resulting nanohybrid films was studied by using XRD, FTIR, UV–Vis spectroscopies and HRTEM. Both linear and nonlinear optical responses increase with the enhancement of TiO2 crystallinity in the nanohybrids. The highest two-photon absorption coefficient (β) and nonlinear refractive index (n2) were observed for the nanohybrid thin films with highest TiO2 crystallinity, as confirmed by open and closed aperture Z-scan techniques using 250 fs laser pulses at 800 nm, having a value of 2260 cm GW−1 and 6.2 × 10−2 cm2 GW−1, respectively.

Compositional and structural alteration of pyrrhotite surfaces in solution: XPS and XRD studies

Ground pyrrhotite (Fe1−xS) surfaces oxidised by exposure to (i) air, (ii) water and (iii) de-oxygenated perchloric acid solution (0.05–1M) were examined using X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). In air or water, the surfaces form amorphous layers containing carbonate species; sulfate species; iron(III) oxide/hydroxides; and an iron-deficient sulfide species with an S(2p) doublet shifted 1.0–1.8 eV to higher binding energy (BE). After acid reaction, the surface partly restructures to a crystalline, defective tetragonal Fe2S3 product in which linear chains of Sn atoms have a S-S distance similar to elemental sulfur (S8) but the S(2p) BE is still 0.2–0.6 eV less than S8. Initially, the acid-reacted surface may be partly hydrophobic, giving flotation separation, but, as oxidation proceeds, hydrophilic iron hydroxides deposit on the surface depressing flotation. The chemical forms of Fe and S in the surface layers are discussed in detail with changes in the proportion of the oxidised and iron-deficient sulfide products.

Large-scale preparation of carbon-encapsulated cobalt nanoparticles by the catalytic method

With strategical selection of the water-soluble sodium chloride (NaCl) as the supporting material, we realized largescale production of carbon-encapsulated cobalt nanoparticles with a productivity of almost 100%. The products can be fully separated from the supporting materials by simple washing process. When NaCl, NaF and Al2O3 were used as supporting materials, the morphologies of the carbon products changed from carbon-encapsulated magnetic nanoparticles (CEMNs) to an intermediate state (quasi-nanocages) between CEMNs and carbon nanotubes (CNTs), and then to CNTs, respectively. NaCl shows strong inhibiting effects on the growth of CNTs, favoring the formation of CEMNs. 2002 Published by Elsevier Science B.V.

Deposition of titanium nitride thin films on stainless steel—AISI 304 substrates using a plasma focus device

Abstract A 3.3 kJ pulsed plasma focus device was used to deposit thin films of titanium nitride (TiN) at room temperature onto the stainless steel—AISI 304 substrates. The small plasma focus device, fitted with solid titanium anode instead of the usual hollow copper anode, was operated with nitrogen as the filling gas for deposition of TiN thin films. Films were deposited with different numbers of focus shots, at different distances from the top of the anode, and at different angular positions with respect to the anode axis. Deposited films have been characterized for their structure by X-ray diffractometry (XRD), surface morphology by scanning electron microscopy (SEM), elemental composition and distribution mapping by energy dispersive X-ray (EDX) analysis and hardness using a nanoindenter. XRD patterns show the growth of as-deposited polycrystalline TiN thin film. Diffraction patterns for films deposited along the anode axis show induction of a phase corresponding to iron chromium nickel on the film–substrate interface. SEM pictures confirm uniformly distributed TiN grains with hardly any crack over the film surface. Conglomeration of smaller TiN grains, to form bigger size grains, is seen to occur at the films deposited with higher total ion flux. The EDX spectra show the presence of expected constituent elements. EDX mapping confirms the uniform distribution of TiN on the film surface. The variation in structure, morphology, thickness and hardness of the deposited films with the variation of film deposition parameters is explained, qualitatively, on the basis of ion emission characteristics of the focus device. Polycrystalline, smooth and hard thin films of TiN are successfully deposited at room temperature stainless steel—AISI 304 substrates using the plasma focus device.