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Paul A Midgley

Publications and source records attributed to Paul A Midgley.

16 recordsLinked to original sources
PubMed2006

Incorporation of platinum nanoparticles in ordered mesoporous carbon.

Platinum nanoparticles were incorporated within the pore system of ordered mesoporous carbon (OMC) by impregnating the carbon with a water-in-oil (w/o) microemulsion containing dissolved platinum salt followed by reduction of the platinum ions in situ inside the carbon pore system. The procedure provides preparation of metallic nanoparticles from hydrophilic precursors inside the hydrophobic carbon support structure with simultaneous control of the maximum metal particle size. Electron tomography was used to verify the presence of platinum nanoparticles inside the carbon material.

Journal Article↗
PubMed2006

Reducing the missing wedge: High-resolution dual axis tomography of inorganic materials.

Electron tomography is a powerful technique that can probe the three-dimensional (3-D) structure of materials. Recently, this technique has been successfully applied to inorganic materials using Z-contrast imaging in a scanning transmission electron microscope to image nanomaterials in 3-D with a resolution of 1 nm in all three spatial dimensions. However, an artifact intrinsic to this technique limits the amount of information obtainable from any object, namely the missing wedge. One way to circumvent this problem is to acquire data from two perpendicular tilt axes, a technique called "dual axis tomography." This paper presents the first dual axis data at high resolution for inorganic materials, and by studying a CdTe tetrapod sample, demonstrates the increase in information obtained using this technique.

Journal Article↗
PubMed2006

Improved CO oxidation activity in the presence and absence of hydrogen over cluster-derived PtFe/SiO2 catalysts.

The catalytic performance of cluster-derived PtFe/SiO(2) bimetallic catalysts for the oxidation of CO has been examined in the absence and presence of H(2) (PROX) and compared to that of Pt/SiO(2). PtFe(2)/SiO(2) and Pt(5)Fe(2)/SiO(2) samples were prepared from PtFe(2)(COD)(CO)(8) and Pt(5)Fe(2)(COD)(2)(CO)(12) organometallic cluster precursors, respectively. FTIR data indicate that both clusters can be deposited intact on the SiO(2) support. The clusters remained weakly bonded to the SiO(2) surface and could be extracted with CH(2)Cl(2) without any significant changes in their structure. Subsequent heating in H(2) led to complete decarbonylation of the supported clusters at approximately 350 degrees C and the formation of Pt-Fe nanoparticles with sizes in the 1-2 nm range, as indicated by HRTEM imaging. A few larger nanoparticles enriched in Pt were also observed, indicating that a small fraction of the deposited clusters were segregated to the individual components following the hydrogen treatment. A higher degree of metal dispersion and more homogeneous mixing of the two metals were observed during HRTEM/XEDS analysis with the cluster-derived samples, as compared to a PtFe/SiO(2) catalyst prepared through a conventional impregnation route. Furthermore, the cluster-derived PtFe(2)/SiO(2) and Pt(5)Fe(2)/SiO(2) samples were more active than Pt/SiO(2) and the conventionally prepared PtFe/SiO(2) sample for the oxidation of CO in air. However, substantial deactivation was also observed, indicating that the properties of the Pt-Fe bimetallic sites in the cluster-derived samples were altered by exposure to the reactants. The Pt(5)Fe(2)/SiO(2) sample was also more active than Pt/SiO(2) for PROX with a selectivity of approximately 92% at 50 degrees C. In this case, the deactivation with time on stream was substantially slower, indicating that the highly reducing environment under the PROX conditions helps maintain the properties of the active Pt-Fe bimetallic sites.

Journal Article↗
PubMed2006

Crystallographic order in multi-walled carbon nanotubes synthesized in the presence of nitrogen.

Multi-walled carbon nanotubes were synthesized by chemical vapor deposition from pure toluene and toluene/diazine mixtures using ferrocene as a catalyst precursor at 760 degrees C. As recently announced, characterization of the resulting nanotube films showed that, unlike pure carbon nanotubes, those grown in the presence of nitrogen have an extremely high degree of internal order, both in terms of the uniform chirality in the nanotube walls and of the crystallographic register between them. Here, the structure, defects, and morphology of the nanotubes were analyzed in depth using advanced electron microscopy techniques, and compared with existing models and observations. Nitrogen, which seems to be responsible for the dramatic structural order, was found to segregate preferentially within the core of the nanotubes.

Computer Simulation↗
PubMed2006

Four-dimensional spectral tomography of carbonaceous nanocomposites.

There is considerable interest in the adhesion of polymers to carbon nanotubes for nanocomposite applications.(1-4) One example is multiwalled carbon nanotubes (MWCNTs) dispersed in nylon 6,6.(5) We will show that high-contrast tomographic reconstructions can be created from plasmon-loss electrons that show the three-dimensional structural complexity of the MWCNT-nylon composite at the nanoscale. Further, by recording a series of energy-loss images at successive tilts, it is possible to interrogate subvolumes to extract energy-loss spectra from the reconstructed "volume spectra".

Journal Article↗
PubMed2005

Direct visualisation, by aberration-corrected electron microscopy, of the crystallisation of bimetallic nanoparticle catalysts.

Using a scanning transmission electron microscope, corrected for aberration, ultra-high resolution images of the internal structure of nanoparticle clusters, as well as the number of atoms present per cluster, may be directly determined: it is shown that individual bimetallic clusters of Ru10Pt2 have a "molecular" structure and that when they coalesce into larger entities containing ca. 200 atoms they adopt the regular crystalline, and facetted, state of a bulk metal.

Journal Article↗
PubMed2005

Highly anisotropic distribution of iron nanoparticles within MCM-41 Mesoporous Silica.

Electron microscopy techniques are used to visualize the spatial distribution of iron nanoparticles inside a mesoporous MCM-41 molecular sieve. Direct observation of the iron oxide nanoparticles by STEM-HAADF imaging reveals a highly non-uniform spatial distribution inside the mesopores. These particles are retained in the pores after a reduction treatment unlike the behavior found in other similar systems. It is found that thermal treatments induce changes in its morphology, creating nanowires from particle strings.

Image Processing, Computer-Assisted↗
PubMed2005

Conventional and back-side focused ion beam milling for off-axis electron holography of electrostatic potentials in transistors.

Off-axis electron holography is used to characterize a linear array of transistors, which was prepared for examination in cross-sectional geometry in the transmission electron microscope (TEM) using focused ion beam (FIB) milling from the substrate side of the semiconductor device. The measured electrostatic potential is compared with results obtained from TEM specimens prepared using the more conventional 'trench' FIB geometry. The use of carbon coating to remove specimen charging effects, which result in electrostatic fringing fields outside 'trench' specimens, is demonstrated. Such fringing fields are not observed after milling from the substrate side of the device. Analysis of the measured holographic phase images suggests that the electrically inactive layer on the surface of each FIB-milled specimen typically has a thickness of 100 nm.

Journal Article↗
PubMed2005

Off-axis electron holography of unbiased and reverse-biased focused ion beam milled Si p-n junctions.

Off-axis electron holography is used to measure electrostatic potential profiles across a silicon p-n junction, which has been prepared for examination in the transmission electron microscope (TEM) in two different specimen geometries using focused ion beam (FIB) milling. Results are obtained both from a conventional unbiased FIB-milled sample and using a novel sample geometry that allows a reverse bias to be applied to an FIB-milled sample in situ in the TEM. Computer simulations are fitted to the results to assess the effect of TEM specimen preparation on the charge density and the electrostatic potential in the thin sample.

Journal Article↗
PubMed2004

High-resolution transmission electron microscopy: the ultimate nanoanalytical technique.

To be able to determine the elemental composition and morphology of individual nanoparticles consisting of no more than a dozen or so atoms that weigh a few zeptograms (10(-21) g) is but one of the attainments of modern electron microscopy. With slightly larger specimens (embracing a few unit cells of the structure) their symmetry, crystallographic phase, unit-cell dimension, chemical composition and often the valence state (from parallel electron spectroscopic measurements) of the constituent atoms may also be determined using a scanning beam of electrons of ca. 0.5 nm diameter. Nowadays electron crystallography, which treats the digital data of electron diffraction (ED) and high-resolution transmission electron microscope (HRTEM) images of minute (ca. 10(-18)g) specimens in a quantitatively rigorous manner, solves hitherto unknown structures just as X-ray diffraction does with bulk single crystals. In addition, electron tomography (see cover photograph and its animation) enables a three-dimensional picture of the internal structure of minute objects, such as nanocatalysts in a single pore, as well as structural faults such as micro-fissures, to be constructed with a resolution of 1 nm from an angular series of two-dimensional (projected) images. Very recently (since this article was first written) a new meaning has been given to electron crystallography as a result of the spatio-temporal resolution of surface phenomena achieved on a femtosecond timescale.

Journal Article↗
PubMed2003

Extending energy-filtered transmission electron microscopy (EFTEM) into three dimensions using electron tomography.

The length scales on which materials microstructures are being formed, grown, and even designed are becoming increasingly small and increasingly three-dimensional. For such complex structures two-dimensional transmission electron microscopy (TEM) analysis is often inadequate and occasionally misleading. One approach to this problem is the modification of electron tomography techniques, developed for structural biology, for use in materials science. Energy-Filtered (EF) TEM elemental distribution images approximate to true projections of structure, and, as such, can be used to reconstruct the three-dimensional distribution of chemical species. A sample holder has been modified to allow the high tilt (+/-60 degrees ) required for tomography and a semiautomatic acquisition script designed to manage energy-loss acquisition. Tilt series data sets have been acquired from two widely different experimental systems, Cr carbides in 316 stainless steel and magnetite nanocrystals in magnetotactic bacteria, demonstrating single- and multiple-element tomography. It is shown that both elemental maps and jump-ratio images are suitable for reconstruction, despite the effects of diffraction contrast in the former and thickness changes in the latter. It is concluded that the image contrast, signal, and signal-to-noise ratio (SNR) are key to the achievable reconstruction quality and, as such, the technique may be of limited value for high energy loss/small inelastic cross section edges.

Electrons↗
PubMed2003

High-performance nanocatalysts for single-step hydrogenations.

Bimetallic nanoparticles (Ru(6)Pd(6), Ru(6)Sn, Ru(10)Pt(2), Ru(5)Pt, Ru(12)Cu(4), and Ru(12)Ag(4)) anchored within silica nanopores exhibit high activities and frequently high selectivities, depending upon the composition of the nanocatalyst, in a number of single-step (and often solvent-free) hydrogenations at low temperatures (333-373 K). The selective hydrogenations of polyenes (such as 1,5,9-cyclododecatriene and 2,5-norbornadiene) are especially efficient. Good performance is found with these nanoparticle catalysts in the hydrogenation of dimethyl terephthalate to 1,4 cyclohexanedimethanol and of benzoic acid to cyclohexanecarboxylic acid or to cyclohexene-1-carboxylic acid, and also in the conversion of benzene to cyclohexene (or cyclohexane), the latter being an increasingly important reaction in the context of the production of Nylon. Isolated atoms of noble metals (Pd, Rh, and Pt) in low oxidation states, appropriately complexed and tethered to the inner walls of nanoporous (ca. 3 nm diameter) silica, are very promising enantioselective hydrogenation catalysts. Nanoporous carbons, as well as other nanoporous oxides, may also be used to anchor and tether the kind of catalysts described here.

Journal Article↗
PubMedDate not supplied

Charge-ordered ferromagnetic phase in La(0.5)Ca(0.5)MnO3.

Mixed-valent manganites are noted for their unusual magnetic, electronic and structural phase transitions. For example, the La(1-x)Ca(x)MnO(3) phase diagram shows that below transition temperatures in the range 100-260 K, compounds with 0.2 < x < 0.5 are ferromagnetic and metallic, whereas those with 0.5 < x < 0.9 are antiferromagnetic and charge ordered. In a narrow region around x = 0.5, these totally dissimilar ground states are thought to coexist. It has been shown that charge order and charge disorder can coexist in the related compound, La(0.25)Pr(0.375)Ca(0.375)MnO(3). Here we present electron microscopy data for La(0.5)Ca(0.5)MnO(3) that shed light on the distribution of these coexisting phases, and uncover an additional, unexpected phase. Using electron holography and Fresnel imaging, we find micrometre-sized ferromagnetic regions spanning several grains coexisting with similar-sized regions with no local magnetization. Holography shows that the ferromagnetic regions have a local magnetization of 3.4 +/- 0.2 Bohr magnetons per Mn atom (the spin-aligned value is 3.5 micro (B) per Mn). We use electron diffraction and dark-field imaging to show that charge order exists in regions with no net magnetization and, surprisingly, can also occur in ferromagnetic regions.

Journal Article↗