John B. Claridge

Recent advances in the conversion of methane to synthesis gas

Abstract A brief review on the recent developments of alternative routes for synthesis gas production, namely catalytic methane partial oxidation and methane reforming with carbon dioxide, is presented. Particular attention is given to reaction thermodynamics, catalyst formulation, reaction mechanism and problems of carbon deposition.

An Adaptable Peptide-Based Porous Material

Swelling Pores Porosity is a key parameter when selecting materials for catalysts, chemical separations, gas storage, host-guest interactions, and related chemical processes. In most cases the porosity of a material is fixed. Rabone et al. (p. 1053; see the Perspective by Wright) have described a molecular material in which the size of the pores changed during the sorption process. The porosity increased because a dipeptide linker between metal centers reoriented during uptake of some gases, thus improving the capacity of the material to adsorb. Conformational changes in a porous material during the sorption of small molecules lead to a dynamic increase in porosity. Porous materials find widespread application in storage, separation, and catalytic technologies. We report a crystalline porous solid with adaptable porosity, in which a simple dipeptide linker is arranged in a regular array by coordination to metal centers. Experiments reinforced by molecular dynamics simulations showed that low-energy torsions and displacements of the peptides enabled the available pore volume to evolve smoothly from zero as the guest loading increased. The observed cooperative feedback in sorption isotherms resembled the response of proteins undergoing conformational selection, suggesting an energy landscape similar to that required for protein folding. The flexible peptide linker was shown to play the pivotal role in changing the pore conformation.

A study of carbon deposition on catalysts during the partial oxidation of methane to synthesis gas

The deposition of carbon on catalysts during the partial oxidation of methane to synthesis gas has been investigated and it has been found that the relative rate of carbon deposition follows the order Ni>Pd>Rh>Ir. Methane decomposition was found to be the principal route for carbon formation over a supported nickel catalyst, and electron micrographs showed that both “whisker” and “encapsulate” forms of carbon are present on the catalyst. Negligible carbon deposition occurred on iridium catalysts, even after 200 h.

Methane Oxyforming for Synthesis Gas Production

This article is concerned with the reforming of methane to synthesis gas; a review of the steam reforming Rxn is presented, and the dry reforming and partial oxidation Rxns introduced. Collectively, these processes are known as “oxyforming.” A background to oxyforming, industrial practice, and some of the most important latest developments will be presented, along with a section on the uses of synthesis gas. The current understanding of the Rxn mechanisms for the three processes and the problem of deactivation by carbon deposition will be discussed in detail. Finally, the economics of synfuel production will be addressed and compared with the production of other fuels, and the future directions and outlook for oxyforming will be forwarded. This article should allow the reader to make comparisons between these three important industrial reactions.

The size distribution, imaging and obstructing properties of C60 and higher fullerenes formed within arc-grown single walled carbon nanotubes

Abstract The relative size distributions of molecules of C60 and higher fullerenes observed in single walled carbon nanotubes (SWNTs) produced by arc vaporization of carbon in the presence of a mixed Ni/Y catalyst are described. The experimental and calculated imaging properties of the fullerenes, which were observed in ca. 5–10% of SWNTs, are also described. The in situ e-beam irradiation in a 300 kV field emission gun transmission electron microscope causes rapid coalescence of the fullerenes within the SWNTs. The incorporated fullerenes also directly impede crystal growth in SWNTs when their cavities are filled by the liquid phase capillary method.

Interstitial oxide ion conductivity in the layered tetrahedral network melilite structure

High-conductivity oxide ion electrolytes are needed to reduce the operating temperature of solid-oxide fuel cells. Oxide mobility in solids is associated with defects. Although anion vacancies are the charge carriers in most cases, excess (interstitial) oxide anions give high conductivities in isolated polyhedral anion structures such as the apatites. The development of new families of interstitial oxide conductors with less restrictive structural constraints requires an understanding of the mechanisms enabling both incorporation and mobility of the excess oxide. Here, we show how the two-dimensionally connected tetrahedral gallium oxide network in the melilite structure La(1.54)Sr(0.46)Ga(3)O(7.27) stabilizes oxygen interstitials by local relaxation around them, affording an oxide ion conductivity of 0.02-0.1 S cm(-1) over the 600-900 degrees C temperature range. Polyhedral frameworks with central elements exhibiting variable coordination number can have the flexibility needed to accommodate mobile interstitial oxide ions if non-bridging oxides are present to favour cooperative network distortions.

Dry reforming of methane to synthesis gas over supported molybdenum carbide catalysts

The dry reforming of methane at elevated pressure over supported molybdenum carbide catalysts, prepared from oxide precursors using ethane TPR, has been studied. The relative stability of the catalysts is Mo2C/Al2O3>Mo2C/ZrO2>Mo2C/SiO2>Mo2C/TiO2, and calcination of the oxide precursor for short periods was found to be beneficial to the catalyst stability. Although the support appears to play no beneficial role in the methane dry reforming reaction, the alumina-supported material was stable for long periods of time; this may be important for the production of pelletised industrial catalysts. The evidence suggests that the differences in the stabilities may be due to interaction at the precursor stage between MoO3 and the support, while catalyst deactivation is due to oxidation of the carbide to MoO2, which is inactive for methane dry reforming.

Tilt engineering of spontaneous polarization and magnetization above 300 K in a bulk layered perovskite

Tilting toward two properties Opposing electronic and symmetry constraints can make it difficult to combine some pairs of material properties in a single crystalline material. Magnetization and electrical polarization are such a pair, but their combination could be useful for applications such as magnetoelectric information storage. Pitcher et al. now show that careful design of chemical substitutions in a layered perovskite are both electrically polar and weakly ferromagnetic at temperatures up to 330 K. Science, this issue p. 420 Chemical substitutions produce atomic displacements in a crystal that lead to both electrical polarization and magnetization. Crystalline materials that combine electrical polarization and magnetization could be advantageous in applications such as information storage, but these properties are usually considered to have incompatible chemical bonding and electronic requirements. Recent theoretical work on perovskite materials suggested a route for combining both properties. We used crystal chemistry to engineer specific atomic displacements in a layered perovskite, (CaySr1–y)1.15Tb1.85Fe2O7, that change its symmetry and simultaneously generate electrical polarization and magnetization above room temperature. The two resulting properties are magnetoelectrically coupled as they arise from the same displacements.

High-resolution electron microscopy studies of a microporous carbon produced by arc-evaporation

The soot produced as a byproduct of fullerene synthesis by arc-evaporation consists of a microporous carbon with a surface area, after activation with carbon dioxide, of ca. 700 m2 g–1. Here, we investigate the structure of this material, and its appearance after electron irradiation and high-temperature heat treatment, using high-resolution electron microscopy. We show that the heat treatment transforms the new carbon into a structure containing large, tube-like pores, rather than into polycrystalline graphite. This suggests that the arc-evaporated carbon may have a novel, fullerene-related microstructure, and that it may be the precursor for nanotube formation.

Visible Light Photo-oxidation of Model Pollutants Using CaCu3Ti4O12: An Experimental and Theoretical Study of Optical Properties, Electronic Structure, and Selectivity

Charge transfer between metal ions occupying distinct crystallographic sublattices in an ordered material is a strategy to confer visible light absorption on complex oxides to generate potentially catalytically active electron and hole charge carriers. CaCu3Ti4O12 has distinct octahedral Ti4+ and square planar Cu2+ sites and is thus a candidate material for this approach. The sol−gel synthesis of high surface area CaCu3Ti4O12 and investigation of its optical absorption and photocatalytic reactivity with model pollutants are reported. Two gaps of 2.21 and 1.39 eV are observed in the visible region. These absorptions are explained by LSDA+U electronic structure calculations, including electron correlation on the Cu sites, as arising from transitions from a Cu-hybridized O 2p-derived valence band to localized empty states on Cu (attributed to the isolation of CuO4 units within the structure of CaCu3Ti4O12) and to a Ti-based conduction band. The resulting charge carriers produce selective visible light photodegradation of 4-chlorophenol (monitored by mass spectrometry) by Pt-loaded CaCu3Ti4O12 which is attributed to the chemical nature of the photogenerated charge carriers and has a quantum yield comparable with commercial visible light photocatalysts.