The octahedral sheet of metamorphic 2M1-phengites: A combined EMPA and AXANES study

Two types of metamorphic phengites are known: one is linked to high pressure and is 3T; the other is 2M{sub 1}, and its composition is linked to rock-compositional constraints. This work investigates the octahedral sheet crystal-chemical differences between the two phengite types. Seven dioctahedral micas were studied: (1) one 3T phengite from an ultrahigh-pressure metagranitoid in the Dora Maira massif, Italy (P {approx} 4.3 GPa, T {approx} 730 C); (2) five 2M{sub 1} phengites from medium-P orthogneisses in the Eastern Alps metamorphic basement, Italy (P {le} 0.7 GPa, T {approx} 500-600 C); and (3) one 2M{sub 1} ferroan muscovite from pegmatite in Antarctica (P {le} 0.2 GPa, T {approx}500 C). All micas display significant extents of celadonite substitution. In particular, the 2M{sub 1}-phengite formulae (calculated on the basis of 11 O) have 0.68 < {sup IV}Al < 0.82 atoms per formula unit (apfu); octahedral atoms are dominated by Al (1.6-1.8 apfu), with minor and variable Fe (0.20-0.35 apfu) and Mg (0.05-0.17 apfu), and very minor Ti, Mn, and Cr. Total octahedral occupancies are slightly above 2.00 apfu, i.e., there seems to be partial occupancy of the third M site. For all micas, we recorded XAFS spectra on mosaics of carefullymore » separated flakes oriented flat on a plastic support that could be rotated so as to account for the polarization of the synchrotron radiation beam, and we processed them on the basis of the AXANES theory. Spectra show angle-dependent absorption variations for Al and Fe, which can be deconvoluted and fitted by dichroic effects. Pre-edges consistently show most Fe to be Fe{sup 3+} and little angle-dependent intensity variations. The 2M{sub 1}-ferroan muscovite from Antarctica displays the same AXANES behavior as 2M{sub 1}-phengites. By contrast, the ultrahigh-pressure 3T-phengite from Dora Maira (having {sup IV}Al = 0.42 apfu, and Al and Mg as the dominant octahedral constituents) has XAFS spectra that differ significantly. Not only is the {sup IV}Al feature strongly reduced, in agreement with the increased Si content, but also Fe XAFS spectra show one broad feature only, indicating that all Fe is Fe{sup 2+} in a fully disordered distribution with no angle-dependent variations. We conclude that this 3T-phengite is actually contaminated by exsolved Fe-bearing pyrope platelets, which cannot be resolved under SEM examination; by contrast, the 2M{sub 1}-phengites, unrelated to high-pressure, suggest Al/Fe{sup 3+} order over the M1 and (M2, M3) sites, as also does the 2M{sub 1} pegmatitic muscovite.« les

Interlayer potassium and its neighboring atoms in micas : Crystal-chemical modeling and XANES spectroscopy

A detailed description of the interlayer site in trioctahedral true micas is presented based on a statistical appraisal of crystal-chemical, structural, and spectroscopic data determined on two sets of trioctahedral micas extensively studied by both X-ray diffraction refinement on single crystals (SC-XRD) and X-ray absorption fine spectroscopy (XAFS) at the potassium K -edge. Spectroscopy was carried out on both random powders and oriented cleavage flakes, the latter setting taking advantage of the polarized character of synchrotron radiation. Such an approach (AXANES) is shown to be complementary to crystal-chemical investigation based on SC-XRD refinement. However, the results are not definitive as they focus on few samples having extreme features only (e.g., end-members, unusual compositions, and samples with extreme and well-identified substitution mechanisms). The experimental absorption K -edge (XANES) for potassium was decomposed by calculation and extrapolated into a full in-plane absorption component (σ||) and a full out-of-plane absorption component (σ⊥). These two patterns reflect different structural features: σ|| represents the arrangement of the atoms located in the mica interlayer space and facing tetrahedral sheets; σ⊥ is associated with multiple-scattering interactions entering deep into the mica structure, thus also reflecting interactions with the heavy atoms (essentially Fe) located in the octahedral sheet. The out-of-plane patterns also provide insights into the electronic properties of the octahedral cations, such as their oxidation states (e.g., Fe2+ and Fe3+) and their ordering (e.g., trans - vs. cis -setting). It is also possible to distinguish between F- and OH-rich micas due to peculiar absorption features originating from the F vs. OH occupancy of the O4 octahedral site. Thus, combining crystal-chemical, structural, and spectroscopic information is shown to be a practical method that allows, on one hand, assignment of the observed spectroscopic features to precise structural pathways followed by the photoelectron within the mica structure and, on the other hand, clarification of the amount of electronic interactions and forces acting onto the individual atoms at the various structural sites

The interlayer structure of trioctahedral lithian micas: An AXANES spectroscopy study at the potassium K-edge

abstra C t We recorded angle-dependent XANES (AXANES) spectra at the potassium K-edge for three compositionally intermediate polylithionite-siderophyllite trioctahedral 1 M-micas using polarized synchrotron radiation. We evaluated the experimental spectra for both their in-plane and out-of-plane component fractions of the electric dipole contribution using the analytical formulae of Brouder (1990), referring to theory to extract the origin of their multiple-scattering pathways of Natoli et al. (2003). This analysis was extended to a fourth lithian mica studied previously and allowed characterization of the local environment and ordering around the potassium atoms in the interlayer of the entire set of micas. The AXANES in-plane components are notably similar to the XANES spectra recorded on randomly oriented powders, provided these are oriented at the "magic angle" (Pettifer et al. 1992). Most observed contributions arise from multiple-scattering interactions of the photoelectron ejected from the potassium absorber colliding with atoms located in the interlayer itself. Note that this includes not only interactions with other coplanar potassium and/or alkali atoms distributed along the interlayer plane, but also with their near- and next-nearest neighboring oxygen atoms which lie on the basal planes of the tetrahedral sheets facing the interlayer. By contrast, the AXANES out-of-plane component suggests that several multiple-scattering pathways cross the energetic and structural barrier represented by the tetrahedral sheets. They reach not only the X anions that are located on the upper level of the octahedral sheets, at the center of the open cavity in the tetrahedral sheet, but also the metal cations centering the octahedral sheet itself. Therefore, the out-of-plane components provide indirect information on the number of independent octahedral sites, the cation oxidation state, and the trans- vs. cis-orientation of the anionic sites

Next-near-neighbour interactions with Al in Li+- and Rb+-exchanged Na+ β-aluminas, detected by synchrotron X-ray absorption spectroscopy

Synchrotron X-ray absorption near-edge structure (XANES) spectroscopy studies have been carried out on the electronic and crystal structure environments around the Al atom in Na+β-alumina and in two β-aluminas with Na+exchanged by Li+and Rb+. The aim is to define the type of interaction, if any, existing between the Al located in the `spinel block' and the fast-conducting cations in the `conduction plane'. Na+β′′-alumina has also been studied for comparison. All β-alumina spectra differ from that of α-alumina (corundum) by showing additional features due to the presence of tetrahedral Al. Moreover, they all show a much greater degree of local disorder. There are definite, but small, interactions between tetrahedral Al (and, possibly, also octahedral Al) in the `spinel block' and the Na+and Rb+cations in the `conduction plane'; Na+and Rb+β-aluminas have similar AlK-edge XANES features, but with intensities that change in relation to the weight of the `conduction plane' atom. Despite differences in composition and structure, Na+β′′-alumina shows the same behaviour, thus confirming the substantial similarity of the Al local environments. Li+-exchanged β-alumina has an AlK-edge XANES spectrum that apparently differs from all others, but actually conveys the same basic information. Indeed, interaction between Al and Li is much greater than in any other β-alumina because Li+moves laterally off the `conduction plane' to become close to a facing tetrahedral Al, and strongly interacts with it. Thus, this study also draws attention to the fact that β-aluminas react differently to alkali exchange

Selective oxidation of biomass-derived 5‑hydroxymethylfurfural catalyzed by an iron-grafted metal–organic framework with a sustainably sourced ligand

The efficient conversion of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is a major challenge under base-free conditions with inexpensive catalysts. We report a precious-metal-free recyclable MOF-based catalyst (CAU-28), constructed from the FDC ligand, with grafted redox-active Fe sites. This enables the conversion of HMF to FDCA under solvothermal heating or microwave-assisted methods in base-free aqueous conditions. The optimized process achieves 100% HMF conversion producing FDCA at the gram scale with a 70–80% yield in 1 h. The turnover frequency (TOF) and cost-normalized TOF for the best catalyst are >800 h–1 and >1000 h–1 £–1, respectively, surpassing those of conventional catalysts and processes using precious elements or basic additives for HMF conversion. The economic viability and practical applicability of the process are further realized by utilizing the catalytically derived FDCA (without purification) for the successful construction of pristine CAU-28 MOFs and formation of the biodegradable plastic polyethylene furanoate (PEF) after purification

Influence of the Cation on the Reaction Mechanism of Sodium Uptake and Release in Bivalent Transition Metal Thiophosphate Anodes: A Case Study of Fe2_2P2_2S6_6

The layered active material Fe$_2$P$_2$S$_6$ was examined as anode material in sodium-ion batteries (SIBs) and compared to previously investigated Ni$_2$P$_2$S$_6$. A reversible specific capacity of 540 mAh g$^{−1}$ was achieved after 250 cycles, depicting similar electrochemical performance as observed for Ni$_2$P$_2$S$_6$. The rate capability and long-term behavior of these two materials are also very similar. Another objective was to elucidate the reaction mechanism during discharging and charging by applying several techniques such as X-ray diffraction, pair distribution function analysis as well as X-ray absorption and solid state NMR spectroscopy. The results clearly demonstrate that the majority of Fe$^{2+}$ is reduced to elemental Fe during the uptake of 5 Na/f.u., while an amorphous intermediate is generated, which was identified as Na$_4$P$_2$S$_6$ by solid state NMR spectroscopy. Completely discharging against a Na metal counter electrode leads to the formation of nanocrystalline Na$_2$S and indications of the formation of polymeric phosphorus were found. In sum, the Na uptake reaction process observed for Fe$_2$P$_2$S$_6$ coincides with the previously unraveled reaction pathway of Ni$_2$P$_2$S$_6$. We therefore conclude that a universal reaction takes places for bivalent transition metal thiophosphate (M$_2$P$_2$S$_6$) electrodes in SIBs

Letter. On the activation of [CrCl3{R-SN(H)S-R}] catalysts for selective trimerization of ethene: a freeze-quench Cr K-edge XAFS study

Homogeneous chromium catalysts for the selective conversion of ethene to hex-1-ene are formed from Cr(III) reagents, amino-thioether ligands of the type HN(CH2CH2SR)2, and aluminum reagents. In this study the early activation steps are investigated by EPR, UV-visible and Cr K-edge XAFS spectroscopy; rapid stopped-flow mixing and a freeze-quench allows good quality EXAFS analysis of a species formed in ~ 1 second of reaction. This is shown to involve reduction to Cr(II) and deprotonation of a NH group of the auxiliary ligand. This 4-coordinate metal-center may act as precursor for the coordination of ethene and subsequent selective oligomerization

Niobium tungsten oxides for high-rate lithium-ion energy storage.

The maximum power output and minimum charging time of a lithium-ion battery depend on both ionic and electronic transport. Ionic diffusion within the electrochemically active particles generally represents a fundamental limitation to the rate at which a battery can be charged and discharged. To compensate for the relatively slow solid-state ionic diffusion and to enable high power and rapid charging, the active particles are frequently reduced to nanometre dimensions, to the detriment of volumetric packing density, cost, stability and sustainability. As an alternative to nanoscaling, here we show that two complex niobium tungsten oxides-Nb16W5O55 and Nb18W16O93, which adopt crystallographic shear and bronze-like structures, respectively-can intercalate large quantities of lithium at high rates, even when the sizes of the niobium tungsten oxide particles are of the order of micrometres. Measurements of lithium-ion diffusion coefficients in both structures reveal room-temperature values that are several orders of magnitude higher than those in typical electrode materials such as Li4Ti5O12 and LiMn2O4. Multielectron redox, buffered volume expansion, topologically frustrated niobium/tungsten polyhedral arrangements and rapid solid-state lithium transport lead to extremely high volumetric capacities and rate performance. Unconventional materials and mechanisms that enable lithiation of micrometre-sized particles in minutes have implications for high-power applications, fast-charging devices, all-solid-state energy storage systems, electrode design and material discovery.K.J.G. gratefully acknowledges support from The Winston Churchill Foundation of the United States, the Herchel Smith Scholarship, and the Science and Technology Facilities Council Futures Early Career Award. K.J.G and C.P.G thank the EPSRC via the LIBATT grant (EP/P003532/1). L.E.M. was funded by the European Union’s Horizon 2020 – European Union research and innovation program under the Marie Skłodowska–Curie grant agreement No. 750294. We thank Dr. Ieuan Seymour, University of Cambridge, and Prof. Bruce Dunn, University of California, Los Angeles, for fruitful discussions. We thank Drs. Jeremy Skepper and Heather Greer, University of Cambridge, for assistance with the electron microscopy and Dr. Maxim Avdeev, Bragg Institute, for his bond valence sum mapping program. We thank Dr. Olaf Borkiewicz, Advanced Photon Source, Argonne National Laboratory and Alisha Kasam, University of Cambridge for diffraction data reduction scripts. We thank Diamond Light Source for access to beamline B18 (SP14956, SP16387, SP17913) that contributed to the results presented here. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE- AC02-06CH11357

Incorporation of Sb5+ into CeO2 : local structural distortion of the fluorite structure from a pentavalent substituent

Hydrothermal crystallisation of CeO2 from aqueous sodium hydroxide solution at 240oC using CeCl3·7H2O in the presence of hydrogen peroxide with addition of either SbCl3 or SbCl5 yields polycrystalline samples of antimony-containing ceria directly from solution. Powder X-ray diffraction shows a contraction of the cubic lattice parameter with increasing Sb content, and also a broadening of Bragg peaks, from which Scherrer analysis yields crystallite domain sizes of 5 - 20 nm. Scanning transmission electron microscopy provides consistent results with observation of highly crystalline particles of a few nm in diameter. X-ray absorption near edge structure spectroscopy at the Ce LIII and Sb K edges reveals the presence of Ce4+ and Sb5+ in the solids. To balance charge the presence of co-included Na is proposed, corroborated by elemental analysis. The general chemical formula of the materials can thus be written as (Ce1 xSbx)1 yNayO2-δ (where x < 0.4 and y ≥ x/3). Sb K-edge extended X-ray absorption fine structure spectroscopy of the substituted ceria samples shows that the local structure of Sb resembles that in NaSbO3, where six-coordinate metal sites are found, but with evidence of a longer interatomic correlation due to surrounding Ce/Sb atoms in the fluorite structure; this implies that the Sb is displaced from the ideal eight-coordinate site of the fluorite structure. This structural distortion gives materials that are unstable under reducing conditions, coupled by the ease of reduction to elemental antimony, which is extruded leading to phase separation

Chromium (VI) Inhibition of Low pH Bioleaching of Limonitic Nickel-Cobalt Ore

Limonitic layers of the regolith, which are often stockpiled as waste materials at laterite mines, commonly contain significant concentrations of valuable base metals, such as nickel, cobalt, and manganese. There is currently considerable demand for these transition metals, and this is projected to continue to increase (alongside their commodity values) during the next few decades, due in the most part to their use in battery and renewable technologies. Limonite bioprocessing is an emerging technology that often uses acidophilic prokaryotes to catalyse the oxidation of zero-valent sulphur coupled to the reduction of Fe (III) and Mn (IV) minerals, resulting in the release of target metals. Chromium-bearing minerals, such as chromite, where the metal is present as Cr (III), are widespread in laterite deposits. However, there are also reports that the more oxidised and more biotoxic form of this metal [Cr (VI)] may be present in some limonites, formed by the oxidation of Cr (III) by manganese (IV) oxides. Bioleaching experiments carried out in laboratory-scale reactors using limonites from a laterite mine in New Caledonia found that solid densities of ∼10% w/v resulted in complete inhibition of iron reduction by acidophiles, which is a critical reaction in the reductive dissolution process. Further investigations found this to be due to the release of Cr (VI) in the acidic liquors. X-ray absorption near edge structure (XANES) spectroscopy analysis of the limonites used found that between 3.1 and 8.0% of the total chromium in the three limonite samples used in experiments was present in the raw materials as Cr (VI). Microbial inhibition due to Cr (VI) could be eliminated either by adding limonite incrementally or by the addition of ferrous iron, which reduces Cr (VI) to less toxic Cr (III), resulting in rates of extraction of cobalt (the main target metal in the experiments) of >90%