Functional Nanostructures from Sol-Gel Synthesis Using Keggin Polyoxometallate Phosphotungstic Acid as a Precursor.

Subjecting phosphotungstic acid solutions to low pH in combination with introduction of polyvalent cations led to the formation of nanostructured microspheres of approximately 2 µm in size, as shown by scanning electron microscopy, which were almost insoluble and resistant to degradation at neutral and high pH. These microspheres were composed of secondary nanospheres with diameters around 20 nm as revealed by transmission electron microscopy and atomic force microscopy. Investigations of the crystal structure of a potential intermediate of this process, namely, acidic lanthanum phosphotungstate, [La(H2O)9](H3O)3[PW12O40]2(H2O)19, showed a tight network of hydrogen bonding, permitting closer packing of phosphotungstic acid anions, thereby confirming the mechanism of the observed self-assembly process. The new material demonstrated promising electrochemical properties in oxygen evolution reactions with the high stability of the obtained electrode material.

Electrocatalytic Glycerol Oxidation with Concurrent Hydrogen Evolution Utilizing an Efficient MoOx /Pt Catalyst.

Glycerol electrolysis affords a green and energetically favorable route for the production of value-added chemicals at the anode and H2 production in parallel at the cathode. Here, a facile method for trapping Pt nanoparticles at oxygen vacancies of molybdenum oxide (MoOx ) nanosheets, yielding a high-performance MoOx /Pt composite electrocatalyst for both the glycerol oxidation reaction (GOR) and the hydrogen evolution reaction (HER) in alkaline electrolytes, is reported. Combined electrochemical experiments and theoretical calculations reveal the important role of MoOx nanosheets for the adsorption of glycerol molecules in GOR and the dissociation of water molecules in HER, as well as the strong electronic interaction with Pt. The MoOx /Pt composite thus significantly enhances the specific mass activity of Pt and the kinetics for both reactions. With MoOx /Pt electrodes serving as both cathode and anode, two-electrode glycerol electrolysis is achieved at a cell voltage of 0.70 V to reach a current density of 10 mA cm-2 , which is 0.90 V less than that required for water electrolysis.

Synthesis and Characterization of the Aurivillius Phase CoBi2O2F4.

The new CoBi2O2F4 compound was synthesized by a hydrothermal method at 230 °C. Single-crystal X-ray diffraction data were used to determine the crystal structure. The compound is layered and belongs to the Aurivillius family of compounds. The present compound is the first oxo-fluoride Aurivillius phase containing Co2+. Inclusion of a d-block cation with such a low oxidation state as 2+ was achieved by partially replacing O2- with F- ions. The crystal structure is best described in the tetragonal noncentrosymmetric space group I4̅ with unit-cell parameters a = 3.843(2) Å and c = 16.341(8) Å. The crystal structure consists of two main building units: [BiO4F4] distorted cubes and [CoF6] octahedra. Interestingly, since the octahedra [CoF6] tilt between four equivalent positions, the F atoms occupy a 4-fold split position at room temperature. For the investigation of the structural disorder, Raman scattering data were collected in the range from 10 K to room temperature. As the temperature decreases, sharper phonon peaks appear and several modes clearly appear, which indicates a reduction of the disorder. Magnetic susceptibility and heat capacity measurements evidence long-range antiferromagnetic ordering below the Néel temperature of ∼50 K. The magnetic susceptibility is in agreement with the Curie-Weiss law above 75 K with a Curie-Weiss temperature of θCW = -142(2) K.

Synthesis and Physical Properties of the Oxofluoride Cu2(SeO3)F2.

Single crystals of the new compound Cu2(SeO3)F2 were successfully synthesized via a hydrothermal method, and the crystal structure was determined from single-crystal X-ray diffraction data. The compound crystallizes in the orthorhombic space group Pnma with the unit cell parameters a = 7.066(4) Å, b = 9.590(4) Å, and c = 5.563(3) Å. Cu2(SeO3)F2 is isostructural with the previously described compounds Co2TeO3F2 and CoSeO3F2. The crystal structure comprises a framework of corner- and edge-sharing distorted [CuO3F3] octahedra, within which [SeO3] trigonal pyramids are present in voids and are connected to [CuO3F3] octahedra by corner sharing. The presence of a single local environment in both the 19F and 77Se solid-state MAS NMR spectra supports the hypothesis that O and F do not mix at the same crystallographic positions. Also the specific phonon modes observed with Raman scattering support the coordination around the cations. At high temperatures the magnetic susceptibility follows the Curie-Weiss law with Curie temperature of Θ = -173(2) K and an effective magnetic moment of µeff ∼ 2.2 µB. Antiferromagnetic ordering below ∼44 K is indicated by a peak in the magnetic susceptibility. A second though smaller peak at ∼16 K is tentatively ascribed to a magnetic reorientation transition. Both transitions are also confirmed by heat capacity measurements. Raman scattering experiments propose a structural phase instability in the temperature range 6-50 K based on phonon anomalies. Further changes in the Raman shift of modes at ∼46 K and ∼16 K arise from transitions of the magnetic lattice in accordance with the susceptibility and heat capacity measurements.

Direct Synthesis of Two Inorganic Catalysts on Carbon Fibres for the Electrocatalytic Oxidation of Water.

Two electrodes for anodic water oxidation made by direct synthesis of inorganic catalysts onto conductive carbon fibre sheets are evaluated. As catalysts two Co- and Sb-containing phases were tested, that is, Co3 Sb4 O6 F6 and the new compound CoSbO4 . The compounds express large differences in their morphology: CoSbO4 grows as thin needles whereas Co3 Sb4 O6 F6 grows as larger facetted crystals. Despite the smaller surface area the latter compound shows a better catalytic performance. When the compound Co3 Sb4 O6 F6 was used it gave a low increase of +0.028 mV h-1 at an overpotential of η=472 mV after 10 h and a stability of +0.48 mV h-1 at an overpotential of η=488 mV after 60 h. The leakages of Co and Sb were negligible and only <0.001 at % Co and approximately 0.02 at % Sb were detected in the electrolyte.

Hydrothermal Synthesis of the Oxofluoride FeSbO2F2-An Anti-ferromagnetic Spin S = 5/2 Compound.

The new oxofluoride compound FeSbO2F2 was synthesized by hydrothermal techniques at 230 °C. Its crystal structure was determined from single-crystal X-ray diffraction data. The compound crystallizes in the monoclinic space group C2/c with one crystallographic site for Fe3+ and Sb3+, respectively. The crystal structure is made of [FeO2F4] octahedra and seesaw [SbO4] building blocks. These are connected to form [FeO2F2]n layers and [SbO2]n chains that bond together via the oxygen atoms to form the three-dimensional framework structure. Magnetic susceptibility and heat capacity measurements indicate long-range anti-ferromagnetic ordering below a Néel temperature of ∼175 K. Two-dimensional anti-ferromagnetic short-range order in the square planar net of the Fe3+ cations extends to temperatures far above the Néel temperature.

Hydrothermal Synthesis and Magnetic Characterization of the Quaternary Oxide CoMo2Sb2O10.

The new quaternary layered oxide CoMo2Sb2O10 was synthesized by hydrothermal synthesis techniques, and its structure was determined from single-crystal X-ray diffraction data. CoMo2Sb2O10 crystallizes in the monoclinic space group C2/c with one Sb3+, Mo6+, and Co2+ atom site per unit cell, respectively. The crystal structure contains building units consisting of [Co2O8]n, [Mo2O8]n, and [SbO2]n chains. These are connected through corner sharing to form charge-neutral [CoMo2Sb2O10]n layers. Thermal decomposition of CoMo2Sb2O10 starts at 550 °C. The magnetic susceptibility follows a Curie-Weiss law above 50 K with a Curie constant of C = 3.46 emu·K·mol-1 corresponding to an effective moment of µeff = 5.26 µB per cobalt atom and a Curie-Weiss temperature θ = -13.2 K. Short-range anti-ferromagnetic ordering dominates below 5 K. Magnetic susceptibility and heat capacity data can be successfully modeled by the predictions from an Ising linear chain with an intrachain spin exchange of ca. -7.8 K.

Chemical Synthesis of Iron Antimonide (FeSb2) and Its Thermoelectric Properties.

Low temperature thermoelectric (TE) materials are in demand for more efficient cooling and power generation applications. Iron antimonide (FeSb2) draws great attention over the past few years because of its enhanced power factor values. Polycrystalline bulk FeSb2 nanopowder was prepared via a low-temperature molten salts approach followed by subsequent thermal treatment in synthetic air and hydrogen gas for calcination and reduction reactions, respectively. Structural analysis confirms the desired final phase with submicrometer grain size and high compaction density after consolidation using spark plasma sintering (SPS). TE transport properties revealed that the material is n-type below 150 K and p-type above this temperature; this suggests antimony vacancies in FeSb2. The electrical conductivity increased significantly, and the highest conductivity achieved was 6000 S/cm at 100 K. The maximum figure-of-merit, ZT, of 0.04 is achieved at 500 K, which is about 6 times higher than the earlier reported state-of-the art ZT value for the same material.

An Oxofluoride Catalyst Comprised of Transition Metals and a Metalloid for Application in Water Oxidation.

The application of the recently discovered oxofluoride solid solution (Cox Ni1-x )3 Sb4 O6 F6 as a catalyst for water oxidation is demonstrated. The phase exhibits a cubic arrangement of the active metal that forms oxo bridges to the metalloid with possible catalytic participation. The Co3 Sb4 O6 F6 compound proved to be capable of catalyzing 2H2 O→O2 +4H(+) +4e(-) at 0.33 V electrochemical and ≤0.39 V chemical overpotential with a TOF of 4.4⋅10(-3) , whereas Ni3 Sb4 O6 F6 needs a higher overpotential. Relatively large crystal cubes (0.3-0.5 mm) are easily synthesized and readily handled as they demonstrate both chemical resistance to wear after repeated in situ tests under experimental conditions, and have a mechanical hardness of 270 V0.1 using Vickers indentation. The combined properties of this compound offer a potential technical advantage for incorporation to a catalytic interface in future sustainable fuel production.

Crystal structure and magnetic properties of the S = 1/2 quantum spin system Cu7(TeO3)6F2 with mixed dimensionality.

The new oxofluoride Cu7(TeO3)6F2 has been synthesized by hydrothermal synthesis. It crystallizes in the triclinic system, space group P1. The crystal structure constitutes a Cu-O framework with channels extending along [001] where the F(-) ions and the stereochemically active lone-pairs on Te(4+) are located. From magnetic susceptibility, specific heat, and Raman scattering measurements we find evidence that the magnetic degrees of freedom of the Cu-O-Cu segments in Cu7(TeO3)6F2 lead to a mixed dimensionality with single Cu S = (1)/2 moments weakly coupled to spin-chain fragments. Due to the weaker coupling of the single moments, strong fluctuations exist at elevated temperatures, and long-range magnetic ordering evolves at comparably low temperatures (TN = 15 K).

Crystal structure and magnetic properties of FeSeO(3)F--alternating antiferromagnetic S = 5/2 chains.

The new oxofluoride FeSeO3F, which is isostructural with FeTeO3F and GaTeO3F, was prepared by hydrothermal synthesis, and its structure was determined by X-ray diffraction. The magnetic properties of FeSeO3F were characterized by magnetic susceptibility and specific heat measurements, by evaluating its spin exchanges on the basis of density functional theory (DFT) calculations, and by performing a quantum Monte Carlo simulation of the magnetic susceptibility. FeSeO3F crystallizes in the monoclinic space group P21/n and has one unique Se(4+) ion and one unique Fe(3+) ion. The building blocks of FeSeO3F are [SeO3] trigonal pyramids and cis-[FeO4F2] distorted octahedra. The cis-[FeO4F2] octahedra are condensed by sharing the O-O and F-F edges alternatingly to form [FeO3F]∞ chains, which are interconnected via the [SeO3] pyramids by corner-sharing. The magnetic susceptibility of FeSeO3F is characterized by a broad maximum at 75(2) K and a long-range antiferromagnetic order below ∼45 K. The latter is observed by magnetic susceptibility and specific heat measurements. DFT calculations show that the Fe-F-Fe spin exchange is stronger than the Fe-O-Fe exchange, so each [FeO3F]∞ chain is a Heisenberg antiferromagnetic chain with alternating antiferromagnetic spin exchanges. The temperature dependence of the magnetic susceptibility is well-reproduced by a quantum-Monte Carlo simulation.

Tuneable C3 product selectivity of glycerol electrooxidation on cubic and dendritic Pt nanocatalysts.

Glycerol, being an abundant and cheap by-product of biodiesel production, has emerged as a raw material that can be recycled into value-added compounds. In the present study, Pt nanoparticles of cubic (PtCUBE) and dendritic (PtDEND) morphologies were investigated as catalysts for the glycerol electrooxidation reaction (GEOR) at 20 °C. To optimise the electrocatalytic performance and GEOR selectivity towards three-carbon (C3) products, namely lactate, glycerate, and tartronate, the effects of morphology, electrolyte composition, and applied potential were studied. At low glycerol concentrations, C-C bond cleavage was more favoured, especially on PtDEND. Both PtCUBE and PtDEND showed high C3 product selectivity up to 91% at 0.67 V vs. RHE, with lactate reaching a maximum selectivity of 68% on PtCUBE, which also exhibited the best mass and specific activities compared to PtDEND.

Synthesis and crystal structure of the solid solution Co3(SeO3)3-x(PO3OH)x(H2O) involving crystallographic split positions of Se4+ and P5+.

Three new cobalt selenite hydroxo-phosphates laying in the solid solution Co3(SeO3)3-x(PO3OH)x(H2O), with x = 0.8, x = 1.0, and x = 1.2 are reported. Single crystals were obtained by hydrothermal synthesis and the crystal structure was determined by single crystal X-ray diffraction. The structure can be described as a 3D framework having selenite and hydroxo-phosphate groups protruding into channels in the crystal structure. Se(4+) and P(5+) share a split position in the structure so that either SeO3 groups having a stereochemically active lone pair or tetrahedrally coordinated PO3OH groups are present. The OH-group is thus only present when the split position is occupied by P(5+). The crystal water is coordinated to a cobalt atom and TG and IR measurements show that the water and hydroxyl groups leave the structure at unusually high temperatures (>450 °C). Magnetic susceptibility measurements show antiferromagnetic coupling below 16 K and a magnetic moment of 4.02(3) µB per Co atom was observed.

The synthetic cobalt vanadium selenite, Co2V2Se2O11.

The crystal structure of dicobalt(II) divanadium(V) disel-enium(IV) undeca-oxide, Co2V2Se2O11, exhibits a three-dimensional framework, the building units being distorted CoO6 octa-hedra and VO5 square pyramids arranged so as to form alternate chains along [010]. The framework has channels along [100] and [010] in which the two Ψ-SeO3E (site symmetries m; E being the 4s² lone electron pair of Se(IV)) tetra-hedra reside and connect to the other building blocks. The structure contains corner- and edge-sharing CoO6 octa-hedra, corner- and edge-sharing VO5 square pyramids and edge-sharing Ψ-SeO3E tetra-hedra. Co2V2Se2O11 is the first oxide containing all the cations Co(II), V(V) and Se(IV).

Bi2CoO2F4-A Polar, Ferrimagnetic Aurivillius Oxide-Fluoride.

Aurivillius oxides have been a research focus due to their ferroelectric properties, but by replacing oxide ions by fluoride, divalent magnetic cations can be introduced, giving Bi2 MO2F4 (M = Fe, Co, and Ni). Our combined experimental and computational study on Bi2CoO2F4 indicates a low-temperature polar structure of P21 ab symmetry (analogous to ferroelectric Bi2WO6) and a ferrimagnetic ground state. These results highlight the potential of Aurivillius oxide-fluorides for multiferroic properties. Our research has also revealed some challenges associated with the reduced tendency for polar displacements in the more ionic fluoride-based systems.

Crystal structure and magnetic properties of two new antiferromagnetic spin dimer compounds; FeTe3O7X (X = Cl, Br).

Two new isostructural layered oxohalides FeTe(3)O(7)X (X = Cl, Br) were synthesized by chemical vapor transport reactions, and their crystal structures and magnetic properties were characterized by single-crystal X-ray diffraction, Raman spectroscopy, magnetic susceptibility and magnetization measurements, and also by density functional theory (DFT) calculations of the electronic structure and the spin exchange parameters. FeTe(3)O(7)X crystallizes in the monoclinic space group P2(1)/c with the unit cell parameters a = 10.7938(5), b = 7.3586(4), c = 10.8714(6) Å, ß = 111.041(5)°, Z = 4 for FeTe(3)O(7)Cl, and a = 11.0339(10), b = 7.3643(10), c = 10.8892(10) Å, ß = 109.598(10)°, Z = 4 for FeTe(3)O(7)Br. Each compound has one unique Fe(3+) ion coordinating a distorted [FeO(5)] trigonal bipyramid. Two such groups share edges to form [Fe(2)O(8)] dimers that are isolated from each other by Te(4+) ions. The high-temperature magnetic properties of the compounds as well as spectroscopic investigations are consistent with an isolated antiferromagnetic spin dimer model with almost similar spin gaps of ~35 K for X = Cl and Br, respectively. However, deviations at low temperatures in the magnetic susceptibility and the magnetization data indicate that the dimers couple via an interdimer coupling. This interpretation is also supported by DFT calculations which indicate an interdimer exchange which amounts to 25% and 10% of the intradimer exchange for X = Cl and Br, respectively. The magnetic properties support the counterion character and a weak integration of halide ions into the covalent network similar to that in many other oxohalides.

On the Stability of Uranium Carbide in Aqueous Solution-Effects of HCO3 - and H2O2.

Uranium carbide (UC) is a candidate fuel material for future Generation IV nuclear reactors. As part of a general safety assessment, it is important to understand how fuel materials behave in aqueous systems in the event of accidents or upon complete barrier failure in a geological repository for spent nuclear fuel. As irradiated nuclear fuel is radioactive, it is important to consider radiolysis of water as a process where strongly oxidizing species can be produced. These species may display high reactivity toward the fuel itself and thereby influence its integrity. The most important radiolytic oxidant under repository conditions has been shown to be H2O2. In this work, we have studied the dissolution of uranium upon exposure of UC powder to aqueous solutions containing HCO3 - and H2O2, separately and in combination. The experiments show that UC dissolves quite readily in aqueous solution containing 10 mM HCO3 - and that the presence of H2O2 increases the dissolution further. UC also dissolves in pure water after the addition of H2O2, but more slowly than in solutions containing both HCO3 - and H2O2. The experimental results are discussed in view of possible mechanisms.

Oxidative cleavage of C-C bonds in lignin.

Lignin is an aromatic polymer that constitutes up to 30 wt% of woody biomass and is considered the largest source of renewable aromatics. Valorization of the lignin stream is pivotal for making biorefining sustainable. Monomeric units in lignin are bound via C-O and C-C bonds. The majority of existing methods for the production of valuable compounds from lignin are based on the depolymerization of lignin via cleavage of relatively labile C-O bonds within lignin structure, which leads to yields of only 36-40 wt%. The remaining fraction (60 wt%) is a complex mixture of high-molecular-weight lignin, generally left unvalorized. Here we present a method to produce additional valuable monomers from the high-molecular-weight lignin fraction through oxidative C-C bond cleavage. This oxidation reaction proceeds with a high selectivity to give 2,6-dimethoxybenzoquinone (DMBQ) from high-molecular-weight lignin in 18 wt% yield, thus increasing the yield of monomers by 32%. This is an important step to make biorefining competitive with petroleum-based refineries.

Minute-Made, High-Efficiency Nanostructured Bi2Te3 via High-Throughput Green Solution Chemical Synthesis.

Scalable synthetic strategies for high-quality and reproducible thermoelectric (TE) materials is an essential step for advancing the TE technology. We present here very rapid and effective methods for the synthesis of nanostructured bismuth telluride materials with promising TE performance. The methodology is based on an effective volume heating using microwaves, leading to highly crystalline nanostructured powders, in a reaction duration of two minutes. As the solvents, we demonstrate that water with a high dielectric constant is as good a solvent as ethylene glycol (EG) for the synthetic process, providing a greener reaction media. Crystal structure, crystallinity, morphology, microstructure and surface chemistry of these materials were evaluated using XRD, SEM/TEM, XPS and zeta potential characterization techniques. Nanostructured particles with hexagonal platelet morphology were observed in both systems. Surfaces show various degrees of oxidation, and signatures of the precursors used. Thermoelectric transport properties were evaluated using electrical conductivity, Seebeck coefficient and thermal conductivity measurements to estimate the TE figure-of-merit, ZT. Low thermal conductivity values were obtained, mainly due to the increased density of boundaries via materials nanostructuring. The estimated ZT values of 0.8-0.9 was reached in the 300-375 K temperature range for the hydrothermally synthesized sample, while 0.9-1 was reached in the 425-525 K temperature range for the polyol (EG) sample. Considering the energy and time efficiency of the synthetic processes developed in this work, these are rather promising ZT values paving the way for a wider impact of these strategic materials with a minimum environmental impact.