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The family of rare earth molybdenum bronzes, reduced ternary molybdates of composition LnMo{sub 16}O{sub 44,} was synthesized and a detailed structural study carried out. Bond valence sum (BVS) calculations clearly show that the molybdenum ions in tetrahedral coordination are hexavalent while the electron count in the primitive unit cell is odd. Yet, measurements show that the phases are semiconductors. The temperature dependence of the magnetic susceptibility of samples containing several different rare earth elements was measured. These measurements verified the presence of a 6.5 K magnetic phase transition not arising from the rare earth constituent, but likely associated with the unique isolated ReO{sub 3}-type Mo{sub 8}O{sub 36} structural subunits in this phase. To better understand the behavior of these materials, electronic structure calculations were performed within density functional theory. Results suggest a magnetic state in which these structural moieties have an internal ferromagnetic arrangement, with small ~1/8 μ{sub B} moments on each Mo. We suggest that the Mo{sub 8}O{sub 36} units behave like pseudoatoms with spin 1/2 derived from a single hole distributed over the eight Mo atoms that are strongly hybridized with the O atoms of the subunit. Interestingly, while the compound is antiferromagnetic, our calculations suggest that a field-stabilized ferromagnetic state, if achievable, will be a narrow band half-metal. - Graphical abstract: LnMo{sub 16}O{sub 44} phases comprise corner sharing tetrahedral and octahedral molybdenum ions. The MoO{sub 6} octahedra form Mo{sub 8}O{sub 36} units that are well separated and act like pseudo-atoms, accommodating 11 electrons each. - Highlights: • Single crystal X-ray diffraction refinements of LnMo{sub 16}O{sub 44} single crystals for Ln=Ce, Pr, Nd, Tb, Dy and Ho. • DFT calculations based on LaMo{sub 16}O{sub 44}. • [Mo{sub 8}O{sub 36}] units behaving as superatoms with a net magnetic moment of 1 µ{sub B}. • Bronze structure containing equal number of molybdenum tetrahedra and octahedral.
Highlights: • A series of rare earth urinates, RE{sub 6}UO{sub 12}, were synthesized using the solid state method. • The crystal structures of RE{sub 6}UO{sub 12} were refined using the Rietveld method. • Magnetic properties were measured and AF ordering was observed in RE = Gd, Tb, Dy. - Abstract: A series of rare earth uranates, RE{sub 6}UO{sub 12-δ} (RE = La, Nd, Sm – Dy, Er and Yb), were synthesized via the solid state method and their structures were determined using the Rietveld method. These compounds crystallize in the rhombohedral space group R-3H with the lattice parameters a = 10.47005(3) Å and c = 9.98034(3) Å for the La analogue. The temperature and field dependent magnetization are reported for each analogue. Antiferromagnetic ordering is observed for RE = Gd, Tb, and Dy with Néel temperatures of 2.1 K, 5.8 K, and 2.8 K, respectively. Magnetic measurements on the La{sub 6}UO{sub 12} analogue indicate the presence of some U{sup 5+}, and therefore, oxygen vacancies in the structure. The variability of the U valence is examined.
Highlights: • N{sub 2}O emissions from waste incineration with SNCR NO{sub x} removal are 51.5 ± 10.6 g t{sup −1}. • This is significantly lower than the reported Swiss emission factor of 120 g t{sup −1} (FOEN, 2013). • N{sub 2}O contributes <0.3% and ≈2.5% of GHG emissions from SCR and SNCR plants. • Measured isotopic SP of 17.7‰ is likely characteristic for N{sub 2}O emissions from SNCR. • CH{sub 4} emitted by waste incineration is negligible, contributing <0.01% to total GHGs. - Abstract: Solid waste incineration accounts for a growing proportion of waste disposal in both developed and developing countries, therefore it is important to constrain emissions of greenhouse gases from these facilities. At five Swiss waste incineration facilities with grate firing, emission factors for N{sub 2}O and CH{sub 4} were determined based on measurements of representative flue gas samples, which were collected in Tedlar bags over a one year period (September 2010–August 2011) and analysed with FTIR spectroscopy. All five plants burn a mixture of household and industrial waste, and two of the plants employ NO{sub x} removal through selective non-catalytic reduction (SNCR) while three plants use selective catalytic reduction (SCR) for NO{sub x} removal. N{sub 2}O emissions from incineration plants with NO{sub x} removal through selective catalytic reduction were 4.3 ± 4.0 g N{sub 2}O tonne{sup −1} waste (wet) (hereafter abbreviated as t{sup −1}) (0.4 ± 0.4 g N{sub 2}O GJ{sup −1}), ten times lower than from plants with selective non-catalytic reduction (51.5 ± 10.6 g N{sub 2}O t{sup −1}; 4.5 ± 0.9 g N{sub 2}O GJ{sup −1}). These emission factors, which are much lower than the value of 120 g N{sub 2}O t{sup −1} (10.4 g N{sub 2}O GJ{sup −1}) used in the 2013 Swiss national greenhouse gas emission inventory, have been implemented in the most recent Swiss emission inventory. In addition, the isotopic composition of N{sub 2}O emitted from the two plants with SNCR, which had considerable N{sub 2}O emissions, was measured using quantum cascade laser spectroscopy. The isotopic site preference of N{sub 2}O – the enrichment of {sup 14}N{sup 15}NO relative to {sup 15}N{sup 14}NO – was found to be 17.6 ± 0.8‰, with no significant difference between the two plants. Comparison to previous studies suggests SP of 17–19‰ may be characteristic for N{sub 2}O produced from SNCR. Methane emissions were found to be insignificant, with a maximum emission factor of 2.5 ± 5.6 g CH{sub 4} t{sup −1} (0.2 ± 0.5 g CH{sub 4} GJ{sup −1}), which is expected due to high incinerator temperatures and efficient combustion.
The transition from fossil fuels to renewable energy requires the development of efficient and cost-effective energy storage technologies. A promising way forward is to harness the energy of intermittent renewable sources, such as solar and wind, to perform (electro)catalytic reactions to generate fuels, thus storing energy in the form of chemical bonds. Furthermore, current catalysts rely on the use of expensive, rare, or geographically localized elements, such as platinum. Widespread adoption of new (electro)catalytic technologies hinges on the discovery and development of materials containing earth-abundant elements, which can efficiently catalyze an array of (electro)chemical reactions.
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The clean activation of methane at low temperatures remains an eminent challenge and a field of competitive research. In particular, on late transition metal surfaces such as Pt(111) or Ni(111), higher temperatures are necessary to activate the hydrocarbon molecule, but a massive deposition of carbon makes the metal surface useless for catalytic activity. However, on very low-loaded M/CeO 2 (M = Pt, Ni, or Co) surfaces, the dissociation of methane occurs at room temperature, which is unexpected considering simple linear scaling relationships. This intriguing phenomenon has been studied using a combination of experimental techniques (ambient-pressure X-ray photoelectron spectroscopy, time-resolved X-ray diffraction, and X-ray absorption spectroscopy) and density functional theory-based calculations. The experimental and theoretical studies show that the size and morphology of the supported nanoparticles together with strong metal–support interactions are behind the deviations from the scaling relations. These findings point toward a possible strategy for circumventing scaling relations, producing active and stable catalysts that can be employed for methane activation and conversion.
Nanoparticles with well-defined facets enable quantitative correlations between surface features and catalytic activity. In this work, we explore the role of geometric and acid–base properties in the mechanism of aldol condensation catalyzed by ceria nanoshapes. In the crucial C–C coupling step, the two carbonyl adsorbates are bound to two adjacent cations. On the CeO 2 (110) plane, all atoms lie on the same layer, favoring the interaction between adsorbates and facilitating the bimolecular C–C coupling. Thus, the initial unimolecular deprotonation is rate-limiting. In contrast, the (100) and (111) planes have an open structure with O on the top layer and Ce on the layer below. The former O layer interferes between adsorbates linked to Ce sites, making the C–C coupling rate-limiting. Water helps in overcoming this spatial hindrance by remote bond polarization via H-bonds. Therefore, water promotion is only observed on those planes for which the bimolecular step is rate-limiting.
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Palladium nanotubes (PdNTs) were synthesized by templated vapor deposition and investigated for formic acid electrooxidation. Annealed PdNTs are 2.4 times more active (2.19 mA/cm 2 ) than commercial carbon-supported palladium (0.91 mA/cm 2 ) at 0.3 V vs RHE. Bismuth modification improved nanotube performance over 4 times (3.75 mA/cm 2 ) vs Pd/C and nearly 2 times vs unmodified PdNTs. A surface Bi coverage of 80% results in optimal site-specific activity by drastically reducing surface-poisoning CO generation during formic acid electrooxidation. The Bi-modified PdNTs are exceptionally stable, maintaining 2 times the area-normalized current density as Pd/C after 24 h at 0.2 V vs RHE. As a result, we attribute the enhanced activity and stability of the nanotube catalysts to the presence of highly coordinated surfaces, mimicking a flat polycrystal while retaining high surface area geometry.
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