Disorder effects in the quantum Heisenberg model: An Extended Dynamical mean-field theory analysis

We investigate a quantum Heisenberg model with both antiferromagnetic and disordered nearest-neighbor couplings. We use an extended dynamical mean-field approach, which reduces the lattice problem to a self-consistent local impurity problem that we solve by using a quantum Monte Carlo algorithm. We consider both two- and three-dimensional antiferromagnetic spin fluctuations and systematically analyze the effect of disorder. We find that in three dimensions for any small amount of disorder a spin-glass phase is realized. In two dimensions, while clean systems display the properties of a highly correlated spin-liquid (where the local spin susceptibility has a non-integer power-low frequency and/or temperature dependence), in the present case this behavior is more elusive unless disorder is very small. This is because the spin-glass transition temperature leaves only an intermediate temperature regime where the system can display the spin-liquid behavior, which turns out to be more apparent in the static than in the dynamical susceptibility.Comment: 15 pages, 7 figure

Intrinsic susceptibility and bond defects in the novel 2D frustrated antiferromagnet Ba2_{2}Sn2_{2}ZnCr7p_{7p}Ga10−7p_{10-7p}O22_{22}

We present microscopic and macroscopic magnetic properties of the highly frustrated antiferromagnet Ba$_{2}$Sn$_{2}$ZnCr$_{7p}$Ga$_{10-7p}$O$_{22}$, respectively probed with NMR and SQUID experiments. The $T$-variation of the intrinsic susceptibility of the Cr$^{3+}$ frustrated kagom\'{e} bilayer, $\chi_{kag}$, displays a maximum around 45 K. The dilution of the magnetic lattice has been studied in detail for $0.29 \leq p \leq0.97$. Novel dilution independent defects, likely related with magnetic bond disorder, are evidenced and discussed. We compare our results to SrCr$_{9p}$Ga$_{12-9p}$O$_{19}$. Both bond defects and spin vacancies do not affect the average susceptibility of the kagom\'{e} bilayers.Comment: Published in Phys. Rev. Lett. 92, 217202 (2004). Only minor changes as compared to previous version. 4 pages, 4 figure

Nematicidal and fertilizing effects of chicken manure, fresh and composted olive mill wastes on organic melon

Abstract The fertilizing and nematicidal effects of three organic amendments were evaluated in a pot experiment on melon plants infested by the root-knot nematode Meloidogyne incognita. A soil artificially infested with 4 eggs and juveniles/ ml soil of the nematode was amended with: a) virgin olive pomace (VOP); b) composted olive pomace (COP); c) chicken manure based fertilizer (CM) and d) chicken manure based fertilizer combined with the biological control agent Paecilomyces lilacinus strain 251, brand name BioAct WG (CMB). VOP was applied at doses of 11 (VOP-A), 22 (VOP-B) and 44 t/ha (VOP-C); COP at 4.5 (COP-A), 9 (COP-B) and 18 t/ha (COP-C); CM at 3 t/ha and CMB at 3 t/ha combined with 4 kg/ha of BioAct WG. Untreated soil was used as control. The treatments CM, CMB, VOP-B and COP-B were established on the basis of N requirement of melon plants (120 kg/ha) taking into account soil and amendments N availability. Two weeks later amendment application and nematode inoculation, the soil was poured in 4.8 l clay pots which were arranged in a greenhouse according to a randomized block design with ten replications for each treatment. A one-month old melon seedling (cv. Galia) was transplanted in each pot and organic farming management practices were used during the growing period. At the end of the experiment, 60 days after transplant, plants were uprooted and height, fresh and dry shoot and root weights were recorded. Root gall index, on the roots, caused by the nematode attack, was estimated according to a 0–5 scale. Final nematode population density and reproduction rate were also calculated for each pot. All data were subjected to statistical analysis of variance (ANOVA) and means compared according to Least Significant Difference's Test. Nematode population and root infestation were significantly suppressed by the addition of all amendments, compared to untreated control. However, CM and CMB resulted in a total more suppressive effect and in a significantly higher plant growth in comparison to all the other treatments. A significant correlation was found between root gall index and eggs and juveniles/g root and final nematode population density. No signifycant correlations were found between nematological parameters or plant growth parameters and amendment doses

Do observations on surface coverage-reactivity correlations always describe the true catalytic process? A case study on ceria

In situ (operando) investigations aim at establishing structure-function and/or coverage-reactivity correlations. Herein, we investigated the gas-phase HCl oxidation (4HCl + O2 → 2Cl2 + 2H2O) over ceria. Despite its remarkable performance, under low oxygen over-stoichiometry, this oxide is prone to a certain extent to subsurface/bulk chlorination, which leads to deactivation. In situ Prompt Gamma Activation Analysis (PGAA) studies evidenced that the chlorination rate is independent of the pre-chlorination degree but increases at lower oxygen over-stoichiometry, while dechlorination is effective in oxygen-rich feeds, and its rate is higher for a more extensively pre-chlorinated ceria. Even bulk CeCl3 could be transformed into CeO2 under oxygen excess. Electron Paramagnetic Resonance experiments strongly suggested that oxygen activation is inhibited by a high surface chlorination degree. The coverages of most abundant surface intermediates, OH and Cl, were monitored by in situ infrared spectroscopy and PGAA under various conditions. Higher temperature and p(O2) led to enhanced OH coverage, reduced Cl coverage, and increased reactivity. Variation of p(HCl) gave rise to opposite correlations, while raising p(Cl2) did not induce any measurable increase in the Cl coverage, despite the strong inhibition of the reaction rate. The results indicate that only a small fraction of surface sites is actively involved in the reaction, and most of the surface species probed in the in situ observation are spectators. Therefore, when performing in situ steady-state experiments, a large set of variables should be considered to obtain accurate conclusions

Supported CeO₂ catalysts in technical form for sustainable chlorine production

Bulk CeO2 has been recently reported as a promising catalyst for the oxidation of HCl to Cl2. In order to undertake the scale up of this system, various oxides (TiO2, Al2O3 , and low- and high-surface area ZrO2) have been evaluated as carriers. Supported CeO2 catalysts (3–20 wt.% Ce) prepared by dry impregnation were isothermally tested at the lab scale. Their performance was ranked as: CeO2/ZrO2 ≫ CeO2/Al2O3 ≥ CeO2/TiO2. Kinetic data revealed a lower activation energy and a similar activity dependence on the partial pressure of O2 for CeO2/ZrO2 compared to bulk CeO2. Pilot-scale testing over 3-mm pellets of this catalyst evidenced outstanding stability for 700 h on stream. In-depth characterization of the carriers and fresh catalysts by N2 sorption, Hg porosimetry, X-ray diffraction, temperature-programmed reduction with H2, Raman spectroscopy, electron microscopy, and in situ prompt gamma activation analysis, enabled to rationalize the different catalytic behavior of the materials. ZrO2 stabilizes nanostructures of CeO2 and a Ce–Zr mixed oxide phase, which offer high dispersion and improved oxidation properties. The catalyst also shows reduced chlorine uptake, and overall stands as a better Deacon material compared to bulk CeO2 and other supported systems. CeO2 is present on Al2O3 predominantly as well-distributed nanoparticles. Still, alumina does not induce any electronic effect, thus the supported phase behaves similarly to bulk ceria. TiO2, likely due to the structural collapse and dramatic sintering suffered during calcination, leads to the formation of very large ceria particles. Based on our results, CeO2/ZrO2 appears as a robust and cost-effective alternative to the current RuO2-based catalysts for large-scale chlorine recovery

Performance, structure, and mechanism of CeO₂ in HCl oxidation to Cl₂

Experimental and theoretical studies reveal performance descriptors and provide molecular-level understanding of HCl oxidation over CeO2. Steady-state kinetics and characterization indicate that CeO2 attains a significant activity level, which is associated with the presence of oxygen vacancies. Calcination of CeO2 at 1173 K prior to reaction maximizes both the number of vacancies and the structural stability of the catalyst. X-ray diffraction and electron microscopy of samples exposed to reaction feeds with different O2/HCl ratios provide evidence that CeO2 does not suffer from bulk chlorination in O2-rich feeds (O2/HCl ≥ 0.75), while it does form chlorinated phases in stoichiometric or sub-stoichiometric feeds (O2/HCl ≤ 0.25). Quantitative analysis of the chlorine uptake by thermogravimetry and X-ray photoelectron spectroscopy indicates that chlorination under O2-rich conditions is limited to few surface and sub-surface layers of CeO2 particles, in line with the high energy computed for the transfer of Cl from surface to sub-surface positions. Exposure of chlorinated samples to a Deacon mixture with excess oxygen rapidly restores the original activity levels, highlighting the dynamic response of CeO2 outermost layers to feeds of different composition. Density functional theory simulations reveal that Cl activation from vacancy positions to surface Ce atoms is the most energy-demanding step, although chorine-oxygen competition for the available active sites may render re-oxidation as the rate-determining step. The substantial and remarkably stable Cl2 production and the lower of CeO2 make it an attractive alternative to RuO2 for catalytic chlorine recycling in industry