Magnetic-Field Induced Quantum Critical Point in YbRh2_2Si2_2

We report low-temperature calorimetric, magnetic and resistivity measurements on the antiferromagnetic (AF) heavy-fermion metal YbRh$_2$Si$_2$ (${T_N =}$ 70 mK) as a function of magnetic field $B$. While for fields exceeding the critical value ${B_{c0}}$ at which ${T_N\to0}$ the low temperature resistivity shows an ${AT^2}$ dependence, a ${1/(B-B_{c0})}$ divergence of ${A(B)}$ upon reducing $B$ to ${B_{c0}}$ suggests singular scattering at the whole Fermi surface and a divergence of the heavy quasiparticle mass. The observations are interpreted in terms of a new type of quantum critical point separating a weakly AF ordered from a weakly polarized heavy Landau-Fermi liquid state.Comment: accepted for publication in Phys. Rev. Let

Influence of nanoscale surface arrangements on the oxygen transfer ability of ceria-zirconia mixed oxide

Ceria-based materials, and particularly CeO2-ZrO2 (CZ) solid solutions are key ingredient in catalyst formulations for several applications due to the ability of ceria to easily cycling its oxidation state between Ce4+ and Ce3+. Ceria-based catalysts have a great soot oxidation potential and the mechanism deeply relies on the degree of contact between CeO2 and carbon. In this study, carbon soot has been used as solid reductant to better understand the oxygen transfer ability of ceria-zirconia at low temperatures; the effect of different atmosphere and contact conditions has been investigated. The difference in the contact morphology between carbon soot and CZ particles is shown to strongly affect the oxygen transfer ability of ceria; in particular, increasing the carbon-ceria interfacial area, the reactivity of CZ lattice oxygen is significantly improved. In addition, with a higher degree of contact, the soot oxidation is less affected by the presence of NOx. The NO oxidation over CZ in the presence of soot has also been analyzed. The existence of a core/shell structure strongly enhances reactivity of interfacial oxygen species while affecting negatively NO oxidation characteristics. These findings are significant in the understanding of the redox chemistry of substituted ceria and help determining the role of active species in soot oxidation reaction as a function of the degree of contact between ceria and carbon

Potential of Ceria-Based Catalysts for the Oxidation of Landfill Leachate by Heterogeneous Fenton Process

In this study, ceria and ceria-zirconia solid solutions were tested as catalyst for the treatment of landfill leachate with a Fenton-like process. The catalysts considered in this work were pure ceria and ceria-zirconia solid solutions as well as iron-doped samples. All the catalysts were extensively characterized and applied in batch Fenton-like reactions by a close batch system, the COD (chemical oxygen demand) and TOC (total organic carbon) parameters were carried out before and after the treatments in order to assay oxidative abatement. Results show a measurable improvement of the TOC and COD abatement using ceria-based catalysts in Fenton-like process and the best result was achieved for iron-doped ceria-zirconia solid solution. Our outcomes point out that heterogeneous Fenton technique could be effectively used for the treatment of landfill leachate and it is worth to be the object of further investigations

Thermoelectric Behaviour Near Magnetic Quantum Critical Point

We use the coupled 2d-spin-3d-fermion model proposed by Rosch {\sl et. al.} (Phys. Rev. Lett. {\bf 79}, 159 (1997)) to study the thermoelectric behaviour of a heavy fermion compound when it is close to an antiferromagnetic quantum critical point. When the low energy spin fluctuations are quasi two dimensional, as has been observed in ${\rm YbRh}_2{\rm Si}_2$ and ${\rm CeCu}_{6-x}{\rm Au}_x$, with a typical 2d ordering wavevector and 3d Fermi surface, the ``hot'' regions on the Fermi surface have a finite area. Due to enhanced scattering with the nearly critical spin fluctuations, the electrons in the hot region are strongly renormalized. We argue that there is an intermediate energy scale where the qualitative aspects of the renormalized hot electrons are captured by a weak-coupling perturbative calculation. Our examination of the electron self energy shows that the entropy carried by the hot electrons is larger than usual. This accounts for the anomalous logarithmic temperature dependence of specific heat observed in these materials. We show that the same mechanism produces logarithmic temperature dependence in thermopower. This has been observed in ${\rm CeCu}_{6-x}{\rm Au}_x$. We expect to see the same behaviour from future experiments on ${\rm YbRh}_2{\rm Si}_2$.Comment: RevTex, two-column, 7 pages, 2 figure

The break up of heavy electrons at a quantum critical point

The point at absolute zero where matter becomes unstable to new forms of order is called a quantum critical point (QCP). The quantum fluctuations between order and disorder that develop at this point induce profound transformations in the finite temperature electronic properties of the material. Magnetic fields are ideal for tuning a material as close as possible to a QCP, where the most intense effects of criticality can be studied. A previous study on theheavy-electron material $YbRh_2Si_2$ found that near a field-induced quantum critical point electrons move ever more slowly and scatter off one-another with ever increasing probability, as indicated by a divergence to infinity of the electron effective mass and cross-section. These studies could not shed light on whether these properties were an artifact of the applied field, or a more general feature of field-free QCPs. Here we report that when Germanium-doped $YbRh_2Si_2$ is tuned away from a chemically induced quantum critical point by magnetic fields there is a universal behavior in the temperature dependence of the specific heat and resistivity: the characteristic kinetic energy of electrons is directly proportional to the strength of the applied field. We infer that all ballistic motion of electrons vanishes at a QCP, forming a new class of conductor in which individual electrons decay into collective current carrying motions of the electron fluid.Comment: Pdf files of article available at http://www.physics.rutgers.edu/~coleman/online/breakup.pdf, pdf file of news and views article available at http://www.physics.rutgers.edu/~coleman/online/nvbreakup.pd

The f-electron challenge: localized and itinerant states in lanthanide oxides united by GW@LDA+U

Many-body perturbation theory in the GW approach is applied to lanthanide oxides, using the local-density approximation plus a Hubbard U correction (LDA+U) as the starting point. Good agreement between the G0W0 density of states and experimental spectra is observed for CeO2 and Ce2O3. Unlike the LDA+U method G0W0 exhibits only a weak dependence on U in a physically meaningful range of U values. For the whole lanthanide sesquioxide (Ln2O3) series G0W0@LDA+U reproduces the main features found for the optical experimental band gaps. The relative positions of the occupied and unoccupied f-states predicted by G0W0 confirm the experimental conjecture derived from phenomenological arguments.Comment: 4 pages including 3 figures; related publications can be found at http://www.fhi-berlin.mpg.de/th/th.htm

Performance and Stability of Doped Ceria–Zirconia Catalyst for a Multifuel Reforming

In the present work, the catalytic behavior of nickel-based catalysts supported on ceria/zirconia, undoped and doped with lanthanum and neodymium (3.5Ni/Ce0.8La0.5Nd0.2Zr0.13O2−x), was investigated under different reactions: steam reforming, partial oxidation and autothermal reforming of different fuels (methane, biogas, and propane). The catalytic properties of these catalysts were evaluated at a temperature of 800 °C, under atmospheric pressure, at GSHV = 120,000 h−1, using steam/carbon and oxygen/carbon ratio, respectively, of S/C = 2.5 and O/C = 0.5 and, in the case of autothermal conditions, with the addition of H2S (100 ppm) as a contaminant. Depending on the tested fuel, ATR, SR, and POX reactions over doped and undoped catalysts showed different results. In particular, the doped catalyst, due to neodymium and lanthanum doping, better distributed nickel species on the catalyst surface, promoting a higher concentration of defect groups and oxygen vacancies. This resulted in improved catalytic performance and resistance to deactivation. Endurance catalytic test also confirmed the beneficial effect of the doped catalysts

Hall-effect evolution across a heavy-fermion quantum critical point

A quantum critical point (QCP) develops in a material at absolute zero when a new form of order smoothly emerges in its ground state. QCPs are of great current interest because of their singular ability to influence the finite temperature properties of materials. Recently, heavy-fermion metals have played a key role in the study of antiferromagnetic QCPs. To accommodate the heavy electrons, the Fermi surface of the heavy-fermion paramagnet is larger than that of an antiferromagnet. An important unsolved question concerns whether the Fermi surface transformation at the QCP develops gradually, as expected if the magnetism is of spin density wave (SDW) type, or suddenly as expected if the heavy electrons are abruptly localized by magnetism. Here we report measurements of the low-temperature Hall coefficient ($R_H$) - a measure of the Fermi surface volume - in the heavy-fermion metal YbRh2Si2 upon field-tuning it from an antiferromagnetic to a paramagnetic state. $R_H$ undergoes an increasingly rapid change near the QCP as the temperature is lowered, extrapolating to a sudden jump in the zero temperature limit. We interpret these results in terms of a collapse of the large Fermi surface and of the heavy-fermion state itself precisely at the QCP.Comment: 20 pages, 3 figures; to appear in Natur

The influence of nano-architectured CeOx supports in RhPd/CeO2 for the catalytic ethanol steam reforming reaction

The ethanol steam reforming (ESR) reaction has been tested over RhPd supported on polycrystalline ceria in comparison to structured supports composed of nanoshaped CeO2 cubes and CeO2 rods tailored toward the production of hydrogen. At 650-700 K the hydrogen yield follows the trend RhPd/CeO(2)cubes >RhPd/CeO2-rods >RhPd/CeO2-polycrystalline, whereas at temperatures higher than 800K the catalytic performance of all samples is similar and close to the thermodynamic equilibrium. The improved performance of RhPd/CeO2-cubes and RhPd/CeO2-rods for ESR at low temperature is mainly ascribed to higher water-gas shift activity and a strong interaction between the bimetallic-oxide support interaction. STEM analysis shows the existence of RhPd alloyed nanoparticles in all samples, with no apparent relationship between ESR performance and RhPd particle size. X-ray diffraction under operating conditions shows metal reorganization on {1 0 0} and {1 1 0} ceria crystallographic planes during catalyst activation and ESR, but not on {1 1 1} ceria crystallographic planes. The RhPd reconstructing and tuned activation over ceria nanocubes and nanorods is considered the main reason for better catalytic activity with respect to conventional catalysts based on polycrystalline ceria. (C) 2015 Elsevier B.V. All rights reserved.Postprint (author's final draft

Quantum phase transitions in the Bose-Fermi Kondo model

We study quantum phase transitions in the Bose-Fermi Kondo problem, where a local spin is coupled to independent bosonic and fermionic degrees of freedom. Applying a second order expansion in the anomalous dimension of the Bose field we analyze the various non-trivial fixed points of this model. We show that anisotropy in the couplings is relevant at the SU(2) invariant non Fermi liquid fixed points studied earlier and thus the quantum phase transition is usually governed by XY or Ising-type fixed points. We furthermore derive an exact result that relates the anomalous exponent of the Bose field to that of the susceptibility at any finite coupling fixed point. Implications on the dynamical mean field approach to locally quantum critical phase transitions are also discussed.Comment: 13 pages, 9 figures, some references added/correcte