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Intermetallic compounds (IMCs) are interesting materials in the field of heterogeneous catalysis due to their ordered structure and tunable electronic properties. These IMCs can act as precursor to synthesize metal/metal oxide composite catalysts that are more active than just the starting IMCs. In this work, Sm2Co7 and SmCo5 IMCs were used as precursors to prepare highly active and stable Co_SmO, Co_Sm2O3 and Co3O4_Sm2O3 catalysts via controlled modification. Transmission electron microscopy (TEM) demonstrated that Co and Sm2O3 Nano crystallites were formed after the modification of the IMC. IMCs derived Co_SmO and Co_Sm2O3 were stable and active in NH3 synthesis with very low activation energy of 55 and 77 kJ mol−1 respectively. The structural, morphological and surface characterization revealed that a strong metal support interaction existed between Co and Sm2O3 (electronic effect) along with the presence of surface steps and edges of Co nano crystallites (structural effect) that activate the N2 at low temperature (360 °C). Similarly, Co3O4_Sm2O3 derived from the IMC were found to exhibit high CO2 and butane conversion in butane dry reforming at low temperature (550 °C) with excellent stability. The study revealed that the presence of Co3O4 and Sm2O3 active sites in close proximity (geometrical effect) promoted the simultaneous adsorption or activation of butane and CO2. The Co_Sm2O3 and Co3O4_Sm2O3 derived from IMCs exhibited superior catalytic performance in both NH3 synthesis and butane dry reforming compared to similar compositional catalyst synthesized by hydrothermal route. These studies pave the way to potential uses of IMCs as precursors to derive composite metal/metal oxide catalysts that are highly stable and active despite their low surface areas.

We have investigated the pressure (P) effect on structural (up to 10 GPa), transport [R(T): up to 10 GPa], and magnetic [(M(T): up to 1 GPa)] properties and analyzed the flux pinning mechanism of the Fe0.99Mn0.01Se0.5Te0.5 superconductor. The maximum superconducting transition temperature (T c) of 22 K with the P coefficient of T c dT c/dP = +2.6 K/GPa up to 3 GPa (dT c/dP = -3.6 K/GPa, 3 ≤ P ≥ 9 GPa) was evidenced from R(T) measurements. The high-pressure diffraction and density functional theory (DFT) calculations reveal structural phase transformation from tetragonal to hexagonal at 5.9 GPa, and a remarkable change in the unit cell volume is observed at ∼3 GPa where the T c starts to decrease, which may be due to the reduction of charge carriers, as evidenced by a reduction in the density of states (DOS) close to the Fermi level. At higher pressures of 7.7 GPa ≤ P ≥ 10.2 GPa, a mixed phase (tetragonal + hexagonal phase) is observed, and the T c completely vanishes at 9 GPa. A significant enhancement in the critical current density (J C) is observed due to the increase of pinning centers induced by external pressure. The field dependence of the critical current density under pressure shows a crossover from the δl pinning mechanism (at 0 GPa) to the δT c pinning mechanism (at 1.2 GPa). The field dependence of the pinning force at ambient condition and under pressure reveals the dense point pinning mechanism of Fe0.99Mn0.01Se0.5Te0.5. Moreover, both upper critical field (H C2) and J C are enhanced significantly by the application of an external P and change over to a high P phase (hexagonal ∼5.9 GPa) faster than a Fe0.99Ni0.01Se0.5Te0.5 (7.7 GPa) superconductor.

We report the synthesis, at 7 GPa and 923 K, and the thermoelastic characterization, up to 16 GPa and 850 K, of a single crystal of Mg-sursassite, Mg5Al5Si6O21(OH)7. In situ high-pressure and high-temperature single-crystal diffraction allowed the study of structural variation at non-ambient conditions and the determination of bulk elastic properties. The refined parameters of a second-order Birch-Murnaghan equation of state (BM-II EoS) are V0 = 446.02(1) Å3 and KT0 = 135.6(7) GPa. The thermal expansion coefficients of a Berman-type EoS are α0 = 3.14 (5) × 10−5 K−1, α1 = 2.50(16) × 10−8 K−2, and V0 = 445.94(3). For comparison, the P-V EoS is determined for a natural sursassite sample, ideally Mn4Al6Si6O22(OH)6. The refined parameters of BM-II EoS [V0 = 470.2(3) Å3, KT0 = 128(4) GPa] indicate that composition has a minimal effect on elastic properties. The similarity of density and bulk properties of Mg-sursassite if compared to olivine and other anhydrous mantle minerals suggests that this phase could be overseen by geophysical methods.

Defect aggregates in doped ceria play a crucial role in blocking the movement of oxygen vacancies and hence in reducing ionic conductivity. Nevertheless, evaluation of their amount and the correlation between domain size and transport properties is still an open issue. Data derived from a high-pressure X-ray diffraction investigation performed on the Ce1–x(Nd0.74Tm0.26)xO2–x/2 system are employed to develop a novel approach aimed at evaluating the defect aggregate content; the results are critically discussed in comparison to the ones previously obtained from Sm- and Lu-doped ceria. Defect clusters are present even at the lowest considered x value, and their content increases with increasing x and decreasing rare earth ion (RE3+) size; their amount, distribution, and spatial correlation can be interpreted as a complex interplay between the defects’ binding energy, nucleation rate, and growth rate. The synoptic analysis of data derived from all of the considered systems also suggests that the detection limit of the defects by X-ray diffraction is correlated to the defect size rather than to their amount, and that the vacancies’ flow through the lattice is hindered by defects irrespective of their size and association degree., A novel approach to the treatment of high-pressure X-ray diffraction data is applied to several rare earth-doped ceria systems with the aim of providing an evaluation of the amount of defect aggregates and of the composition of the CeO2-based solid solution. By this method, it is possible to effectively correlate the structural properties and ionic conductivity of the studied material.

Orthorhombic GeSe is a promising thermoelectric material. However, large band gap and strong covalent bonding result in a low thermoelectric figure of merit, zT≈0.2. Here, we demonstrate a maximum zT≈1.35 at 627 K in p-type polycrystalline rhombohedral (GeSe)0.9 (AgBiTe2 )0.1 , which is the highest value reported among GeSe based materials. The rhombohedral phase is stable in ambient conditions for x=0.8-0.29 in (GeSe)1-x (AgBiTe2 )x . The structural transformation accompanies change from covalent bonding in orthorhombic GeSe to metavalent bonding in rhombohedral (GeSe)1-x (AgBiTe2 )x . (GeSe)0.9 (AgBiTe2 )0.1 has closely lying primary and secondary valence bands (within 0.25-0.30 eV), which results in high power factor 12.8 μW cm-1 K-2 at 627 K. It also exhibits intrinsically low lattice thermal conductivity (0.38 Wm-1 K-1 at 578 K). Theoretical phonon dispersion calculations reveal vicinity of a ferroelectric instability, with large anomalous Born effective charges and high optical dielectric constant, which, in concurrence with high effective coordination number, low band gap and moderate electrical conductivity, corroborate metavalent bonding in (GeSe)0.9 (AgBiTe2 )0.1 . We confirmed the presence of low energy phonon modes and local ferroelectric domains using heat capacity measurement (3-30 K) and switching spectroscopy in piezoresponse force microscopy, respectively.

Here we address the challenging problem of pressure induced hydrogen sublattice disordering in layered hydroxides using synchrotron X-ray powder diffraction (XRPD) and first-principles calculations...

A study on the crystal structure of monoclinic HfO2 has been performed using synchrotron X-ray and neutron diffraction data separately, as well as a combination of both. The precision of the structural parameters increases significantly due to application of the neutron diffraction technique. The experimental oxygen positions in HfO2, derived precisely, are visualized only by semi-local density functional calculations in terms of the calculated electronic band gap, but are not captured as accurately by using hybrid functionals.

In this study the firstin situhigh-pressure single-crystal X-ray diffraction experiments at Xpress, the Indo-Italian beamline of the Elettra synchrotron, Trieste (Italy), are reported. A description of the beamline experimental setup and of the procedures for single-crystal centring, data collection and processing, using diamond anvil cells, are provided. High-pressure experiments on a synthetic crystal of clinoenstatite (MgSiO3), CaCO3polymorphs and a natural sample of leucophoenicite [Mn7Si3O12(OH)2] validated the suitability of the beamline experimental setup to: (i) locate and characterize pressure-induced phase transitions; (ii) solveab initiothe crystal structure of high-pressure polymorphs; (iii) perform fine structural analyses at the atomic scale as a function of pressure; (iv) disclose complex symmetry and structural features undetected using conventional X-ray sources.

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Heteroatom-rich porous-organic-polymers (POPs) comprising highly cross-linked robust skeletons with high physical and thermal stability, high surface area, and tunable pore size distribution have garnered significant research interest owing to their versatile functionalities in a wide range of applications. Here, we report a newly developed organogel-assisted porous-organic-polymer (POP) supported Cu catalyst (Cu@TpRb-POP). The organogel was synthesized via a temperature induced gelation strategy, employing Schiff-base coupling between 2,4,6-triformylphloroglucinol aldehyde (Tp) and pararosaniline base (Rb). The gel is subsequently transformed to hierarchical porous organic structures without the use of any additive, thereby offering advantageous features including extremely low density, high surface area, a highly cross-linked framework, and a heteroatom-enriched backbone of the polymer. During the semi-hydrogenation of terminal and internal alkynes, the Cu@TpRb-POP-B catalyst with Cu embedded in the TpRb-POP structure consistently demonstrated improved selectivity towards alkenes compared to Cu@TpRb-POP-A, which contains Cu NPs exposed at the exterior surfaces of the POP support. Additionally, Cu@TpRb-POP-B showed higher stability and reusability than Cu@TpRb-POP-A. The superior performance of the Cu@TpRb-POP-B catalyst is attributed to the steric hindrance effect, which controls the product selectivity, as well as the synergistic interaction between the heteroatom-rich POP framework and the embedded Cu NPs. Both the effects are corroborated by experimental characterization of the catalysts and density functional theory (DFT) calculations. Submitted/Accepted version R. P. and S. C. S. acknowledge DST-INSPIRE (GAP-0799) and the Council of Scientific and Industrial Research (CSIR), New Delhi, for their respective senior research fellowships. J. M. acknowledges the Department of Science and Technology, India, for the DST-INSPIRE Faculty Research Project Grant (GAP-0522), CSIR-YSA Research Grant (reference no. HRDG/ YSA-19/02/21(0045)/2019) and Focused Basic Research (FBR) Grant under the CLP theme (reference no. 34/1/TD-CLP/ NCP-FBR 2020-RPPBDD-TMD-SeMI) for financial support at CSIR-IICT, Hyderabad.

The local structure of La(Fe1-xMnx)AsO, showing suppression of long-range magnetic order by Mn-substitution, has been studied. Extended X-ray absorption fine structure (EXAFS) measurements at As K-edge and Fe K-edge are used to probe the atomic correlations in the FeAs-layer. We have found that both Fe-As and Fe-Fe bondlengths tend to increase with increasing Mn concentration. The associated mean square relative displacements (MSRD) reveal a gradual increase indicating increased local disorder in the FeAs-layer with Mn content. The results reveal that the FeAs-layer thickness, measured by the As-height (hAs) from the Fe-Fe plane, is correlated with the Neel temperature. Furthermore, Fe Kβ X-ray emission spectroscopy (XES) shows a sharp increase in the Fe local magnetic moment with Mn substitution. The importance of the FeAs layer thickness in describing magnetic correlations in La(Fe1−xMnx)AsO is discussed.

The application of an external pressure on Metal Halide Perovskite (MHPs) has become a fascinating way of tuning their optical properties, achieving also novel features. Here, the pressure response of 2D MHPs including a long alkyl chain made of ten carbon atoms, namely decylammonium (DA), has been investigated as a function of the central atom in DA2PbI4 and DA2GeI4. The two systems share a common trend in the phase stability, displaying a transition from an orthorhombic to a monoclinic phase around 2 GPa, followed by a phase separation in two monoclinic phases characterized by different c-axis. The optical properties show rather different behavior due to the presence of Pb or Ge. DA2PbI4 shows a progressive red shift of the band gap from 2.28 eV at ambient conditions, to 1.64 eV at 11.5 GPa, with a narrow PL emission composed by two components, with the second one appearing in concomitance with the phase separation and significantly shifted to lower energy. On the other hand, DA2GeI4, changes from a non-PL system at ambient pressure, to a clear broadband emitter centered around 730 nm (FWHM ~ 170 nm), with a large stoke shift, and an intensity maximum at about 3.7 GPa. This work sheds light on the structural stability of 2D perovskites characterized by extended alkyl chains, to date limited to four carbon atoms, and shows the pressure-induced emergence of broad emission in a novel lead-free perovskite, DA2GeI4. The evidence of wide emission by a moderate pressure in a germanium-based 2D MHP represents a novel result which may open the design, by chemical pressure, of efficient wide or even white lead-free emitters.

Manipulation by external pressure of the optical response of 2D Metal Halide Perovskites (MHPs) is a fascinating route to tune their properties and promote the emergence of novel features. We investigate here DA

International audience; Recently, filling zeolites with gaseous hydrocarbons at high pressures in diamond anvil cells has been carried out to synthesize novel polymer-guest/zeolite-host nanocomposites with potential, intriguing applications, although the small amount of materials, 10–7 cm3, severely limited true technological exploitation. Here, liquid phenylacetylene, a much more practical reactant, was polymerized in the 12 Å channels of the aluminophosphate Virginia Polytechnic Institute—Five (VFI) at about 0.8 GPa and 140 °C, with large volumes in the order of 0.6 cm3. The resulting polymer/VFI composite was investigated by synchrotron X-ray diffraction and optical and 1H, 13C, and 27Al nuclear magnetic resonance spectroscopy. The materials, consisting of disordered π-conjugated polyphenylacetylene chains in the pores of VFI, were deposited on quartz crystal microbalances and tested as gas sensors. We obtained promising sensing performances to water and butanol vapors, attributed to the finely tuned nanostructure of the composites. High-pressure synthesis is used here to obtain an otherwise unattainable true technological material.

Hydrostatic pressure response of $\mathrm{LaAu}{\mathrm{Sb}}_{2}$ charge density wave (CDW) system is investigated using electrical transport, x-ray diffraction (XRD), and density-functional theory (DFT). Resistivity data at ambient pressure evidence a clear CDW transition at 83 K. X-ray diffraction at ambient pressure reveals that in plane and out of plane axes show opposite behavior with decreasing temperature, in particular, out of plane $c$ axis develops a distinct change at \ensuremath{\sim}250 K, much above the observed CDW transition at 83 K. The CDW transition shifts to low temperature with increasing pressure. Our resistivity data indicate a complete suppression of the CDW transition at \ensuremath{\sim}3.6 GPa. High-pressure XRD revealed a change from the linear trend for the out of plane ($c$) and the in plane ($a$) lattice parameters for pressure above 3.8 GPa. With compression, DFT indicated an anomaly in the c/a ratio around 8 GPa. The calculated electronic structure also indicated minor changes in the band structure in this pressure range. In addition, high-pressure DFT structural investigations reveal the $\mathrm{LaAu}{\mathrm{Sb}}_{2}$ system to be stable up to pressures as high as 150 GPa.

The effort to find thermoelectric materials suitable for different applications is an intense research topic of a large material science community. In this context, A-site-deficient La1/3NbO3, which shows an irreversible pressure-induced amorphization at above 15 GPa, has attracted recent attention. Here, we present a temperature-dependent Nb K-edge extended x-ray absorption fine structure (EXAFS) study of La1/3NbO3 in the range 77-500 K probing the Nb-O bond correlations. These results are compared with the Nb-O bond correlations in two related oxides NbO2 and Nb2O5. In comparison with NbO2 and Nb2O5, the Nb-O bond mean square relative displacements in La1/3NbO3 show much weaker temperature dependence revealing its enhanced spring constant. The “A” site deficiency in La1/3NbO3 may allow the oxygen atoms to preserve their local geometry and thus are less responsive to the external stimuli like temperature, which may be important in determining the thermal and electrical conductivity properties of this system.

Among the various methods employed in the synthesis of nanostructures, those involving high operating temperature and sharp thermal gradients often lead to the establishment of new exotic properties. Herein, we report on the formation of Cu-Ni metallic alloy nanoparticles with greatly enhanced stiffness achieved through direct-current transferred arc-thermal plasma assisted vapour-phase condensation. High pressure synchrotron X-ray powder diffraction (XRPD) at ambient temperature as well as XRPD in the temperature range 180 to 920 K, show that the thermal arc-plasma route resulted in alloy nanoparticles with much enhanced bulk modulus compared to their bulk counterparts. Such a behaviour may find an explanation in the sudden quenching assisted by the retention of a large amount of local strain due to alloying, combined with the perfect miscibility of the elemental components during the thermal plasma synthesis process.

By means of in situ synchrotron X-ray diffraction and Raman spectroscopy under hydrostatic pressure, we investigate the structural stability of the quadruple perovskite LaMn7O12. At 34 GPa, the data unveil a first-order structural phase transition from monoclinic I2/m to cubic Im-3 symmetry characterized by a pronounced contraction of the unit cell and by a significant modifications in the Raman phonon modes. The phase transition is also marked by the suppression of Jahn-Teller distortion which is present in the ambient monoclinic phase. In addition, above 20 GPa pressure, a sudden and simultaneous broadening is observed in several Raman modes which suggests the onset of a sizable electron-phonon interaction and incipient charge mobility. Considering that LaMn7O12 is paramagnetic insulator at ambient, and Jahn-Teller distortion is frozen in the high-pressure Im-3 phase, we argue that this phase could be a potential candidate to host a purely electronic insulator-metal transition with no participation of the lattice, 6 pages, 4 figures

Physical review materials 5(11), 113607 (2021). doi:10.1103/PhysRevMaterials.5.113607, The thermodynamic stability of the premartensite (PM) phase has been a topic of extensive investigation in shape memory alloys as it affects the main martensite phase transition and the related physical properties. In general, the PM phase is stable over a rather narrow temperature-composition range. We present here evidence for chemical pressure induced suppression of the main martensite transition and stabilization of the PM phase over a very wide temperature range from 300 to ���5K in a magnetic shape memory alloy (MSMA), Ni$_{50}$Mn$_{34}$In$_{16}$, using magnetic susceptibility, synchrotron x-ray powder diffraction (SXRPD) studies, and first-principles calculations. The ac-susceptibility studies show a highly skewed and smeared peak around 300 K without any further transition up to the lowest temperature of our measurement (5 K) for ���5% Al substitution. The temperature evolution of the SXRPD patterns confirms the appearance of the PM phase related satellite peaks at T���300K without any splitting of the main austenite (220) peak showing preserved cubic symmetry. This is in marked contrast to the temperature evolution of the SXRPD patterns of the martensite phase of the Al free as well as ���3% Al substituted compositions where the austenite (220) peak shows a clear splitting due to Bain distortion signalling symmetry breaking transition. Our theoretical calculations support the experimental findings and reveal that the substitution at the In site by a smaller size atom, like Al, can stabilize the PM phase with preserved cubic symmetry. Our results demonstrate that Al-substituted Ni-Mn-In MSMAs provide an ideal platform for investigating the physics of various phenomena related to the PM state., Published by APS, College Park, MD

Magnetic skyrmions are vortex-like spin textures, which can be manipulated by external stress or pressure via magnetoelastic effects. Here, we present the observation of isostructural phase transition in a biskyrmion host hexagonal MnNiGa at a pressure around 4 GPa using pressure-dependent synchrotron x-ray powder diffraction (XRD) data analysis. Our XRD data reveals anisotropic compression behavior with pressure with different compression rates of the a-axis in the basal plane and the c-axis in the prismatic plane. However, the hexagonal symmetry remains unchanged for pressure up to 14 GPa. Fitting of unit cell volume with pressure using a second-order Birch-Murnagan equation of state reveals that the data to fall into two distinct curves for those above and below 4 GPa. The present study contributes to the understanding of crystal structure with the application of hydrostatic pressure in the biskyrmion host MnNiGa, wherein the skyrmion textures can be manipulated by pressure due to their magnetoelastic character.

Non-communicable diseases constitute a significant part of the overall morbidity and mortality in Nepal.Prevention of non-communicable diseases involves lifestyle modification which is directly dependent onthe awareness of the population of the risk factors for diseases and methods of prevention. The aim of thisstudy was to estimate the levels of awareness about three common non-communicable diseases among theresidents of remote villages in Nepal. The study was conducted in villages in 5 districts of Nepal using a directinterview method after obtaining verbal consent of the participants. The study included 218 participants,of whom 127 were female and 91 were male. The participants ranged in age from 18-93 years. Levels ofawareness about causative factors of hypertension, asthma and diabetes among the respondents were 62.2%,22.5% and 50.9% respectively. Levels of awareness of preventive methods among the participants were52.8%, 38.9% and 55.3% for hypertension, asthma and diabetes respectively. The difference in levels ofawareness among both genders, different age groups and differing educational status was also studied.

The chromium terephthalate MIL-101 is a mesoporous metal-organic framework (MOF) with unprecedented adsorption capacities due to the presence of giant pores. The application of an external pressure can effectively modify the open structure of MOFs and its interaction with guest molecules. In this work, we study MIL-101 under pressure by synchrotron X-ray diffraction and infrared (IR) spectroscopy with several pressure transmitting media (PTM). Our experimental results clearly show that when a solid medium as NaCl is employed, an irreversible amorphization of the empty structure occurs at about 0.4 GPa. Using a fluid PTM, as Nujol or high-viscosity silicone oil, results in a slight lattice expansion and a strong modification of the peak frequency and shape of the MOF hydroxyl vibration below 0.1 GPa. Moreover, the framework stability is enhanced under pressure with the amorphization onset shifted to about 7 GPa. This coherent set of results points out the insertion of the fluid inside the MIL-101 pores. Above 7 GPa, concomitantly to the nucleation of the amorphous phase, we observe a peculiar medium-dependent lattice expansion. The behavior of the OH stretching vibrations under pressure is profoundly affected by the presence of the guest fluid, showing that OH bonds are sensitive vibrational probes of the host-guest interactions. The present study demonstrates that even a polydimethylsiloxane silicone oil, although highly viscous, can be effectively inserted into the MIL-101 pores at a pressure below 0.2 GPa. High pressure can thus promote the incorporation of large polymers in mesoporous MOFs.

The ${\mathrm{BiS}}_{2}$-based layered materials are characterized by a highly susceptible physical state, revealing a large response to external conditions. A particular case is the ${\mathrm{EuFBiS}}_{2}$ compound, showing a superconducting transition temperature ${T}_{c}\ensuremath{\sim}0.3$ K at ambient pressure. Upon increasing external pressure, ${T}_{c}$ goes through a large amplification, accompanied by a structural phase transition (SPT) from tetragonal to monoclinic symmetry. Here, we use a combination of Eu ${\phantom{\rule{4pt}{0ex}}L}_{3}$ - edge x-ray absorption spectroscopy and synchrotron x-ray diffraction to unveil the evolution of the Eu valence and lattice symmetry under high pressure. We find that the average Eu valence increases gradually with pressure, exhibiting a pressure plateau near the SPT, at which the ${T}_{c}$ increases sharply. Since in ${\mathrm{EuFBiS}}_{2}$ the charge carriers are introduced via self-doping induced by the mixed valence of the Eu ions, our findings clearly indicate that the role of the charge doping is marginal in the ${T}_{c}$ enhancement. On the other hand, the structural distortions, taking place at the SPT, play a central role in enhancing the superconducting properties of the ${\mathrm{EuFBiS}}_{2}$ system.

A study on the crystal structure of monoclinic HfO

Enormous efforts have been initiated in the production of biobased fuels and value-added chemicals

In the heavy-fermion system $Yb_2Pd_2In_{1-x}Sn_x$, the interplay of crystal-field splitting, Kondo effect, and Ruderman-Kittel-Kasuya-Yosida interactions leads to complex chemical-, pressure-, and magnetic-field phase diagrams, still to be explored in full detail. By using a series of techniques, we show that even modest changes of parameters other than temperature are sufficient to induce multiple quantum-critical transitions in this highly susceptible heavy-fermion family. In particular, we show that, above $\sim 10$ kbar, hydrostatic pressure not only induces an antiferromagnetic phase at low temperature, but it likely leads to a reorientation of the Yb magnetic moments and/or the competition among different antiferromagnetic configurations.

Physical review / B 101(2), 020508 (2020). doi:10.1103/PhysRevB.101.020508, The coexistence of phases, characterized by different electronic degrees of freedom, commonly occurs in layered superconductors. Among them, alkaline intercalated chalcogenides are model systems showing the microscale coexistence of paramagnetic (PAR) and antiferromagnetic (AFM) phases, however, the temporal behavior of different phases is still unknown. Here, we report a visualization of the atomic motion in the granular phase of KxFe2−ySe2 using x-ray photon correlation spectroscopy. Unlike the PAR phase, the AFM texture reveals an intermittent dynamics with avalanches as in martensites. When cooled down across the superconducting transition temperature Tc, the AFM phase goes through an anomalous slowing behavior, suggesting a direct relationship between the atomic motions in the AFM phase and the superconductivity. In addition to providing compelling evidence of avalanchelike dynamics in a layered superconductor, the results provide a basis for different theoretical models to describe the quantum states in inhomogeneous solids., Published by Inst., Woodbury, NY

Enormous efforts have been initiated in the production of biobased fuels and value-added chemicals via biorefinery owing to the scarcity of fossil resources and huge environmental synchronization. Herein, non-noble metal-based metal/mixed metal oxide supported on carbon employing a metal-organic framework as a sacrificial template is demonstrated for the first time in the selective hydrodeoxygenation (HDO) of biomass-derived furfural (FFR) to 2-methyl furan (MF). The aforementioned catalyst (referred to as Cu/CuFe2O4@C-A) exhibited extraordinary catalytic proficiency (100% selectivity toward MF) compared with the conventional Cu/CuFe2O4@C-B catalyst which was prepared by the wet impregnation method. High-resolution transmission electron microscopy and synchrotron X-ray diffraction studies evidenced the existence of both metal (Cu) and mixed metal oxide (CuFe2O4) phases, in which the metal could help in hydrogenation to alcohol and metal oxide could assist in the hydroxyl group removal step during HDO reaction. The stabilization of encapsulated metal/metal oxide nanoparticles in the carbon matrix, modulation of the electronic structure, and regulation of geometric effects in the Cu/CuFe2O4@C-A are thought to play an important role in its excellent catalytic performance, confirmed by X-ray photoelectron spectroscopy and X-ray absorption spectroscopy investigations. Furthermore, the structure and activity interconnection was confirmed by in situ attenuated total reflection-IR studies, which manifested the strong interfacial interaction between FFR and the Cu/CuFe2O4@C-A catalyst. This finding was further supported by NH3 temperature-programmed desorption analysis, which suggested that the presence of more Lewis/weak acidic sites in this catalyst was beneficial for the hydrogenolysis step in HDO reaction. Additionally, H2 temperature-programmed reduction studies revealed that the adsorption of H2 was stronger on the Cu/CuFe2O4@C-A than that over the conventional Cu/CuFe2O4@C-B catalyst; thus, the former catalyst promoted activation of H2. A detailed kinetic analysis which demonstrated the lower activation energy barrier along with dual active sites attributed for the activation of the two separate reactions in the HDO process on the Cu/CuFe2O4@C-A catalyst. This work has great implication in developing a highly stable catalyst for the selective upgradation of biomass without deactivation of metal sites in extended catalytic cycles and opens the door of opportunity for developing a sustainably viable catalyst in biomass refinery industries.