Microwave-assisted synthesis and electrochemical evaluation of VO2 (B) nanostructures

Understanding how intercalation materials change during electrochemical operation is paramount to optimizing their behaviour and function and in situ characterization methods allow us to observe these changes without sample destruction. Here we first report the improved intercalation properties of bronze phase vanadium dioxide VO2 (B) prepared by a microwave-assisted route which exhibits a larger electrochemical capacity (232 mAh g-1) compared with VO2 (B) prepared by a solvothermal route (197 mAh g-1). These electrochemical differences have also been followed using in situ X-ray absorption spectroscopy allowing us to follow oxidation state changes as they occur during battery operation

Constant real-space fractal dimensionality and structure evolution in Ti62Cu38 metallic glass under high pressure

The structure of binary Ti62Cu38 metallic glass is investigated under pressures up to 33.8 GPa using the pair distribution function analysis based on high-energy x-ray scattering and reverse Monte Carlo (RMC) simulations. At a global scale, its relative volume shows a continuously smooth curve as a function of pressure. The isothermal bulk modulus of Ti62Cu38 metallic glass is estimated as B0=132(3)GPa with B0′=5.8(0.4). At a local scale, the atomic packing structure under compression conditions, which is extracted from RMC simulations, shows that the topological short-range order is dominated by the deformed icosahedron polyhedra and basically maintains stable. From the relationship between the relative volume and changing ratio of the atomic separation distances, the real-space fractal dimensionality of this metallic glass is determined as about 2.5 for all of the first four peaks. This experimental result reveals the consistent nature of the fractal feature on the degree of self-similarity in this sample within the entire experimental pressure range

Hydrostatic low-range pressure applications of the Paris–Edinburgh cell utilizing polymer gaskets for diffuse X-ray scattering measurements

The use of a polymeric (Torlon or polyamide–imide) gasket material in a Paris–Edinburgh pressure cell for in situ high-pressure X-ray scattering measurements is demonstrated. The quality of the data obtained in this way is suitable for Bragg and pair distribution function analysis

Orbital Dimer Model for Spin-Glass State in Y2_2Mo2_2O7_7

The formation of a spin glass usually requires both structural disorder and frustrated magnetic interactions. Consequently, the origin of spin-glass behaviour in Y$_2$Mo$_2$O$_7$ $-$ in which magnetic Mo$^{4+}$ ions occupy a frustrated pyrochlore lattice with minimal compositional disorder $-$ has been a longstanding question. Here, we use neutron and X-ray pair-distribution function (PDF) analysis to develop a disorder model that resolves apparent incompatibilities between previously-reported PDF, EXAFS and NMR studies and provides a new and physical mechanism for spin-glass formation. We show that Mo$^{4+}$ ions displace according to a local "2-in/2-out" rule on each Mo$_4$ tetrahedron, driven by orbital dimerisation of Jahn-Teller active Mo$^{4+}$ ions. Long-range orbital order is prevented by the macroscopic degeneracy of dimer coverings permitted by the pyrochlore lattice. Cooperative O$^{2-}$ displacements yield a distribution of Mo$-$O$-$Mo angles, which in turn introduces disorder into magnetic interactions. Our study demonstrates experimentally how frustration of atomic displacements can assume the role of compositional disorder in driving a spin-glass transition.Comment: 6 pages, 3 figure

Understanding improved electrochemical properties of NiO-doped NiF2-C composite conversion materials by X-ray absorption spectroscopy and pair distribution function analysis.

The conversion reactions of pure NiF2 and the NiO-doped NiF2-C composite (NiO-NiF2-C) were investigated using X-ray absorption spectroscopy (XAS) and pair distribution function (PDF) analysis. The enhanced electronic conductivity of NiO-NiF2-C is associated with a significant improvement in the reversibility of the conversion reaction compared to pure NiF2. Different evolutions of the size distributions of the Ni nanoparticles formed during discharge were observed. While a bimodal nanoparticle size distribution was maintained for NiO-NiF2-C following the 1st and 2nd discharge, for pure NiF2 only smaller nanoparticles (∼14 Å) remained following the 2nd discharge. We postulate that the solid electrolyte interphase formed upon the 1st discharge at large overpotential retards the growth of metallic Ni leading to formation of smaller Ni particles during the 2nd discharge. In contrast, the NiO doping and the carbon layer covering the NiO-NiF2-C possibly facilitate the conversion process on the surface preserving the reaction kinetics upon the 2nd discharge. Based on the electronic conductivity and surface properties, the resulting size of the Ni nanoparticles is associated with the conversion kinetics and consequently the cyclability

A high-performance solid-state synthesized LiVOPO4 for lithium-ion batteries

Funding Information: This research was funded by U.S. Department of Energy , Office of Energy Efficiency and Renewable Energy (EERE) program under BMR award no. DE-EE0006852 . The structural characterization using NMR and PDF techniques was supported by the NorthEast Center for Chemical Energy Storage (NECCES), an Energy Frontier Research Center supported by the U.S. Department of Energy , Office of Science, Office of Basic Energy Sciences under award no. DE-SC0012583 . This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. We thank Dr. Fengxia Xin for help with TG-MS data acquisition, and Drs. Jatinkumar Rana and Jia Ding, for many helpful discussions. Funding Information: This research was funded by U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy (EERE) program under BMR award no. DE-EE0006852. The structural characterization using NMR and PDF techniques was supported by the NorthEast Center for Chemical Energy Storage (NECCES), an Energy Frontier Research Center supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under award no. DE-SC0012583. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. We thank Dr. Fengxia Xin for help with TG-MS data acquisition, and Drs. Jatinkumar Rana and Jia Ding, for many helpful discussions. Publisher Copyright: © 2019 The AuthorsPeer reviewe

Adsorbate-induced structural changes in 1-3 nm platinum nanoparticles

We investigated changes in the Pt–Pt bond distance, particle size, crystallinity, and coordination of Pt nanoparticles as a function of particle size (1–3 nm) and adsorbate (H2, CO) using synchrotron radiation pair distribution function (PDF) and X-ray absorption spectroscopy (XAS) measurements. The ∼1 nm Pt nanoparticles showed a Pt–Pt bond distance contraction of ∼1.4%. The adsorption of H2 and CO at room temperature relaxed the Pt–Pt bond distance contraction to a value close to that of bulk fcc Pt. The adsorption of H2 improved the crystallinity of the small Pt nanoparticles. However, CO adsorption generated a more disordered fcc structure for the 1–3 nm Pt nanoparticles compared to the H2 adsorption Pt nanoparticles. In situ XANES measurements revealed that this disorder results from the electron back-donation of the Pt nanoparticles to CO, leading to a higher degree of rehybridization of the metal orbitals in the Pt-adsorbate system

Diverse Physical States of Amorphous Precursors in Zeolite Sol Gel Syntheses

The assembly and structural evolution of amorphous precursors during zeolite crystallization is an important area of interest owing to their putative roles in the nucleation and growth of aluminosilicate microporous materials. Precursors range in complexity from oligomeric molecules and colloidal particles to gels comprised of heterogeneous silica and alumina domains. The physical state of precursors in most zeolite syntheses is generally not well understood; however, it is evident that the physicochemical properties of precursors depend on a wide range of conditions that include (but are not limited to) the selection of reagents, the composition of growth mixtures, the methods of preparation, and the use of inorganic and/or organic structure-directing agents. The fact that precursors evolve in size, shape, and/or microstructure during the course of nucleation and potentially throughout crystallization leads to questions pertaining to their mode of action in the formation of zeolites. This also highlights the diversity of species that are present in growth media, thus rendering the topic of zeolite synthesis essentially a black box to those attempting to better understand the fundamental role(s) of precursors. In this Article, we discuss the wide variety of precursors encountered in the synthesis of various framework types, emphasizing their complex physical states and the thermodynamic and kinetic factors that govern their heterogeneity.J.D.R. acknowledges financial support from the National Science Foundation (DMREF Award 1629398), the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0014468, and the Welch Foundation (Award E-1794). N.L. acknowledges support from the University of Alicante under the project GRE15-07. Work done at Argonne and use of the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy Office of Science by Argonne National Laboratory, were supported by the U.S. Department of Energy under Contract No. DE-AC02-06CH11357