Room-Temperature CrI Magnets through Lithiation.

The pursuit of two-dimensional (2D) magnetism is promising for energy-efficient electronic devices, including magnetoelectric random access memory and radio frequency/microwave magnonics, and it is gaining fundamental insights into quantum sensing technology. The key challenge resides in overseeing magnetic exchange interactions through a precise chemical reduction process, wherein manipulation of the arrangement of atoms and electrons is essential for achieving room-temperature 2D magnetism tailoring in a manner compatible with device architectures. Here, we report an electrochemically crafted CrI layered magnet─a van der Waals material─with precisely tailored lithiation and delithiation degrees.

Low-Temperature Decomposition and Oxidation of the Nerve Agent Simulant on Mesoporous Nickel Oxide and Cu-Doped Nickel Oxide.

In an effort to develop the next frontier filtration material for chemical warfare agent (CWA) decomposition, we synthesized mesoporous NiO and CuNiO ( = 0.10 and 0.20) and studied the decomposition of CWA simulant diisopropyl fluorophosphate (DIFP) on their surfaces.

Multiscale characterizations of structural evolution in mesoporous CeO.

ultra-small-angle and wide-angle X-ray scattering enables simultaneous tracking of the structural parameters of mesoporous CeO from the atomic scale to the micron-size scale. This multiscale approach provides a path to better understand structure-property relationships in mesoporous polycrystalline materials under dynamic conditions such as high temperature cycling.

Twisting two-dimensional iron sulfide layers into coincident site superlattices intercalation chemistry.

Layered van der Waals (vdW) materials are susceptible not only to various stacking polymorphs through translations but also twisted structures due to rotations between layers. Here, we study the influence of such layer-to-layer twisting through the intercalation of ethylenediamine (EDA) molecules into tetragonal iron sulfide (Mackinawite FeS). Selected area electron diffraction patterns of intercalated FeS display reflections corresponding to multiple square lattices with a fixed angle between them, contrary to a single square lattice seen in the unintercalated phase.

Experimental Study of the Adsorption and Decomposition of Sarin on Dry Copper(II) Oxide.

Organophosphonates were originally developed as insecticides but were quickly identified as highly toxic acetylcholinesterase inhibitors, leading to their exploitation as chemical warfare agents (CWA). To develop next generation filtration technologies, there must be a fundamental understanding of the molecular interactions occurring with toxic chemicals, such as CWAs. In this paper, we investigate the interaction between dry CuO nanoparticles and sarin (GB), using infrared (IR) spectroscopy in an effort to build an atomic understanding.

Spectroscopic studies of methyl paraoxon decomposition over mesoporous Ce-doped titanias for toxic chemical filtration.

The ever-constant threat of chemical warfare agents (CWA) motivates the design of materials to provide better protection to warfighters and civilians. Cerium and titanium oxide are known to react with organophosphorus compounds such Sarin and Soman. To study the decomposition of methyl paraoxon (CWA simulant) on such materials, we synthesized ordered mesoporous metal oxides (MMO) TiO, CeTiO (x = 0.

Mesoporous perovskite titanates hydrothermal conversion.

We demonstrate the successful hydrothermal conversion of mesoporous TiO to mesoporous perovskite SrTiO. This method allows for control of pore size distribution and can be readily applied for the preparation of other mesoporous titanates such as BaTiO and LiTiO. Such high-surface perovskites have potential in high-temperature applications due to their thermal stability.

Understanding Dimethyl Methylphosphonate Adsorption and Decomposition on Mesoporous CeO.

The increased risk of chemical warfare agent usage around the world has intensified the search for high-surface-area materials that can strongly adsorb and actively decompose chemical warfare agents. Dimethyl methylphosphonate (DMMP) is a widely used simulant molecule in laboratory studies for the investigation of the adsorption and decomposition behavior of sarin (GB) gas. In this paper, we explore how DMMP interacts with the as-synthesized mesoporous CeO.

Orbital Contribution to Paramagnetism and Noninnocent Thiophosphate Anions in Layered LiMPS Where M = Fe and Co.

Transition-metal thiophosphates and selenophosphates are layered systems with the potential for displaying two-dimensional (2D) magnetic phenomena. We present the crystal structures and magnetic properties of two lithium transition-metal thiophosphates, LiCoPS and LiFePS. The previously unreported LiCoPS crystallizes in the trigonal space group 31 with lattice parameters = 6.

On the Electrochemical Phase Evolution of Anti-PbO-Type CoSe in Alkali Ion Batteries.

The reaction mechanism of anti-PbO type CoSe in Li, Na, and K ion half cells is studied. Ex situ X-ray diffraction data is analyzed with the Rietveld method, in conjunction with discharge profiles and extended cycling data. These indicate that intercalation followed by a conversion reaction occur in all systems.

Distinguishing the Intrinsic Antiferromagnetism in Polycrystalline LiCoPO and LiMnPO Olivines.

We report a detailed investigation of the long-range magnetic ordering in polycrystalline samples of LiCoPO and LiMnPO, which belong to a series of well-known olivine cathode materials LiPO (M = Mn, Fe, Co, Ni). Samples were prepared by hydrothermal and solid state methods. The magnetic susceptibility is found to be strongly field-dependent, impacting the antiferromagnetic transition temperature and the bifurcation of the FC and ZFC curves.

Long-range magnetic order in hydroxide-layer-doped (Li Fe Mn OD)FeSe.

The (Li Fe OH)FeSe superconductor has been suspected of exhibiting long-range magnetic ordering due to Fe substitution in the LiOH layer. However, no direct observation such as magnetic reflection from neutron diffraction has been reported. Here, we use a chemical design strategy to manipulate the doping level of transition metals in the LiOH layer to tune the magnetic properties of the (Li Fe Mn OD)FeSe system.

Structural studies of the perovskite series LaSrCoO during chemical looping with methane.

Perovskite oxides are promising materials as oxygen carriers in chemical looping applications. We analyze in situ X-ray diffraction data on the perovskite phases La1-xSrxCoO3-δ for x = 0, 0.25, 0.

Manipulating surface magnetic order in iron telluride.

Control of emergent magnetic orders in correlated electron materials promises new opportunities for applications in spintronics. For their technological exploitation, it is important to understand the role of surfaces and interfaces to other materials and their impact on the emergent magnetic orders. Here, we demonstrate for iron telluride, the nonsuperconducting parent compound of the iron chalcogenide superconductors, determination and manipulation of the surface magnetic structure by low-temperature spin-polarized scanning tunneling microscopy.

Proton and ammonia intercalation into layered iron chalcogenides.

Structurally related to the iron-based superconductors, two new intercalated iron chalcogenides (H0.5NH3)Fe2Ch2 where Ch = S, Se have been prepared. By topochemical conversion, the protons were exchanged by lithium to form (Li0.

Superconductivity and magnetism in iron sulfides intercalated by metal hydroxides.

Inspired by naturally occurring sulfide minerals, we present a new family of iron-based superconductors. A metastable form of FeS known as the mineral mackinawite forms two-dimensional sheets that can be readily intercalated by various cationic guest species. Under hydrothermal conditions using alkali metal hydroxides, we prepare three different cation and metal hydroxide-intercalated FeS phases including (Li Fe OH)FeS, [(Na Fe )(OH)]FeS, and K Fe S.

Metastable Layered Cobalt Chalcogenides from Topochemical Deintercalation.

We present a general strategy to synthesize metastable layered materials via topochemical deintercalation of thermodynamically stable phases. Through kinetic control of the deintercalation reaction, we have prepared two hypothesized metastable compounds, CoSe and CoS, with the anti-PbO type structure from the starting compounds KCoSe and KCoS, respectively. Thermal stability, crystal structure from X-ray and neutron diffraction, magnetic susceptibility, magnetization, and electrical resistivity are studied for these new layered chalcogenides; both CoSe and CoS are found to be weak itinerant ferromagnets with Curie temperatures close to 10 K.

Influence of transition metal electronegativity on the oxygen storage capacity of perovskite oxides.

The selection of highly efficient oxygen carriers (OCs) is a key step necessary for the practical development of chemical looping combustion (CLC). In this study, a series of ABO3 perovskites, where A = La, Ba, Sr, Ca and B = Cr, Mn, Fe, Co, Ni, Cu, are synthesized and tested in a fixed bed reactor for reactivity and stability as OCs with CH4 as the fuel. We find that the electronegativity of the transition metal on the B-site (λB), is a convenient descriptor for oxygen storage capacity (OSC) of our perovskite samples.

Stabilization of cubic Sr2FeMoO6 through topochemical reduction.

Sr2FeMoO6 has been extensively studied for application in spintronic devices. Through the topochemical de-intercalation of oxygen anions with metal hydride reduction, we demonstrate that the high temperature cubic phase is stabilized, at room temperature, whilst leaving the magnetic ordering intact. Synchrotron X-ray and neutron powder diffraction were used to characterize the structure and stoichiometry of the reduced oxide.

PZT-like structural phase transitions in the BiFeO3-KNbO3 solid solution.

Despite the high prominence of the perovskites BiFeO(3) and KNbO(3) the solid solution between the two has received little attention. We report a detailed neutron and synchrotron X-ray powder diffraction, and Raman spectroscopy study which demonstrates an R3c→P4mm→Amm2 series of structural phase transitions similar to that exhibited by the PbZrO(3)-PbTiO(3) solid solution.

Magnetically stabilized Fe8(μ4-S)6S8 clusters in Ba6Fe25S27.

We have prepared Ba6Fe25S27, and studied its magnetic properties and electronic structure. Single crystal diffraction revealed a cubic phase (Pm3[combining macron]m) with a = 10.2057(9) Å and Z = 1.

Synthetic and coordination chemistry of the heavier trivalent technetium binary halides: uncovering technetium triiodide.

Technetium tribromide and triiodide were obtained from the reaction of the quadruply Tc-Tc-bonded dimer Tc2(O2CCH3)4Cl2 with flowing HX(g) (X = Br, I) at elevated temperatures. At 150 and 300 °C, the reaction with HBr(g) yields TcBr3 crystallizing with the TiI3 structure type. The analogous reactions with flowing HI(g) yield TcI3, the first technetium binary iodide to be reported.

Structural disorder, magnetism, and electrical and thermoelectric properties of pyrochlore Nd2Ru2O7.

Polycrystalline Nd2Ru2O7 samples have been prepared and examined using a combination of structural, magnetic, and electrical and thermal transport studies. Analysis of synchrotron x-ray and neutron diffraction patterns suggests some site disorder on the A-site in the pyrochlore sublattice: Ru substitutes on the Nd-site up to 7.0(3)%, regardless of the different preparative conditions explored.

Phase separation and superconductivity in Fe(1+x)Te(0.5)Se(0.5).

Fe(1+x)Te(0.5)Se(0.5) is the archetypical iron-based superconductor.

Magnetic ordering and magnetodielectric phenomena in CoSeO4.

CoSeO(4) has a structure consisting of edge-sharing chains of Co(2+) octahedra which are held together by SeO(4)(2-) tetrahedra via shared oxygen atoms at the edges of the octahedra. DC magnetization measurements indicate a transition to an ordered state below 30 K. Powder neutron diffraction refinements suggest an ordered state with two unique antiferromagnetic chains within the unit cell.