Reza J. Kashtiban

Instant MOFs: continuous synthesis of metal-organic frameworks by rapid solvent mixing.

A continuous flow reactor allows the preparation of porous metal-organic framework materials with crystallisation induced by rapid mixing of streams of preheated water and solutions of reagents in organic solvent: this gives high volume production (132 g h(-1)) with crystallite size of the products from nanoscale to micron.

Water-splitting electrocatalysis in acid conditions using ruthenate-iridate pyrochlores

The pyrochlore solid solution (Na0.33Ce0.67)2(Ir1−xRux)2O7 (0≤x≤1), containing B-site RuIV and IrIV is prepared by hydrothermal synthesis and used as a catalyst layer for electrochemical oxygen evolution from water at pH<7. The materials have atomically mixed Ru and Ir and their nanocrystalline form allows effective fabrication of electrode coatings with improved charge densities over a typical (Ru,Ir)O2 catalyst. An in situ study of the catalyst layers using XANES spectroscopy at the Ir LIII and Ru K edges shows that both Ru and Ir participate in redox chemistry at oxygen evolution conditions and that Ru is more active than Ir, being oxidized by almost one oxidation state at maximum applied potential, with no evidence for ruthenate or iridate in +6 or higher oxidation states.

Van der Waals pressure and its effect on trapped interlayer molecules.

Van der Waals assembly of two-dimensional crystals continue attract intense interest due to the prospect of designing novel materials with on-demand properties. One of the unique features of this technology is the possibility of trapping molecules between two-dimensional crystals. The trapped molecules are predicted to experience pressures as high as 1 GPa. Here we report measurements of this interfacial pressure by capturing pressure-sensitive molecules and studying their structural and conformational changes. Pressures of 1.2±0.3 GPa are found using Raman spectrometry for molecular layers of 1-nm in thickness. We further show that this pressure can induce chemical reactions, and several trapped salts are found to react with water at room temperature, leading to two-dimensional crystals of the corresponding oxides. This pressure and its effect should be taken into account in studies of van der Waals heterostructures and can also be exploited to modify materials confined at the atomic interfaces.

Atomically resolved imaging of highly ordered alternating fluorinated graphene

One of the most desirable goals of graphene research is to produce ordered two-dimensional (2D) chemical derivatives of suitable quality for monolayer device fabrication. Here we reveal, by focal series exit wave reconstruction (EWR), that C2F chair is a stable graphene derivative and demonstrates pristine long-range order limited only by the size of a functionalized domain. Focal series of images of graphene and C2F chair formed by reaction with XeF2 were obtained at 80 kV in an aberration-corrected transmission electron microscope. EWR images reveal that single carbon atoms and carbon-fluorine pairs in C2F chair alternate strictly over domain sizes of at least 150 nm(2) with electron diffraction indicating ordered domains ≥ 0.16 μm(2). Our results also indicate that, within an ordered domain, functionalization occurs on one side only as theory predicts. In addition, we show that electron diffraction provides a quick and easy method for distinguishing between graphene, C2F chair and fully fluorinated stoichiometric CF 2D phases.

Structures and Magnetism of the Rare-Earth Orthochromite Perovskite Solid Solution LaxSm1–xCrO3

A new mixed rare-earth orthochromite series, LaxSm1-xCrO3, prepared through single-step hydrothermal synthesis is reported. Solid solutions (x = 0, 0.25, 0.5, 0.625, 0.75, 0.875, and 1.0) were prepared by the hydrothermal treatment of amorphous mixed-metal hydroxides at 370 °C for 48 h. Transmission electron microscopy (TEM) reveals the formation of highly crystalline particles with dendritic-like morphologies. Rietveld refinements against high-resolution powder X-ray diffraction (PXRD) data show that the distorted perovskite structures are described by the orthorhombic space group Pnma over the full composition range. Unit cell volumes and Cr-O-Cr bond angles decrease monotonically with increasing samarium content, consistent with the presence of the smaller lanthanide in the structure. Raman spectroscopy confirms the formation of solid solutions, the degree of their structural distortion. With the aid of shell-model calculations the complex mixing of Raman modes below 250 cm(-1) is clarified. Magnetometry as a function of temperature reveals the onset of low-temperature antiferromagnetic ordering of Cr(3+) spins with weak ferromagnetic component at Néel temperatures (TN) that scale linearly with unit cell volume and structural distortion. Coupling effects between Cr(3+) and Sm(3+) ions are examined with enhanced susceptibilities below TN due to polarization of Sm(3+) moments. At low temperatures the Cr(3+) sublattice is shown to undergo a second-order spin reorientation observed as a rapid decrease of susceptibility.

Low-temperature fabrication of layered self- organized Ge clusters by RF-sputtering

In this article, we present an investigation of (Ge + SiO2)/SiO2 multilayers deposited by magnetron sputtering and subsequently annealed at different temperatures. The structural properties were investigated by transmission electron microscopy, grazing incidence small angles X-ray scattering, Rutherford backscattering spectrometry, Raman, and X-ray photoelectron spectroscopies. We show a formation of self-assembled Ge clusters during the deposition at 250°C. The clusters are ordered in a three-dimensional lattice, and they have very small sizes (about 3 nm) and narrow size distribution. The crystallization of the clusters was achieved at annealing temperature of 700°C.

Incorporation of square-planar Pd2+ in fluorite CeO2: hydrothermal preparation, local structure, redox properties and stability

The direct hydrothermal crystallisation at 240 °C of Pd2+-containing ceria is investigated to study the extent to which precious metal dopants may be introduced into the cubic fluorite lattice. Samples of composition Ce1−xPdxO2−δ, where 0 ≤ x ≤ 0.15 can be produced in which Pd is included within the CeO2 structure to give a linear lattice expansion. Attempts to produce higher Pd2+-substitution result in the formation of PdO as a secondary phase. Ce and Pd were determined to be in the +4 and +2 oxidation states, respectively, by X-ray absorption near edge structure, suggesting oxide deficiency as the mechanism of charge balance. Extended X-ray absorption fine structure (EXAFS) analysis at the Pd K-edge reveals that Pd2+ has local square-planar coordination, as expected, and that a structural model can fitted in which the average fluorite structure is maintained, but with Pd2+ sitting in the square faces of oxide ions present in the local cubic geometry of Ce. This model, consistent with previous modelling studies, gives an excellent fit to the EXAFS spectra, and explains the observed lattice expansion. Transmission electron microscopy analysis shows that Pd is well dispersed in the nanocrystalline ceria particles, and in situ powder XRD shows that upon heating in air the samples remain stable up to 800 °C. H2-TPR shows that Pd-substitution leads to low temperature (<200 °C) reduction of the oxide, which increases in magnitude with increasing Pd-substitution. On prolonged heating, however, the Pd is lost from the ceria lattice to give dispersed Pd metal, suggesting an inherent instability of Pd-doped CeO2.

Raman spectroscopy of optical transitions and vibrational energies of ∼1 nm HgTe extreme nanowires within single walled carbon nanotubes

This paper presents a resonance Raman spectroscopy study of ∼1 nm diameter HgTe nanowires formed inside single walled carbon nanotubes by melt infiltration. Raman spectra have been measured for ensembles of bundled filled tubes, produced using tubes from two separate sources, for excitation photon energies in the ranges 3.39-2.61 and 1.82-1.26 eV for Raman shifts down to ∼25 cm(-1). We also present HRTEM characterization of the tubes and the results of DFT calculations of the phonon and electronic dispersion relations, and the optical absorption spectrum based upon the observed structure of the HgTe nanowires. All of the evidence supports the hypothesis that the observed Raman features are not attributable to single walled carbon nanotubes, i.e., peaks due to radial breathing mode phonons, but are due to the HgTe nanowires. The observed additional features are due to four distinct phonons, with energies 47, 51, 94, and 115 cm(-1), respectively, plus their overtones and combinations. All of these modes have strong photon energy resonances that maximize at around 1.76 eV energy with respect to incident laser.

Structural variety in iridate oxides and hydroxides from hydrothermal synthesis

We report the results of an exploratory synthetic study of iridium-containing materials using hydrothermal methods from simple metal salts. Three alkali-earth iridium hydroxides are isolated as phase-pure samples and their structures examined by single-crystal or powder diffraction methods: each contains Ir(IV)-centred octahedra, isolated from each other and sharing bridging hydroxides or fluoride with alkali-earth (Ca, Sr or Ba) centres. One of these hydroxides, Ca2IrF(OH)6.OH, possesses a unique open structure, consisting of a positively-charged framework that has one-dimensional channels in which infinite chains of hydrogen-bonded hydroxide anions are encapsulated. The addition of hydrogen peroxide or sodium peroxide to otherwise identical hydrothermal reactions yields dense oxide materials in which iridium is found in an oxidation state between +4 and +5: the novel oxide Na0.8Sr2.2Ir3O10.1 has a KSbO3-type structure with an iridium oxidation state of +5, while the new pyrochlore (Na0.27Ca0.59)2Ir2O6·0.66H2O contains iridium with an average oxidation state close to +4.5. Our results illustrate the utility for hydrothermal synthesis in the discovery of novel complex structures that may be inaccessible using conventional high-temperature synthesis, with control of the metal oxidation state possible with judicious choice of reagents.

Spatially correlated erbium and Si nanocrystals in coimplanted SiO2 after a single high temperature anneal

We present a study of silicon (Si) and erbium (Er) coimplanted silica (SiO2) in which we observe, by combining high resolution scanning transmission electron microscopy and selective electron energy loss spectroscopy (EELS), a high spatial correlation between silicon nanocrystals (Si-NCs), Er, and oxygen (O) after a single high temperature (1100 °C) anneal. The observation of a spatial overlap of the EELS chemical maps of dark field (DF) images at the Er N4,5, Si L2,3, and O K edges is concomitant with an intense room temperature infrared luminescence around 1534 nm. We suggest that these observations correspond to Er–O complexes within an amorphous silicon (a-Si) shell at the Si-NC/SiO2 interface. The presence of a crystalline phase at the Si-NC center, verified by high resolution electron micrographs and DF diffraction contrast images and the low solubility of Er in crystalline Si (c-Si) would tend to suggest a preferential Er agglomeration toward the Si-NC/SiO2 interface during formation, particularly when high concentrations of both Si and Er are obtained in a narrow region of the SiO2 after coimplantation. The absence of narrow Stark related features in the Er emission spectrum at low temperature and an inhomogeneous broadening with increasing temperature, which are characteristic of Er confined by an amorphous, rather than a crystalline host further support these hypotheses. After comparing the luminescence to that from a SiO2:Er control sample prepared in exactly the same manner but without Si-NCs, we find that, despite the observed spatial correlation, only a small fraction ( ∼ 7%) of the Er are sensitized by the Si-NCs. We ascribe this low fraction to a combination of low sensitizer (Si-NC) density and Auger-type losses arising principally from Er ion-ion interactions.