Reactivity of FeMoO4 in CsCl Fluxes and Formation of the Salt-Inclusion Type of Compounds.

The reactivity of FeMoO4 in CsCl fluxes has been investigated by thermal analysis and chemical reactions in evacuated silica ampules. The products have been characterized by ex situ X-ray diffraction methods. Metathesis reactions involving CsCl lead to the formation of Cs2Fe2(MoO4)3 and the salt adduct Cs2FeCl4·CsCl. A side reaction has been observed, which is associated with a decomposition of [MoO4]2- in CsCl fluxes yielding Cs2Mo2O7·CsCl, which contains the rare pyromolybdate anion, [Mo2O7]2-, located in the center of a ∞2[CsCl] hetero-honeycomb arrangement. This salt-inclusion type of compound has been studied further in terms of its formation starting from Cs2MoO4, MoO3, and CsCl. The intermediate adduct phase, Cs2MoO4·MoO3, contains uncharged ∞1[MoO2O2/2] chains that react with CsCl at elevated temperatures to Cs2Mo2O7·CsCl. Furthermore, the site preference for alkaline-metal cations (K+, Rb+, and Cs+) has been evaluated for a mixed substitution series. In accordance with the Pearson concept, the polarizability of the respect cation outweighs any size differences for the occupancy of the salt-intergrowth motif, the honeycomb part of the structure.

Panchromatic Absorption and Oxidation of an Iron(II) Spin Crossover Complex.

In order to expand and exploit the useful properties of d6-iron(II) and d5-iron(III) complexes in potential magnetic, photophysical, or magnetooptical applications, crucial ligand-controlled parameters are the ligand field strength in a given coordination mode and the availability of suitable metal and ligand frontier orbitals for charge-transfer processes. The push-pull ligand 2,6-diguanidylpyridine (dgpy) features low-energy π* orbitals at the pyridine site and strongly electron-donating guanidinyl donors combined with the ability to form six-membered chelate rings for optimal metal-ligand orbital overlap. The electronic ground states of the pseudo-octahedral d6- and d5-complexes mer-[Fe(dgpy)2]2+, cis-fac-[Fe(dgpy)2]2+, and mer-[Fe(dgpy)2]3+ as well as their charge-transfer (CT) and metal-centered (MC) excited states are probed by variable temperature UV/vis absorption, NMR, EPR, and Mössbauer spectroscopy, magnetic susceptibility measurements at variable temperature as well as quantum chemical calculations.

Selective Synthesis of Monodisperse CoO Nanooctahedra as Catalysts for Electrochemical Water Oxidation.

Thermal decomposition is a promising route for the synthesis of metal oxide nanoparticles because size and morphology can be tuned by minute control of the reaction variables. We synthesized CoO nanooctahedra with diameters of ∼48 nm and a narrow size distribution. Full control over nanoparticle size and morphology could be obtained by controlling the reaction time, surfactant ratio, and reactant concentrations. We show that the particle size does not increase monotonically with time or surfactant concentration but passes through minima or maxima. We unravel the critical role of the surfactants in nucleation and growth and rationalize the observed experimental trends in accordance with simulation experiments. The as-synthesized CoO nanooctahedra exhibit superior electrocatalytic activity with long-term stability during oxygen evolution. The morphology of the CoO particles controls the electrocatalytic reaction through the distinct surface sites involved in the oxygen evolution reaction.

Mixed Ligand Shell Formation upon Catechol Ligand Adsorption on Hydrophobic TiO2 Nanoparticles.

Modifying the surfaces of metal oxide nanoparticles (NPs) with monolayers of ligands provides a simple and direct method to generate multifunctional coatings by altering their surface properties. This works best if the composition of the monolayers can be controlled. Mussel-inspired, noninnocent catecholates stand out from other ligands like carboxylates and amines because they are redox-active and allow for highly efficient surface binding and enhanced electron transfer to the surface. However, a comprehensive understanding of their surface chemistry, including surface coverage and displacement of the native ligand, is still lacking. Here, we unravel the displacement of oleate (OA) ligands on hydrophobic, OA-stabilized TiO2 NPs by catecholate ligands using a combination of one- and two-dimensional nuclear magnetic resonance (NMR) spectroscopy techniques. Conclusive pictures of the ligand shells before and after surface modification with catecholate were obtained by 1H and 13C NMR spectroscopy (the 13C chemical shift being more sensitive and with a broader range). The data could be explained using a Langmuir-type approach. Gradual formation of a mixed ligand shell was observed, and the surface processes of catecholate adsorption and OA desorption were quantified. Contrary to the prevailing view, catecholate displaces only a minor fraction (∼20%) of the native OA ligand shell. At the same time, the total ligand density more than doubled from 2.3 nm-2 at native oleate coverage to 4.8 nm-2 at maximum catecholate loading. We conclude that the catecholate ligand adsorbs preferably to unoccupied Ti surface sites rather than replacing native OA ligands. This unexpected behavior, reminiscent of the Vroman effect for protein corona formation, appears to be a fundamental feature in the widely used surface modification of hydrophobic metal oxide NPs with catecholate ligands. Moreover, our findings show that ligand displacement on OA-capped TiO2 NPs is not suited for a full ligand shell refunctionalization because it produces only mixed ligand shells. Therefore, our results contribute to a better understanding and performance of photocatalytic applications based on catecholate ligand-sensitized TiO2 NPs.

Trapping Amorphous Intermediates of Carbonates - A Combined Total Scattering and NMR Study.

Crystallization via metastable phases plays an important role in chemical manufacturing, biomineralization, and protein crystallization, but the kinetic pathways leading from metastable phases to the stable crystalline modifications are not well understood. In particular, the fast crystallization of amorphous intermediates makes a detailed characterization challenging. To circumvent this problem, we devised a system that allows trapping and stabilizing the amorphous intermediates of representative carbonates (calcium, strontium, barium, manganese, and cadmium). The long-term stabilization of these transient species enabled a detailed investigation of their composition, structure, and morphology. Total scattering experiments with high-energy synchrotron radiation revealed a short-range order of several angstroms in all amorphous intermediates. From the synchrotron data, a structural model of amorphous calcium carbonate was derived that indicates a lower coordination number of calcium compared to the crystalline polymorphs. Our study shows that a multistep crystallization pathway via amorphous intermediates is open to many carbonates. We could isolate and characterize these transient species, thereby providing new insights into their crystallization mechanism.

Calcium Sulfate Nanoparticles with Unusual Dispersibility in Organic Solvents for Transparent Film Processing.

Calcium sulfate is one of the most important construction materials. Today it is employed as high-performance compound in medical applications and cement mixtures. We report a synthesis for calcium sulfate nanoparticles with outstanding dispersibility properties in organic solvents without further functionalization. The nanoparticles (amorphous with small γ-anhydrite crystallites, 5-50 nm particle size) form long-term stable dispersions in acetone without any sign of precipitation. 1H NMR spectroscopic techniques and Fourier-transform infrared spectroscopy (FTIR) reveal absorbed 2-propanol on the particle surfaces that induce the unusual dispersibility. Adding water to the nanoparticle dispersion leads to immediate precipitation. A phase transformation to gypsum via bassanite was monitored by an in situ kinetic FT-IR spectroscopic study and transmission electron microscopy (TEM). The dispersibility in a volatile organic solvent and the crystallization upon contact with water open a broad field of applications for the CaSO4 nanoparticles, e.g., as nanogypsum for coatings or the fabrication of hybrid composites.

Screw- Type Motion and Its Impact on Cooperativity in BaNa2Fe[VO4]2.

BaNa2Fe[VO4]2 contains a Jahn-Teller active ion (FeII, 3d6, high-spin) in an octahedral coordination. On the basis of a combination of temperature-dependent X-ray diffraction and Mössbauer and Raman spectroscopies, we demonstrate the coupling of lattice dynamics with the electronic ground state of FeII. We identify three lattice modes combined to an effective canted screw- type motion that drives the structural transition around room temperature from the high-temperature ( P3̅) via intermediate phases to the low-temperature phase ( C2/ c). The dynamics of the electronic ground state of Fe(II) are evident from Mössbauer data with signatures of a motion-narrowed doublet above 320 K, a gradual evolution of the 5Eg electronic state below 293 K, and finally the signature of the thermodynamically preferred orbitally nondegenerate ground state (5Ag) of Fe(II) below 100 K. The continuous nature of the transition is associated with the temperature-dependent phonon parameters derived from Raman spectroscopy, which point out the presence of strong electron-phonon coupling in this compound. We present a microscopic mechanism and evaluate the collective component leading to the structural phase transition.

Controlling the Morphology of Au-Pd Heterodimer Nanoparticles by Surface Ligands.

Controlling the morphology of noble-metal nanoparticles is mandatory to tune specific properties such as catalytic and optical behavior. Heterodimers consisting of two noble metals have been synthesized, so far mostly in aqueous media using selective surfactants or chemical etching strategies. We report a facile synthesis for Au@Pd and Pd@Au heterodimer nanoparticles (NPs) with morphologies ranging from segregated domains (heteroparticles) to core-shell structures by applying a seed-mediated growth process with Au and Pd seed nanoparticles in 1-octadecene (ODE), which is a high-boiling organic solvent. The as-synthesized oleylamine (OAm) functionalized Au NPs led to the formation of OAm-Au@Pd heteroparticles with a "windmill" morphology, having an Au core and Pd "blades". The multiply twinned structure of the Au seed particles (⌀ ≈ 9-11 nm) is associated with a reduced barrier for heterogeneous nucleation. This leads to island growth of bimetallic Au@Pd heteroparticles with less-regular morphologies. The reaction process can be controlled by tuning the surface chemistry with organic ligands. Functionalization of Au NPs (Ø ≈ 9-11 nm) with 1-octadecanethiol (ODT) led to the formation of ODT-Au@Pd NPs with a closed Pd shell through a strong ligand-metal binding, which is accompanied by a redistribution of the electron density. Experiments with varied Pd content revealed surface epitaxial growth of Pd on Au. For OAm-Pd and ODT-Pd seed particles, faceted, Au-rich domain NPs and impeded core-shell NPs were obtained, respectively. This is related to the high surface energy of the small Pd seed particles (⌀ ≈ 5-7 nm). The metal distribution of all bimetallic NPs was analyzed by extended (aberration-corrected) transmission electron microscopy (HR-TEM, HAADF-STEM, EDX mapping, ED). The Au and Pd NPs, as well as the ODT-Au@Pd and OAm-Pd@Au heteroparticles, catalyze the reduction of 4-nitrophenol to 4-aminophenol with borohydride. The catalytic activity is dictated by the particle structure. OAm-Au@Pd heteroparticles with faceted Au domains had the highest activity because of a mixed Au-Pd surface structure, while ODT-Au@Pd NPs, where the active Au core is covered by a Pd shell, had the lowest activity.

Spark Plasma Sintering (SPS)-Assisted Synthesis and Thermoelectric Characterization of Magnéli Phase V6O11.

The Magnéli phase V6O11 was synthesized in gram amounts from a powder mixture of V6O11/V7O13 and vanadium metal, using the spark plasma sintering (SPS) technique. Its structure was determined with synchrotron X-ray powder diffraction data from a phase-pure sample synthesized by conventional solid-state synthesis. A special feature of Magnéli-type oxides is a combination of crystallographic shear and intrinsic disorder that leads to relatively low lattice thermal conductivities. SPS prepared V6O11 has a relatively low thermal conductivity of κ = 2.72 ± 0.06 W (m K)-1 while being a n-type conductor with an electrical conductivity of σ = 0.039 ± 0.005 (µΩ m)-1, a Seebeck coefficient of α = -(35 ± 2) µV K-1, which leads to a power factor of PF = 4.9 ± 0.8 × 10-5W (m K2)-1 at ∼600 K. Advances in the application of Magnéli phases are mostly hindered by synthetic and processing challenges, especially when metastable and nanostructured materials such as V6O11 are involved. This study gives insight into the complications of SPS-assisted synthesis of complex oxide materials, provides new information about the thermal and electrical properties of vanadium oxides at high temperatures, and supports the concept of reducing the thermal conductivity of materials with structural building blocks such as crystallographic shear (CS) planes.

Scope and mechanism of the highly stereoselective metal-mediated domino aldol reactions of enolates with aldehydes.

A one-pot transformation, which involves the reaction of ketones with aldehydes in the presence of metal halides to furnish tetrahydro-2H-pyran-2,4-diols in a highly diastereoselective manner, is investigated thoroughly by experiments and computations. The reaction was also successfully implemented on a flow micro reactor system.

Thermally highly stable amorphous zinc phosphate intermediates during the formation of zinc phosphate hydrate.

The mechanisms by which amorphous intermediates transform into crystalline materials are still poorly understood. Here we attempt to illuminate the formation of an amorphous precursor by investigating the crystallization process of zinc phosphate hydrate. This work shows that amorphous zinc phosphate (AZP) nanoparticles precipitate from aqueous solutions prior to the crystalline hopeite phase at low concentrations and in the absence of additives at room temperature. AZP nanoparticles are thermally stable against crystallization even at 400 °C (resulting in a high temperature AZP), but they crystallize rapidly in the presence of water if the reaction is not interrupted. X-ray powder diffraction with high-energy synchrotron radiation, scanning and transmission electron microscopy, selected area electron diffraction, and small-angle X-ray scattering showed the particle size (≈20 nm) and confirmed the noncrystallinity of the nanoparticle intermediates. Energy dispersive X-ray, infrared, and Raman spectroscopy, inductively coupled plasma mass spectrometry, and optical emission spectrometry as well as thermal analysis were used for further compositional characterization of the as synthesized nanomaterial. (1)H solid-state NMR allowed the quantification of the hydrogen content, while an analysis of (31)P{(1)H} C rotational echo double resonance spectra permitted a dynamic and structural analysis of the crystallization pathway to hopeite.

Anhydrous Amorphous Calcium Oxalate Nanoparticles from Ionic Liquids: Stable Crystallization Intermediates in the Formation of Whewellite.

The mechanisms by which amorphous intermediates transform into crystalline materials are not well understood. To test the viability and the limits of the classical crystallization, new model systems for crystallization are needed. With a view to elucidating the formation of an amorphous precursor and its subsequent crystallization, the crystallization of calcium oxalate, a biomineral widely occurring in plants, is investigated. Amorphous calcium oxalate (ACO) precipitated from an aqueous solution is described as a hydrated metastable phase, as often observed during low-temperature inorganic synthesis and biomineralization. In the presence of water, ACO rapidly transforms into hydrated whewellite (monohydrate, CaC2 O4 ⋅H2 O, COM). The problem of fast crystallization kinetics is circumvented by synthesizing anhydrous ACO from a pure ionic liquid (IL-ACO) for the first time. IL-ACO is stable in the absence of water at ambient temperature. It is obtained as well-defined, non-agglomerated particles with diameters of 15-20 nm. When exposed to water, it crystallizes to give (hydrated) COM through a dissolution/recrystallization mechanism.

Thermoelectric transport in Cu7PSe6 with high copper ionic mobility.

Building on the good thermoelectric performances of binary superionic compounds like Cu2Se, Ag2Se and Cu2S, a better and more detailed understanding of phonon-liquid electron-crystal (PLEC) thermoelectric materials is desirable. In this work we present the thermoelectric transport properties of the compound Cu7PSe6 as the first representative of the class of argyrodite-type ion conducting thermoelectrics. With a huge variety of possible compositions and high ionic conductivity even at room temperature, the argyrodites represent a very good model system to study structure-property relationships for PLEC thermoelectric materials. We particularly highlight the extraordinary low thermal conductivity of Cu7PSe6 below the glass limit, which can be associated with the molten copper sublattice leading to a softening of phonon modes.

Multifunctional two-photon active silica-coated Au@MnO Janus particles for selective dual functionalization and imaging.

Monodisperse multifunctional and nontoxic Au@MnO Janus particles with different sizes and morphologies were prepared by a seed-mediated nucleation and growth technique with precise control over domain sizes, surface functionalization, and dye labeling. The metal oxide domain could be coated selectively with a thin silica layer, leaving the metal domain untouched. In particular, size and morphology of the individual (metal and metal oxide) domains could be controlled by adjustment of the synthetic parameters. The SiO2 coating of the oxide domain allows biomolecule conjugation (e.g., antibodies, proteins) in a single step for converting the photoluminescent and superparamagnetic Janus nanoparticles into multifunctional efficient vehicles for theranostics. The Au@MnO@SiO2 Janus particles were characterized using high-resolution transmission electron microscopy (HR-)TEM, powder X-ray diffraction (PXRD), optical (UV-vis) spectroscopy, confocal laser fluorescence scanning microscopy (CLSM), and dynamic light scattering (DLS). The functionalized nanoparticles were stable in buffer solution or serum, showing no indication of aggregation. Biocompatibility and potential biomedical applications of the Au@MnO@SiO2 Janus particles were assayed by a cell viability analysis by coincubating the Au@MnO@SiO2 Janus particles with Caki 1 and HeLa cells. Time-resolved fluorescence spectroscopy in combination with CLSM revealed the silica-coated Au@MnO@SiO2 Janus particles to be highly two-photon active; no indication for an electronic interaction between the dye molecules incorporated in the silica shell surrounding the MnO domains and the attached Au domains was found; fluorescence quenching was observed when dye molecules were bound directly to the Au domains.

Using crystallographic shear to reduce lattice thermal conductivity: high temperature thermoelectric characterization of the spark plasma sintered Magnéli phases WO2.90 and WO2.722.

Engineering of nanoscale structures is a requisite for controlling the electrical and thermal transport in solids, in particular for thermoelectric applications that require a conflicting combination of low thermal conductivity and low electrical resistivity. We report the thermoelectric properties of spark plasma sintered Magnéli phases WO2.90 and WO2.722. The crystallographic shear planes, which are a typical feature of the crystal structures of Magnéli-type metal oxides, lead to a remarkably low thermal conductivity for WO2.90. The figures of merit (ZT = 0.13 at 1100 K for WO2.90 and 0.07 at 1100 K for WO2.722) are relatively high for tungsten-oxygen compounds and metal oxides in general. The electrical resistivity of WO2.722 shows a metallic behaviour with temperature, while WO2.90 has the characteristics of a heavily doped semiconductor. The low thermopower of 80 µV K(-1) at 1100 K for WO2.90 is attributed to its high charge carrier concentration. The enhanced thermoelectric performance for WO2.90 compared to WO2.722 originates from its much lower thermal conductivity, due to the presence of crystallographic shear and dislocations in the crystal structure. Our study is a proof of principle for the development of efficient and low-cost thermoelectric materials based on the use of intrinsically nanostructured materials rather than artificially structured layered systems to reduce lattice thermal conductivity.

Influence of a nano phase segregation on the thermoelectric properties of the p-type doped stannite compound Cu(2+x)Zn(1-x)GeSe4.

Engineering nanostructure in bulk thermoelectric materials has recently been established as an effective approach to scatter phonons, reducing the phonon mean free path, without simultaneously decreasing the electron mean free path for an improvement of the performance of thermoelectric materials. Herein the synthesis, phase stability, and thermoelectric properties of the solid solutions Cu(2+x)Zn(1-x)GeSe(4) (x = 0-0.1) are reported. The substitution of Zn(2+) with Cu(+) introduces holes as charge carriers in the system and results in an enhancement of the thermoelectric efficiency. Nano-sized impurities formed via phase segregation at higher dopant contents have been identified and are located at the grain boundaries of the material. The impurities lead to enhanced phonon scattering, a significant reduction in lattice thermal conductivity, and therefore an increase in the thermoelectric figure of merit in these materials. This study also reveals the existence of an insulator-to-metal transition at 450 K.

Ab†Initio structure determination of vaterite by automated electron diffraction.

"This is a mineral about which there has been much discussion" is a typical statement about vaterite in older standard textbooks of inorganic chemistry. This polymorph of CaCO(3) was first mentioned by H. Vater in 1897, plays key roles in weathering and biomineralization processes, but occurs only in the form of nanosized crystals, unsuitable for structure determination. Its structure could now be solved by automated electron diffraction tomography from 50 nm sized nanocrystals.

Lithium confinement and dynamics in hexagonal and monoclinic tungsten oxide nanocrystals: a 7Li solid state NMR study.

Mixed-valence tungsten bronzes AxWO3 (A = alkali metal, NH4+, etc.) are a series of compounds with adaptive structural and compositional features that make them a hot research topic in thermoelectrics, electrochromics, catalysis or energy applications in battery electrodes. The mixed hexagonal lithium ammonium bronze Lix(NH4)yWO3 is a new member of this structural family whose properties are compared to those of the pure hexagonal tungsten bronze (NH4)xWO3. Surface and structural (nanoconfined) Li+ cations were characterized by 7Li single pulse excitation and 1H-7Li cross-polarization (CP) NMR experiments. CP build-up curves and two-dimensional heteronuclear correlation solid-state NMR techniques provide information about the spatial connectivity between different proton and Li+ species. At 500 °C the bronze structurally transforms from the hexagonal to a monoclinic phase, and defects are formed that are characterized through the Li+ environment. 7Li exchange spectroscopy (EXSY) NMR experiments provide information about the chemical exchange between the lithium species. The measured 7Li T1 and T2 relaxation time constants and the T1/T2 ratio allow characterizing the local strength of Li+ binding.

High-throughput synthesis of CeO2 nanoparticles for transparent nanocomposites repelling Pseudomonas aeruginosa biofilms.

Preventing bacteria from adhering to material surfaces is an important technical problem and a major cause of infection. One of nature's defense strategies against bacterial colonization is based on the biohalogenation of signal substances that interfere with bacterial communication. Biohalogenation is catalyzed by haloperoxidases, a class of metal-dependent enzymes whose activity can be mimicked by ceria nanoparticles. Transparent CeO2/polycarbonate surfaces that prevent adhesion, proliferation, and spread of Pseudomonas aeruginosa PA14 were manufactured. Large amounts of monodisperse CeO2 nanoparticles were synthesized in segmented flow using a high-throughput microfluidic benchtop system using water/benzyl alcohol mixtures and oleylamine as capping agent. This reduced the reaction time for nanoceria by more than one order of magnitude compared to conventional batch methods. Ceria nanoparticles prepared by segmented flow showed high catalytic activity in halogenation reactions, which makes them highly efficient functional mimics of haloperoxidase enzymes. Haloperoxidases are used in nature by macroalgae to prevent formation of biofilms via halogenation of signaling compounds that interfere with bacterial cell-cell communication ("quorum sensing"). CeO2/polycarbonate nanocomposites were prepared by dip-coating plasma-treated polycarbonate panels in CeO2 dispersions. These showed a reduction in bacterial biofilm formation of up to 85% using P. aeruginosa PA14 as model organism. Besides biofilm formation, also the production of the virulence factor pyocyanin in is under control of the entire quorum sensing systems P. aeruginosa. CeO2/PC showed a decrease of up to 55% in pyocyanin production, whereas no effect on bacterial growth in liquid culture was observed. This indicates that CeO2 nanoparticles affect quorum sensing and inhibit biofilm formation in a non-biocidal manner.

Wet chemical synthesis and a combined X-ray and Mössbauer study of the formation of FeSb2 nanoparticles.

Understanding how solids form is a challenging task, and few strategies allow for elucidation of reaction pathways that are useful for designing the synthesis of solids. Here, we report a powerful solution-mediated approach for formation of nanocrystals of the thermoelectrically promising FeSb(2) that uses activated metal nanoparticles as precursors. The small particle size of the reactants ensures minimum diffusion paths, low activation barriers, and low reaction temperatures, thereby eliminating solid-solid diffusion as the rate-limiting step in conventional bulk-scale solid-state synthesis. A time- and temperature-dependent study of formation of nanoparticular FeSb(2) by X-ray powder diffraction and iron-57 Mössbauer spectroscopy showed the incipient formation of the binary phase in the temperature range of 200-250 °C.