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DOE OSTI2012

Controlled synthesis, formation mechanism and upconversion luminescence of NaYF{sub 4}: Yb, Er nano-/submicrocrystals via ionothermal approach

In order to deepen the fundamental understanding of IL-mediated synthesis of nano-/submicrostructure, hydrophilic ILs ([Emim][BF{sub 4}], [Bmim][BF{sub 4}] and [Omim][BF{sub 4}]), which act as solvents, templates, as well as fluorine source, have been employed to synthesize rare earth doped NaYF{sub 4} upconversion nano-/submicrocrystals (UC-NMCs). The imidazolium cations provide the capping reagent to prevent the nucleation centers from aggregation and growing, while the tetrafluoroborate anions introduce a new fluorine source according to partial hydrolysis. It is demonstrated that the properties of IL, such as viscosity, polarity, solvency and interfacial tension, extremely affect the dissolution, diffusion and nucleation process of lanthanide ions in IL. Morphology and size of the final products can thus be tailored by synthetical parameters, like imidazolium cations, cosolvents, Ln{sup 3+} and fluoride concentrations, as well as ionothermal time. Based on the experimental results, the possible mechanism of the nucleation and growth of UC-NMCs in IL is discussed. - Graphical abstract: The upconversion nano-/submicrocrystals with diverse morphologies and sizes have been synthesized through ionothermal approach. The possible mechanism is concluded, which strengthens the fundamental understanding of IL-mediated synthesis of nano-/submicrostructure. Highlights: Black-Right-Pointing-Pointer The upconversion nano-/submicrocrystals were synthesized through ionothermal approach. Black-Right-Pointing-Pointer The as-prepared products exhibited diverse morphologies and sizes. Black-Right-Pointing-Pointer The possible mechanism of the nucleation and growth process in ILs is concluded.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Hydrothermal synthesis of new rare earth silicate fluorides: A novel class of polar materials

Polar crystals provide an interesting avenue for materials research both in the structures they form and the properties they possess. This work describes the hydrothermal synthesis and structural characterization of three novel silicate fluorides. Compound (1), LiY{sub 3}(SiO{sub 4}){sub 2}F{sub 2} crystallizes in space group C2/c, with a=17.651(4) A, b=4.8868(10) A, c=11.625(2) A and {beta}=131.13(3) Degree-Sign . BaY{sub 2}(Si{sub 2}O{sub 7})F{sub 2} (2) crystallizes in space group P-1, with a=5.1576(10) A, b=6.8389(14) A, c=11.786(2) A, {alpha}=93.02(3) Degree-Sign , {beta}=102.05(3) Degree-Sign and {gamma}=111.55(3) Degree-Sign . Finally, the structure of Ba{sub 2}Y{sub 3}(SiO{sub 4}){sub 2}F{sub 5} (3) was determined in the polar orthorhombic space group Pba2, having unit cell parameters a=8.8864(18) A, b=12.764(3) A and c=5.0843(10) A. The structures are compared based on their building blocks and long range polarities. Aligned silicate tetrahedra segregated into a single layer in (3) impart the observed polarity. - Graphical abstract: The polar structure of Ba{sub 2}Y{sub 3}(SiO{sub 4}){sub 2}F{sub 5}. Highlights: Black-Right-Pointing-Pointer Natural yttrium silicate fluoride minerals are briefly reviewed. Black-Right-Pointing-Pointer The synthesis and structures of LiY{sub 3}(SiO{sub 4}){sub 2}F{sub 2}, BaY{sub 2}(Si{sub 2}O{sub 7})F{sub 2} and Ba{sub 2}Y{sub 3}(SiO{sub 4}){sub 2}F{sub 5} are discussed. Black-Right-Pointing-Pointer Ba{sub 2}Y{sub 3}(SiO{sub 4}){sub 2}F{sub 5} crystallizes in the polar space group Pba2. Black-Right-Pointing-Pointer Polarity occurs primarily through aligned silicate tetrahedra in a segregated layer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Synthesis of YAG nanopowder by the co-precipitation method: Influence of pH and study of the reaction mechanisms

YAG nanopowders with an average grain size of 30 nm have been successfully synthesized by the co-precipitation method using nitrates with precipitant of ammonium hydrogen carbonate. The influence of precipitation conditions such as pH, aging time and calcination temperature on the formation of secondary phases has been studied. The accurate control of pH value at every stage of precipitation process is crucial to avoid the presence of YAM (Yttrium Aluminium Monoclinic, Y{sub 4}Al{sub 2}O{sub 9}) and yttrium oxide (Y{sub 2}O{sub 3}) after calcination. The reaction mechanisms have been investigated using different techniques such as infrared spectroscopy, x-ray diffraction and thermal analyses. The YAG phase is formed around 1050 Degree-Sign C passing through an intermediate phase called YAP (Yttrium Aluminium Perovskite, YAlO{sub 3}). Local chemical heterogeneities are responsible for the deviation of the Y:Al ratio and the formation of YAP during heat treatment. - Graphical abstract: Synthesis of YAG nanopowder by the co-precipitation method: Influence of pH and study of the reaction mechanisms, Marlot et al. Highlights: Black-Right-Pointing-Pointer Synthesis of pure YAG nanoparticles by the co-precipitation method. Black-Right-Pointing-Pointer Influence of pH value on the formation of secondary phases all along the process. Black-Right-Pointing-Pointer Study of the importance of pH using titration method. Black-Right-Pointing-Pointer Chemical evolution of the precursor during calcinations. Black-Right-Pointing-Pointer Proposition for reaction mechanisms.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Monodisperse spindle-like FeWO{sub 4} nanoparticles: Controlled hydrothermal synthesis and enhanced optical properties

Monodisperse FeWO{sub 4} nanoparticles with specific spindle-like morphology have been synthesized in the presence of citric acid through hydrothermal process. In the synthesis route, citric acid played four roles such as the reducing agent, chelating regents, structure-directing agent and stabilizing agents. In addition, the morphology of FeWO{sub 4} was dramatically tuned by the pH value of the precursor medium. The optical properties of FeWO{sub 4} were investigated with UV-Vis spectra and photoluminescence spectroscopy. The photocatalytic experiments demonstrated that the decomposition efficiency of the monodisperse spindle-like FeWO{sub 4} nanoparticles is 74% after 30 min of UV irradiation, which displayed remarkable enhanced photodegradation activity compared with ordinary FeWO{sub 4} sample (57%) and normal TiO{sub 2} photocatalysts P-25 (56%). - Monodisperse spindle-like FeWO{sub 4} nanoparticles with enhanced photocatalytic activities. Highlights: Black-Right-Pointing-Pointer Monodisperse spindle-like FeWO{sub 4} were synthesized with hydrothermal method. Black-Right-Pointing-Pointer Citric acid plays key roles in the hydrothermal synthesis. Black-Right-Pointing-Pointer Their morphology can be tuned with pH value of the precursor medium. Black-Right-Pointing-Pointer They show enhanced photocatalytic activities with irradiation of UV light.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Synthesis of Sr{sub 0.9}K{sub 0.1}FeO{sub 3-{delta}} electrocatalysts by mechanical activation

Potassium-substituted SrFeO{sub 3-{delta}} for possible application as oxygen evolution electrode in alkaline or molten salt media was prepared by mechanical activation and characterized by X-ray diffraction, dilatometric and thermogravimetric analysis, Moessbauer spectroscopy, and electrical conductivity measurements. Room temperature mechanical activation of a mixture of oxide precursors with subsequent thermal treatments at 700-900 Degree-Sign C results in the formation of Sr{sub 0.9}K{sub 0.1}FeO{sub 3-{delta}} with tetragonal perovskite-like structure. Such allows to decrease the synthesis temperature, if compared to the conventional solid-state route, and to prevent possible volatilization of potassium. The results of Moessbauer spectroscopy studies indicate that the oxygen nonstoichiometry in the samples annealed in air at 900-1100 Degree-Sign C with subsequent rapid cooling vary in the range {delta}=0.30-0.32. The electrical conductivity in air exhibits a metal-like behaviour at temperatures above 400 Degree-Sign C and semiconductor behaviour in the low-temperature range, reaching 13-30 S/cm under prospective operation conditions for alkaline electrolyzers ({<=}90 Degree-Sign C). - graphical abstract: XRD patterns of Sr{sub 0.9}K{sub 0.1}FeO{sub 3-{delta}} powders, as-prepared and after annealing at different temperatures. Log({sigma}{center_dot}T) vs. 1000/T plot of the electrical conductivity of Sr{sub 0.9}K{sub 0.1}FeO{sub 3-{delta}}. The inset shows the thermal variation of {sigma}. Ceramics used were prepared by mechanical activation followed by a two-step sintering process at 900 Degree-Sign C for 1 h and 1000 Degree-Sign C for 5 h (82% densification). Highlights: Black-Right-Pointing-Pointer Sr{sub 0.9}K{sub 0.1}FeO{sub 3-{delta}} was successfully obtained by mechanical activation of oxide precursors. Black-Right-Pointing-Pointer Synthesis temperature is significantly lower when compared to a conventional solid-state route. Black-Right-Pointing-Pointer Oxygen nonstoichiometry of annealed samples at 900-1100 Degree-Sign C vary in the range {delta}=0.30-0.32. Black-Right-Pointing-Pointer Sr{sub 0.9}K{sub 0.1}FeO{sub 3-{delta}} shows metal and semiconductor behaviour above and below 400 Degree-Sign C, respectively.

36 MATERIALS SCIENCE↗
DOE OSTI2013

High-pressure synthesis, crystal structure and magnetic property of ilmenite-type FeGeO{sub 3}

We synthesized well-crystallized ilmenite-type FeGeO{sub 3} to investigate its structural and magnetic properties. Ilmenite-type FeGeO{sub 3} were synthesized by high-pressure synthesis technique using a Kawai-type multi-anvil apparatus. Their structural and magnetic properties were examined by XRD analysis with Rietveld refinement, transmission electron microscopy, Moessbauer spectroscopy and SQUID-magnetization measurements. The subsequent annealing after the high-pressure synthesis was effective to improve the crystallinity of the ilmenite-type FeGeO{sub 3}. The primary particle size of ilmenite-type FeGeO{sub 3} was {approx}15 nm. Some particles seemed to be covered with non- or poorly crystalline phase even after the annealing, and others showed a lamellar microstructure parallel to the (0 0 1) plane. Theilmenite-type FeGeO{sub 3} showed typical antiferromagnetic behavior with the Neel temperature of 79 K. - Graphical abstract: Crystal structure, transmission electron micrograph and temperature dependent susceptibility of ilmenite-type FeGeO{sub 3}. Highlights: Black-Right-Pointing-Pointer Ilmenite-type FeGeO{sub 3}, a novel polymorphism of FeGeO{sub 3} was successfully synthesized. Black-Right-Pointing-Pointer It was synthesized by using high pressure technique at 23.5 GPa at 500 Degree-Sign C. Black-Right-Pointing-Pointer Subsequent annealing in vacuum was effective to improve the crystallinity. Black-Right-Pointing-Pointer Its primary particle size was {approx}15 nm, and some grains had lamellar microstructure. Black-Right-Pointing-Pointer It showed typical antiferromagnetic behavior with the Neel temperature of 79 K.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Synthesis and characterization of thermally stable large-pore mesoporous nanocrystallineanatase

Thermally stable mesoporous nanocrystalline TiO{sub 2} with a pure anatase structure was obtained by sol–gel synthesis (in combination with hydrothermal treatment) using titanium tetrabutoxide and dibenzo-18-crown-6 as a structure-directing agent in presence of surfactant and/or La{sup 3+} ions additives. Nanocrystalline TiO{sub 2} demonstrates various textures with a well-defined spherical morphology (micro- and nanospheres), a crystallite size of no greater than 10 nm (XRD), and a narrow pore size distribution. Spherical particles of micrometer scale in the presence of La{sup 3+} ions do not form. TiO{sub 2} calcined (at 500 °C) after hydrothermal treatment (at 175 °C) has a significantly more developed porous structure as compared with TiO{sub 2} which was not treated hydrothermally. For example, specific surface area amounts 137 m{sup 2} g{sup −1} and 69 m{sup 2} g{sup −1}, pore volume 0.98 cm{sup 3} g{sup −1} and 0.21 cm{sup 3} g{sup −1}, pore diameter 17.5 nm and 12.5 nm respectively for samples hydrothermally treated and not treated. - Graphical abstract: Large-pore mesoporous nanocristalline anatase. Highlights: ► Large-pore mesoporous nanocrystalline TiO{sub 2} was obtained by sol–gel synthesis. ► Crown ether was used as template in presence of surfactant and/or La{sup 3+} ions. ► Anatase (crystalline size<11 nm) is the only crystalline phase present in TiO{sub 2}. ► TiO{sub 2} shows well-defined homogeneous spherical morphology (micro- and nano-spheres)

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Vapour phase approach for iron oxide nanoparticle synthesis from solid precursors

A new non-solution mediated approach to the synthesis of iron oxide nanoparticles directly from solid FeCl{sub 2} salt precursors has been developed. The method is rapid, simple and scalable. The structural properties and the phase of the resulting iron oxide particles has been determined by a range of methods including XRD, FT-IR and Mössbauer spectroscopy, and the phase is shown to be maghemite (γ-Fe{sub 2}O{sub 3}). The magnetic properties of the iron oxide particles have been measured using SQUID, confirming superparamagnetic behaviour of the powder and a saturation magnetization of 53.0 emu g{sup −1} at 300 K. Aqueous dispersions at increasing concentrations were prepared and their heating rate under a 400 kHz alternating magnetic field measured. The specific absorption rate (SAR) of the iron oxide was found to be 84.8 W g{sup −1}, which makes the material suitable for the formulation of ferrofluids or ferrogels with RF heating properties. - Graphical Abstract: Superparamagnetic iron oxide nanoparticles obtained by a novel vapour phase approach. Highlights: ► Novel vapour phase (non-solvent) approach for iron oxide nanoparticle synthesis. ► Attractive alternative approach to the present co-precipitation method. ► Better magnetic properties with high coercivity of nanoparticles. ► A high specific absorption rate (SAR) for hyperthermia applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Effect of synthesis atmosphere, wetting, and compaction on the purity of AlB₂

AlB₂ is attractive as an energetic fuel because of its large heat of combustion on a volumetric basis. The formation of AlB₂ from its elements is thermodynamically limited by decomposition into liquid aluminum and α-AlB₁₂ at temperatures approaching 950 °C, and kinetically limited in the reverse reaction, making synthesis of high-purity powders difficult. Minimizing unreacted Al and B makes AlB₂ more resistant to moisture degradation. AlB₂ yield for similarly prepared samples was observed to be significantly higher in He–6% H₂ or vacuum compared to a high-purity Ar atmosphere. Lower AlB₂ yield was generally associated with higher Al₂O₃ content in the reaction products, suggesting that poor Al wetting on oxide surfaces generated by the reaction of Al with B₂O₃ and other sources of oxygen prevented complete reaction. Compaction decreased the amount of oxygen available to the interior of the pellet, and the vacuum and He–6% H₂ environments reduced the amount of oxide impurities in the system, possibly by reducing or subliming them. By optimization of synthesis parameters the purity of AlB₂ was measured as 93 wt%, which was better than the previously reported bulk syntheses. Accounting for unreacted boron is important when using XRD to assess purity since the quantification of secondary phases, such as Al, Al₂O₃, and Al₃BC, allow the amount of boron, which is not easily detected in the scan, to be calculated. - Graphical abstract: Atmosphere and compaction pressure affect AlB₂ purity. Highlights: • Vacuum or He–6% H₂ yielded higher AlB₂ than Ar due to reduced Al₂O₃. • Compaction at 25 MPa prior to heating improved the AlB₂ yield. • XRD can be used to quantify AlB₂ if Al is used to assess the free B content. • Elimination of oxide impurities is the key to making higher purity AlB₂.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Large scale synthesis, second-harmonic generation, and piezoelectric properties of a noncentrosymmetric vanadium phosphate, Li₂VPO₆

The phase pure large scale synthesis, second-harmonic generation, and piezoelectric properties of a vanadium phosphate, Li₂VPO₆ are reported. The material has been synthesized by a standard solid-state reaction using Li₂CO₃, V₂O₅, and NH₄H₂PO₄ as reagents. The phase purity and crystal structure of the reported material have been confirmed by powder X-ray and neutron diffractions. The material crystallizes in orthorhombic space group Pna2₁ (no. 33) with a=10.32581(7) Å, b=4.63728(3) Å, c=8.56606(5) Å, and Z=4. The noncentrosymmetric layered structure is composed of distorted VO₆ octahedra and PO₄ tetrahedra. The V⁵⁺ cations distort either along the approximate [1 0 1] or [-1 0 1] directions attributable to the alignment of distorted VO₆ octahedra, resulting in a polar structure. Powder second-harmonic generating (SHG) measurements on Li₂VPO₆ using 1064 nm radiation, indicate the material has a SHG efficiency of approximately 10 times that of α-SiO₂ and is not phase-matchable (type 1). Converse piezoelectric measurements for the material reveal a piezoelectric coefficient, d₃₃, of 12 pm V⁻¹. - Graphical abstract: A net moment arising from the alignment of the distorted VO₆ octahedra is responsible for the SHG and piezoelectricity for the noncentrosymmetric vanadium phosphate, Li₂VPO₆. Highlights: • Large scale synthesis of a NCS vanadium phosphate, Li₂VPO₆ is reported. • Li₂VPO₆ exhibits a SHG efficiency of 10× that of α-SiO₂. • Li₂VPO₆ reveals a piezoelectric coefficient, d₃₃, of 12 pm V⁻¹. • A net moment is arising from the alignment of the VO₆ octahedra in Li₂VPO₆.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Synthesis of flower-like Boehmite (γ-AlOOH) via a one-step ionic liquid-assisted hydrothermal route

A simple and novel synthesis process, one-step ionic liquid-assisted hydrothermal synthesis route, has been developed in the work to synthesize Bohemithe (γ-AlOOH) with flower-like structure. The samples were characterized by X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR) and Scanning Electron Microscope (SEM). Ionic liquid [Omim]{sup +}Cl{sup −}, as a template, plays an important role in the morphology and pore structure of the products due to its strong interactions with reaction particles. With the increase in the dosage of ionic liquid [Omim]{sup +}Cl{sup −}, the morphology of the γ-AlOOH was changed from initial bundles of nanosheets (without ionic liquid) into final well-developed monodispersed 3D flower-like architectures ([Omim]{sup +}Cl{sup −}=72 mmol). The pore structure was also altered gradually from initial disordered slit-like pore into final relatively ordered ink-bottle pore. Furthermore, the proposed formation mechanism and other influencing factors such as reaction temperature and urea on formation and morphology of the γ-AlOOH have also been investigated. - Graphical abstract: The flower-like γ-AlOOH architectures composed by nanosheets with narrow size distribution (1.6–2.2 μm) and uniform pore size (6.92 nm) have been synthesized via a one-step ionic liquid-assisted hydrothermal route. - Highlights: • The γ-AlOOH microflowers were synthesized via an ionic liquid-assisted hydrothermal route. • Ionic liquid plays an important role on the morphology and porous structure of the products. • Ionic liquid can be easily removed from the products and reused in recycling experiments. • A “aggregation–recrystallization–Ostwald Ripening“formation mechanism may occur.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Hydrothermal synthesis and characterization of zirconia based catalysts

In this work, three equimolar mixed oxides ZrO{sub 2}/CeO{sub 2}, ZrO{sub 2}/TiO{sub 2}, ZrO{sub 2}/La{sub 2}O{sub 3} and a reference ZrO{sub 2} have been synthesized by hydrothermal method. The structural and surface properties of these materials have been fully characterized by X-ray diffraction, transmission electron microscopy, surface area measurement, chemical analysis, XPS, infrared spectroscopy after adsorption of pyridine and adsorption microcalorimetry of NH{sub 3} and SO{sub 2} probe molecules. All investigated mixed oxides are amphoteric and possess redox centers on their surface. Moreover, hydrothermal synthesis leads to catalysts with higher surface area and with better acid–base properties than classical coprecipitation method. Both Lewis and Brønsted acid sites are present on the surface of the mixed oxides. Compared to the other samples, the ZrO{sub 2}/TiO{sub 2} material appears to be the best candidate for further application in acid–base catalysis. - Graphical abstract: Mesoporous amorphous phase with a high surface area of titania zirconia mixed oxide obtained by hydrothermal preparation. - Highlights: • Three zirconia based catalysts and a reference were prepared by hydrothermal synthesis. • Mixed oxides present larger surface areas than the reference ZrO{sub 2}. • ZrO{sub 2}/TiO{sub 2} catalyst presents a mesoporous structure with high surface area. • ZrO{sub 2}/TiO{sub 2} catalyst presents simultaneously strong acidic and basic properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Synthesis and characterization of three-layered zinc phosphites containing tert-octylamine molecules with template and ligand roles

Three-layered zinc phosphites containing single monoamine molecules with different roles have been synthesized using hydro(solvo)thermal methods and characterized by single-crystal X-ray diffraction, thermogravimetric analysis, and infrared spectroscopy. Compound 1, (C{sub 8}H{sub 17}NH{sub 3}){sub 4}Zn{sub 3}(HPO{sub 3}){sub 5}·3H{sub 2}O, consists of 20-ring layer structures sandwiched by water molecules and protonated tert-octylamine molecules. The structure of Zn(C{sub 8}H{sub 17}NH{sub 2})(HPO{sub 3}) (compound 2) is composed of 4.8{sup 2} network structures, wherein the tert-octylamines are coordinated to the Zn atom as pendant groups. Compound 3, (C{sub 8}H{sub 17}NH{sub 3}){sub 2}Zn{sub 4}(C{sub 8}H{sub 17}NH{sub 2})(HPO{sub 3}){sub 5}, was prepared in which the amine plays a dual role as both a ligand and a countercation. In addition, compound 1 is the first layered metal phosphite with large 20-ring windows. This group of substances represents the first example of the preparation of compounds in which the reactivity of incorporated single amine molecules is varied by adjusting the synthesis conditions. - Graphical abstract: The first layered metal phosphite with large 20-ring windows, (C8H17NH3)4Zn3(HPO3)5·3H{sub 2}O (1), sandwiched by water molecules and protonated tert-octylamine molecules. Highlights: • The first example of zinc phosphites contains amine molecules with template and ligand roles. • The reactivity of single amine molecules is varied by adjusting the synthesis conditions. • Compound 1 contains the largest pore opening of 20-rings in known layered metal phosphites. • Compound 3 has dual roles of amine molecules in its structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

A simple facile approach to large scale synthesis of high specific surface area silicon nanoparticles

An inexpensive, facile, and high throughput synthesis of silicon nanoparticles was achieved by the mechano-chemical reduction reaction of magnesium silicide (Mg{sub 2}Si) and silicon monoxide (SiO) using a high energy mechanical milling (HEMM) technique followed by acid leaching. Characterization of the resultant product using X-Ray diffraction, Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and surface area analyses was performed at various stages of the synthesis process. XRD patterns show that the final product formed is single phase silicon and the nanocrystalline nature was confirmed by the shifted transverse optical (TO) band, characteristic of nc-Si determined by Raman analysis. SEM and TEM shows the presence of particles of different sizes in the range of few nanometers to agglomerates of few microns which is consistent with products obtained from mechanical milling. BET measurements show a very high specific surface area (SSA) of ∼190 m{sup 2}/g obtained due to acid leaching which is also validated by the porous nature of the particles confirmed by the SEM images. - Graphical abstract: Schematic showing the large scale production of nanosized silicon and BET surface area of the product formed at various stages.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Sol–gel synthesis of MCM-41 silicas and selective vapor-phase modification of their surface

Silica particles with uniform hexagonal mesopore architecture were synthesized by template directed sol–gel condensation of tetraethoxysilane or mixture of tetraethoxysilane and (3-chloropropyl)triethoxysilane in a water–ethanol–ammonia solution. Selective functionalization of exterior surface of parent materials was carried out by postsynthetic treatment of template-filled MCM-41 and Cl-MCM-41 with vapors of (3-chloropropyl)triethoxysilane and 1,2-ethylenediamine in vacuum. The chemical composition of obtained mesoporous silicas was estimated by IR spectroscopy and chemical analysis of surface products of reactions. Characteristics of porous structure of resulting materials were determined from the data of X-ray, low-temperature nitrogen ad-desorption and transmission electron microscopy measurements. Obtained results confirm invariability of highly ordered mesoporous structure of MCM-41 and Cl-MCM-41 after their selective postsynthetic modification in vapor phase. It was proved that proposed method of vapor-phase functionalization of template-filled starting materials is not accompanied by dissolution of the template and chemical modification of pores surface. This provides preferential localization of grafted functional groups onto the exterior surface of mesoporous silicas. - Graphical abstract: Sol–gel synthesis and postsynthetic chemical modification of template-filled MCM-41 and Cl-MCM-41 with (3-chloropropyl)triethoxysilane and 1,2-ethylenediamine in vapor phase. Display Omitted - Highlights: • Synthesis of MCM-41 silica by template directed sol–gel condensation. • Selective vapor-phase functionalization of template-filled silica particles. • Preferential localization of grafted groups onto the exterior surface of mesoporous silicas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Synchrotron X-ray diffraction and Raman spectroscopy of Ln{sub 3}NbO{sub 7} (Ln=La, Pr, Nd, Sm-Lu) ceramics obtained by molten-salt synthesis

Ln{sub 3}NbO{sub 7} (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) ceramics were obtained by molten-salt synthesis and their structures were systematically investigated by synchrotron X-ray diffraction (SXRD), second harmonic generation (SHG) and Raman spectroscopy. It was observed that ceramics with the largest ionic radii (La, Pr, Nd) crystallized into the Pmcn space group, while the ceramics with intermediate ionic radii (Sm-Gd) exhibited a different crystal structure belonging to the Ccmm space group. For this last group of ceramics, this result was corroborated by SHG and Raman scattering and ruled out any possibility for the non-centrosymmetric C 222{sub 1} space group, solving a recent controversy in the literature. Finally, according to SXRD, Tb-Lu containing samples exhibited an average defect fluorite structure (Fm3{sup ¯}m space group). Nonetheless, broad scattering at forbidden Bragg reflections indicates the presence of short-range domains with lower symmetry. Vibrational spectroscopy showed the presence of six Raman-active modes, inconsistent with the average cubic fluorite structure, and in line with the existence of lower-symmetry nano-domains immersed in the average fluorite structure of these ceramics. - Graphical abstract: Raman spectrum for Sm{sub 3}NbO{sub 7} ceramics showing their 27 phonon modes adjusted through Lorentzian lines. According to synchrotron X-ray diffraction and Raman scattering, this material belongs to the space group Cmcm. Display Omitted - Highlights: • Ln{sub 3}NbO{sub 7} ceramics were obtained by molten-salt synthesis. • SXRD, SHG and Raman scattering confirmed orthorhombic and cubic structures. • Ccmm instead of C222{sub 1} is the correct structure for Sm–Gd ceramics. • Pmcn space group was confirmed for La-, Pr- and Nd-based ceramics. • For Tb–Lu ceramics, ordered domains of a pyrochlore structure were observed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Investigation of some new hydro(solvo)thermal synthesis routes to nanostructured mixed-metal oxides

We present a study of two new solvothermal synthesis approaches to mixed-metal oxide materials and structural characterisation of the products formed. The solvothermal oxidation of metallic gallium by a diethanolamine solution of iron(II) chloride at 240 °C produces a crystalline sample of a spinel-structured material, made up of nano-scale particles typically 20 nm in dimension. XANES spectroscopy at the K-edge shows that the material contains predominantly Fe{sup 2+} in an octahedral environment, but that a small amount of Fe{sup 3+} is also present. Careful analysis using transmission electron microscopy and powder neutron diffraction shows that the sample is actually a mixture of two spinel materials: predominantly (>97%) an Fe{sup 2+} phase Ga{sub 1.8}Fe{sub 1.2}O{sub 3.9}, but with a minor impurity phase that is iron-rich. In contrast, the hydrothermal reaction of titanium bis(ammonium lactato)dihydroxide in water with increasing amounts of Sn(IV) acetate allows nanocrystalline samples of the SnO{sub 2}–TiO{sub 2} solid solution to be prepared directly, as proved by powder XRD and Raman spectroscopy. - Graphical abstract: New solvothermal synthesis approaches to spinel and rutile mixed-metal oxides are reported. - Highlights: • Solvothermal oxidation of gallium metal in organic iron(II) solution gives a novel iron gallate spinel. • Hydrothermal reaction of titanium(IV) complex and tin(IV) acetate produces the complete SnO{sub 2}–TiO{sub 2} solid solution. • Nanostructured mixed-metal oxide phases are produced directly from solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

One-step synthesis of layered yttrium hydroxides in immiscible liquid–liquid systems: Intercalation of sterically-bulky hydrophobic organic anions and doping of europium ions

Inorganic–organic layered rare-earth compounds were synthesized on the basis of a biphasic liquid–liquid system in one pot. Layered yttrium hydroxides (LYHs) were chosen as a host material for the intercalation of hydrophobic organic guest anions such as benzoate, sebacate, or laurate. In a typical synthesis, an organic phase dissolving carboxylic acid was placed in contact with an equal amount of an aqueous phase dissolving yttrium nitrate n-hydrate and urea. At elevated temperatures up to 80 °C, urea was hydrolyzed to release hydroxyl anions which were used to form yttrium hydroxide layers. LYHs were then precipitated with the intercalation of carboxylate anions delivered from the organic phase under the distribution law. The structure and the morphology of the LYHs could be modulated by the intercalated anions. Doped with Eu{sup 3+} ions, the LYHs exhibited red photoluminescence which was enhanced by the intercalated anions due to the antenna effect. - Graphical abstract: The Eu{sup 3+}-doped layered yttrium hydroxide exhibits intense red photoluminescence after intercalation of benzoate ions. Display Omitted - Highlights: • Immiscible biphasic liquid systems were introduced to synthesize layered yttrium hydroxides. • The temperature of the biphasic systems does not exceed 80 °C in one step of the synthesis. • Hydrophobic organic anions were intercalated between the hydroxide layers in one pot. • Structure and morphology of the hydroxides were modulated by changing the kind of organic anions. • Eu{sup 3+}-doping led to red luminescence from the hydroxides in association with the intercalated organic anions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗