Optical activity measurements on solids. 6. Solid state optical activity and circular dichroism measurements of sodium thioantimonate nonahydrate

Summary We have demonstrated that optical circular dichroism (CD) measurements can be carried out on powders suspended in a liquid medium. The refractive indices of the powder and the suspending liquid must be matched, the suspending liquid must not interact significantly with the solid to be measured and must not absorb in the region where the measurements are carried out. Sodium thioantimonate nonahydrate (Na₃SbS₄·9H₂O) powders obtained by grinding oflevo- ordextro-rotatory crystals were found to be excellent examples for the demonstration of this technique. Measurements of the optical rotation forlevo- anddextro-rotatory crystals and powders of Na₃SbS₄·9H₂O were also carried out and provided additional characterization of this salt. In the course of developing the CD measurement technique, CD of NaClO₃ and NaBrO₃ crystals was also measured.Dedicated to Prof. Dr. Karl Schlögl on the occasion of his 70^th birthday with our warmest wishes     

Synthesis and characterization of nanometric powders of UO2+x, (Th,U)O2+x and (La,U)O2+x

This paper describes a new way of preparing nanometric powders of uranium oxide, to fit the needs of studies on UO₂ oxidation, through the electrochemical reduction of U(VI) into U(IV). These powders can also be doped with radionuclides if necessary. The precipitation of oxides occurs in reducing and anoxic conditions. This original method makes it possible to synthesize nanometric UO₂ powders with a calibrated size, as well as the Th- and La-doped UO₂ powders with a predefined composition. The powder characterization by the X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron Microscopy shows the formation of spherical crystallites of UO_2+x, (Th,U)O_2+x and (La,U)O_2+x phases. The composition can be defined by the initial Th/(Th+U) and La/(La+U) ratios in solution and the particle size can be controlled by varying the pH.     

On the thermal decomposition of K2PdCl4 in a hydrogen atmosphere

The decomposition of single crystals and powders of K₂PdCl₄ in a hydrogen atmosphere was investigated by means of thermogravimetry (TG) at temperatures between 85 and 170°C, and by optical microscopy. The rate of decomposition is controlled by a combined process of nucleation and growth. The activation energy was calculated to be 15.2 ± 0.5 kcal mol^?1 for single crystals and 13.5 ± 0.4 kcal mol^?1 for powders. The results are compared with those obtained for K₂PtCl₄.An attempt was made to explain the differences in the orientation relationships, previously determined by X-ray diffraction, between K₂PtCl₄ and K₂PdCl₄, Rb₂PdCl₄ and K₂PdBr₄ and their decomposition products with a different kinetic behaviour.     

High-Density and Thermally Stable Palladium Single-Atom Catalysts for Chemoselective Hydrogenations

Single-atom catalysts (SACs) have shown superior activity and/or selectivity for many energy- and environment-related reactions, but their stability at high site density and under reducing atmosphere remains unresolved. Herein, we elucidate the intrinsic driving force of a Pd single atom with high site density (up to 5 wt %) under reducing atmosphere, and its unique catalytic performance for hydrogenation reactions. In situ experiments and calculations reveal that Pd atoms tend to migrate into the surface vacancy-enriched MoC surface during the carburization process by transferring oxide crystals to carbide crystals, leading to the surface enrichment of atomic Pd instead of formation of particles. The Pd₁/α-MoC catalyst exhibits high activity and excellent selectivity for liquid-phase hydrogenation of substituted nitroaromatics (>99 %) and gas-phase hydrogenation of CO₂ to CO (>98 %). The Pd₁/α-MoC catalyst could endure up to 400 °C without any observable aggregation of single atoms.     

Thermal decomposition of alkaline-earth carbonate samples of extreme thickness

Forward and reverse reactions were studied of the type MCO₃ = MO+CO₂, (M = Mg, Ca, Sr and Ba). The samples were of three types: (1) thick (some mm) crystals; (2) powders; (3) thin layers (about 10 nm).Pressure—temperature data of the reactions are reported from the point of view of reversibility and equilibrium. The effect of repeated isothermal reaction cycles resulted in decreasing conversion of CO₂ uptake.Isothermal and non-isothermal thermal measurements were completed with studies on an electron microprobe analyzer to explain the results.     

Preparation of novel structural nanosized Y2O3 powders and their catalytic activity on the decomposition of NH4ClO4

For the first time, novel structural nanosized Y₂O₃ powders were successfully synthesized by the n-butanol soft-template method. X-ray diffraction, transmission electron microscopy, scanning electron microscopy and Raman spectroscopy were used to characterize the products. The results indicate that these products (calcined at 700°C) were comprised of many Y₂O₃ nanomembranes, and the nanomembranes could change into nanorods when calcined at 1000°C. Interestingly, differential thermal analysis studies suggested that the nanosized Y₂O₃ crystals had intense catalytic activity on the thermal decomposition of ammonium perchlorate.     

On the thermal decomposition of K2PtCl4 in a hydrogen atmosphere

The reaction of single crystals and powders of K₂PtCl₄ with hydrogen is studied by means of thermogravimetry (TG) at temperatures between 175 and 225°C and by optical microscopy. Two different mechanisms are observed. The rate of decomposition of single crystals is determined by the displacement of the reaction interface, which is similar in every crystallographic direction.The rate of decomposition of the powders is limited by the rate of nucleation in the powder particles. For both mechanisms the kinetic parameters are calculated. The activation energy for the displacement of the interface is much higher than the one necessary for nucleation.     

Specific properties of fine SnO<Subscript>2</Subscript> powders connected with surface segregation

The effect of surface segregation in Sb- and In-doped SnO₂ fine-grained powders has been analyzed in comparison with single-crystalline samples. The kinetics and thermodynamics of the Sb and In segregation processes were studied as a function of annealing temperature by X-ray photoelectron spectroscopy (XPS) after annealing in an oxygen-containing atmosphere. Significant differences between diffusion and segregation were revealed for doped powders and single crystals, obviously because of simultaneous diffusion and particle-growth processes proceeding during annealing of powders. For doped single crystals the thermodynamic equilibrium is approached after 24 h annealing above 850 °C and at 1000 °C for Sb and In, respectively. Higher effective activation energies of diffusion are observed for doped powders and the thermodynamic equilibrium is not achieved under technologically relevant annealing conditions. On the basis of dopant profile measurements anomalies in the electrical resistivity at 300 °C of Sb-doped SnO₂ powders annealed at 700 and 900 °C were attributed to an Sb-depleted zone formed beneath the segregated surface during the kinetic regime. To achieve optimum resistivity behavior for commercial application, inhomogeneous doping of powders must be avoided by appropriate preparation steps.     

Properties of methylammonium lead iodide perovskite single crystals

The technique for growing CH₃NH₃PbI₃ single crystals from saturated solutions in concentrated hydroiodic acid is improved by introducing a reducing agent (hypophosphorous acid). The structure of perovskite is confirmed by single crystal XRD. By energy dispersive spectroscopy and X-ray photoelectron spectroscopy it is established that the stoichiometry of the grown crystals corresponds to the CH₃NH₃PbI₃ compound. Changes in the photoluminescence intensity during in-air measurements show that the crystals synthesized using the reducing agent are more stable in the external environment with laser exposure than without it.     

Mechanochemical-hydrothermal synthesis of calcium phosphate powders with coupled magnesium and carbonate substitution

Magnesium- and carbonate-substituted calcium phosphate powders (Mg-, CO₃-CaP) with various crystallinity levels were prepared at room temperature via a heterogeneous reaction between MgCO₃/Ca(OH)₂ powders and an (NH₄)₂HPO₄ solution using the mechanochemical-hydrothermal route. X-ray diffraction, infrared spectroscopy, and thermogravimetric analysis were performed. It was determined that the powders containing both Mg²⁺ and CO₃²⁻ ions were incorporated uniformly into an amorphous calcium phosphate phase while in contrast, the as-prepared powder free of these dopants was crystalline phase-pure, stoichiometric hydroxyapatite. Dynamic light scattering revealed that the average particle size of the room temperature Mg-, CO₃-CaP powders was in the range of 482 nm-700 nm with a specific surface area between 53 and 91 m²/g. Scanning electron microscopy confirmed that the Mg-, CO₃-CaP powders consisted of agglomerates of equiaxed, ≈20-35 nm crystals.     

高硅SSZ-13分子筛膜二次水热生长过程

采用稀释模板剂合成溶胶在管状莫来石支撑体上制备高硅SSZ-13分子筛膜以研究膜的二次水热生长过程。对433 K下二次生长2~72 h的膜和底料进行表征,XRD表明膜和底料中的SSZ-13特征峰均在6 h后出现。底料中的晶粒尺寸基本不随晶化时间的延长而变化。在298 K和0.4 MPa测试条件下,433 K晶化72 h的SSZ-13分子筛膜CO₂渗透通量为2.08×10^-7 mol·m^-2·s^-1·Pa^-1,CO₂/CH₄理想选择性为24。探讨了SSZ-13分子筛膜的生长过程：涂覆在支撑体上的晶种首先溶解并形成大量有序的结构单元,诱导溶胶中晶粒形成并快速生长,晶粒沉积在支撑体的表面共生形成无缺陷的膜层。     

Excellent degradation performance of azo dye by metallic glass/titanium dioxide composite powders

The metallic glass/titanium dioxide powders (MG/TiO₂) with enhanced photocatalytic oxidation activity were synthesized, which exhibit a higher efficiency in decolorizing methylene blue solutions (MB). Compared with the pure TiO₂ and crystalline alloy/TiO₂ (CA/TiO₂) under the same circumstances, its degradation rate was 60 % and 30 % higher, respectively. Furthermore, compared with the CA/TiO₂, the MG/TiO₂ photocatalytic rate was three times faster when decolorizing MB. Considering the excellent intrinsic high-performance photocatalytic degradation under visible light irradiation, these novel powders were proven to have potential applications in water purification industry.     

Photocatalysis enhancement of CaAl<Subscript>2</Subscript>O<Subscript>4</Subscript>:Eu<Superscript>2+</Superscript>, Nd<Superscript>3+</Superscript>@TiO<Subscript>2</Subscript> composite powders

CaAl₂O₄:Eu²⁺, Nd³⁺@TiO₂ composite powders were synthesized by a sol–gel method under mild conditions (i.e. low temperature and ambient pressure). The as-prepared powders were characterized by transmission electron microscopy (TEM) and analyzed by X-ray diffraction (XRD). The photocatalytic behavior of the TiO₂-base surfaces was evaluated by the degradation of nitrogen monoxide gas. It suggested that CaAl₂O₄:Eu²⁺, Nd³⁺@TiO₂ composite powders were composed of anatase titania and that CaAl₂O₄:Eu²⁺, Nd³⁺. TiO₂ particles were deposited on the surface of CaAl₂O₄:Eu²⁺, Nd³⁺ to form uniform film. CaAl₂O₄:Eu²⁺, Nd³⁺@TiO₂ composite powders exhibited higher photocatalytic activity compared with pure TiO₂ under visible light. And the result also clearly indicated that the long afterglow phosphor absorbed and stored lights for the TiO₂ to remain photocatalytic activity in the dark.     

Reactions of ferrocene with phthalonitrile on the surface of oxide powders

The reaction of ferrocene with phthalonitrile at 200°C in a vacuum in the absence of solvents forms crystals of the monoclinic phthalocyanine β phase and ferrocene polymerization products. The use of oxide powders (SiO₂, V₂O₅) as a surface for the reaction of ferrocene with phthalonitrile makes it possible to obtain iron phthalocyanines. The samples of pure compounds and deposited phthalocyanine complexes were analyzed by electronic absorption and IR spectroscopy, and X-ray diffraction.     

Deposition of La2Zr2O7 film by chemical solution deposition

La₂Zr₂O₇ (LZO) formation of bulk powders and of films by chemical solution deposition (CSD) process have been studied using propionates. The treatment involved a one step cycle in the reducing forming gas (Ar-5%H₂) to be compatible with Ni-5at%W RABITS. Large amount of residual carbon was found in LZO powders formed in these conditions (10 wt%). The volume fraction of the cube texture in LZO films on Ni-5at%W RABITS was found to be a function of the speed of the gas flown above sample. This phenomenon is discussed in considering the C deposited from the carbon-containing gases emitted during the pyrolysis of the precursor. Using proper conditions (950 °C and the speed of gas of 6.8 × 10^?2 m/s), LZO films with good surface crystallinity could be obtained on Ni-5at%W RABITS as demonstrated by X-ray diffraction, electron backscattered diffraction and RHEED. The existence of residual carbon in oxide films is a common question to films deposited by CSD processes under reducing condition.     

Preparation of nanocrystalline Fe-doped TiO<Subscript>2</Subscript> powders as a visible-light-responsive photocatalyst

Nanocrystalline Fe-doped TiO₂ powders were prepared using TiOSO₄, urea, and Fe(NO₃)₃ · 9H₂O as precursors through a hydrothermal method. The as-synthesized yellowish-colored powders are composed of anatase TiO₂, identified by X-ray diffraction (XRD). The grain size ranged from 9.7 to 12.1 nm, calculated by Scherrer’s method. The specific surface area ranged from 141 to 170 m²/g, obtained by the Brunauer–Emmett–Teller (BET) method. The transmission electron microscopy (TEM) micrograph of the sample shows that the diameter of the grains is uniformly distributed at about 10 nm, which is consistent with that calculated by Scherrer’s method. Fe³⁺ and Fe²⁺ have been detected on the surface of TiO₂ powders by X-ray photoelectron spectroscopy (XPS). The UV–Vis diffuse reflection spectra indicate that the light absorption thresholds of the Fe-doped TiO₂ powders have been red-shifted into the visible light region. The photocatalytic activity of the Fe-doped TiO₂ was evaluated through the degradation of methylene blue (MB) under visible light irradiation. The Fe-doped TiO₂ powders have shown good visible-light photocatalytic activities and the maximum degradation ratio is achieved within 4.5 h.     

Synthesis of NH<Subscript>4</Subscript>TiOF<Subscript>3</Subscript> Crystals in the Presence of Polyoxyethylene Ethers

The effect of polyoxyethylene ethers as surfactants on the morphology of NH₄TiOF₃ crystals obtained by hydrolysis of (NH₄)₂TiF₆ in the presence of boric acid is analyzed. Depending on the molecular weight of the polyoxyethylene ether, the geometric dimensions (thickness and lateral size) of the crystals change. The obtained samples were characterized by X-ray and electron diffraction, Raman spectroscopy, and scanning electron microscopy. The heat treatment of NH₄TiOF₃ powders gives anatase mesocrystals retaining the initial particle morphology.     

New Solids in As-O-Mo,As(P)-O-Mo(W) and As(P)-O-Nb(W) Systems That Exhibit Nonlinear Optical Properties

Interactions between well-mixed fine powders of As₂O₃, P₂O₅, MoO₃, WO₃ and Nb₂O₅ at different stoichiometry in quartz ampoules under vacuum at ~1000 °C in the presence of metallic molybdenum (or niobium), over several weeks, led to shiny dichroic crystalline materials being formed in cooler parts of the reaction vessel. An addition of small quantities of metals-Mo or Nb-was made with the aim of partially reducing their highly oxidized Mo(VI), W(VI) or Nb(V) species to corresponding Mo(V), W(V) and Nb(IV) centers, in order to form mixed valence solids. Sublimed crystals of four new compounds were investigated using a variety of techniques, with prime emphasis on the X-ray analysis, followed by spectroscopy (diffusion reflectance, IR, Raman and EPR), second harmonic generation (SHG), thermal analysis under N₂ and air atmosphere, and single crystals electrical conductivity studies. The results evidenced the formation of new complex solids of previously unknown compositions and structures. Three out of four compounds crystallized in non-centrosymmetric space groups and represent layered 2D polymeric puckered structures that being stacked on each other form 3D lattices. All new solids exhibit strong second-harmonic-generation (SHG effect; based on YAG 1064 nm tests with detection of 532 nm photons), and a rare photosalient effect when crystals physically move in the laser beam. Single crystals’ electrical conductivity of the four new synthesized compounds was measured, and the results showed their semiconductor behavior. Values of band gaps of these new solids were determined using diffusion reflectance spectroscopy in the visible region. Aspects of new solids’ practical usefulness are discussed.     

Electrical,magnetic, and EPR studies of the quaternary chalcogenides Cu2AIIBIVX4 prepared by iodine transport

Electrical, magnetic, and electron paramagnetic resonance (EPR) measurements have been made on crystals and powders of several quaternary chalcogenides of the type Cu₂A^IIB^IVX₄, where A^II = Zn, Mn, Fe, or Co, B^IV = Si, Ge, or Sn, and X = S or Se. The electrical properties of these compounds are extrinsic, but their magnetic properties do not appear to be affected by impurities. The magnetic moments of the Cu₂MnBX₄ compounds decrease with increasing covalency of the MnX bond, and those of Cu₂FeGeS₄ and Cu₂CoGeS₄ reflect an orbital contribution to the moment. Both the Weiss constants and magnetic ordering temperatures in these compounds show an evolution from antiferromagnetism to ferromagnetism with increasing separation between the moments. Magnetic measurements on single crystals of Cu₂MnGeS₄, Cu₂CoGeS₄, and Cu₂FeGeS₄ indicate that only the latter is anisotropic. EPR measurements on crystals and powders of Cu₂ZnGeS₄ doped nominally with 0.1% Mn reveal that Mn²⁺ experiences an axial distortion and that the bond ionicity is the same as in ZnS.     

Facile Synthesis of Leaf-like Cu(OH)2 and Its Conversion into CuO with Nanopores

Leaf-like Cu(OH)₂ single crystals were synthesized via the controlled emulsion interface method using Span80 (sorbitan monooleate) as the stabilizer of the emulsion system. CuO products with nanopores could be simply obtained by the dehydration of Cu(OH)₂, while maintaining the strip-shaped architecture. The phase structures and morphologies were measured by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectra, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Experimental results showed that Cu(OH)₂ microleaves were single crystals and the growth direction seemed to be in [111] crystal plane of the orthorhombic Cu(OH)₂. The formation of the nanopores should be attributed to the water loss of the transformation from Cu(OH)₂ to CuO. The formation process of Cu(OH)₂ was investigated by taking TEM images at different stages of the reaction. The formed nanoparticles began to rearrange to form nanorods and microleaves possibly via edge-by-edge and side-by-side oriented-attachments because of the formation of larger crystals greatly reducing the interfacial energy. Besides, CuO microarchitectures exhibit blue shifts in UV-Vis spectra and possess larger band gaps compared with those of bulk crystals.