A theoretical analysis of zero-field splitting parameters of Mn doped dicadmium diammonium sulfate Cd2(NH4)2(SO4)3 single crystal

The superposition model (SPM) and crystallographic data are utilized to determine the zero-field splitting (ZFS) parameters (ZFSPs) for Mn²⁺ ions in Cd₂(NH₄)₂(SO₄)₃ single crystal, assuming that the Mn²⁺ ions locate at either Cd²⁺ or NH⁴⁺ site. The SPM results has been verified by the fourth-order perturbation formulae analysis. Experimental suggestions about Mn²⁺ ions substituting at Cd²⁺ sites have been confirmed theoretically for the first time.     

Investigation on the synthesis and quantum confinement effects of pure and Mn added Zn(1−x)CdxS nanocrystals

Zn_(1−x)Cd_xS and Zn_(1−x)Cd_xS:Mn²⁺ semiconductor quantum dots (2-4 nm) have been prepared by a novel solvothermal route assisted microwave heating method. The growth parameters governing the smaller size and higher yield have been optimized. The synthesized QDs exhibit a significant blue shift as compared to their corresponding bulk counterpart in the UV-vis optical absorption spectrum. The dielectric constant value varies from 2.79 to 6.17 (at 40 °C, 1 kHz) depending upon the composition of the alloy; lower value corresponds to Zn_0.75Cd_0.25S:Mn²⁺ and the higher value corresponds to Zn_0.25Cd_0.75S:Mn²⁺. The crystallite size to exciton bohr radius ratio being <1 indicates a strong quantum confinement effect in both CdS and ZnS QDs. The quantum confinement effect exists in the sequence of ZnS:Mn²⁺ < Zn_(1−x)Cd_xS:Mn²⁺ (x < 0.5) < ZnS < Zn_(1−x)Cd_xS < CdS < CdS:Mn²⁺.     

Dielectric and magnetic behavior of BaCd2−xSrxFe16O27 W-type hexagonal ferrites

We have prepared BaCd_2−xSr_xFe₁₆O₂₇ (x = 0, 0.5, 1, 1.5 and 2.0) W-type hexagonal ferrites by standard ceramic method. In this work, the structural, dielectric and magnetic properties have been studied of the prepared samples. The XRD analysis of the samples reveals single phase behavior sintered at 1400 °C for 6 h. The saturation magnetization (M_s) shows increasing behavior with the increasing concentration of Sr²⁺. While the coercivity (H_c) decreases rapidly up to 409 G for x = 1.5 and then increases for (x > 1.5) due to the preference of Cd²⁺ for tetrahedral sites and the number of spin-down magnetic ions. The real and imaginary parts of the dielectric constant (?′,?″) and dielectric loss tangent (tan δ) are determined in the frequency range 0.1-10⁷ Hz. It is observed that both the real and imaginary parts of the dielectric constant and tan δ decrease with the increasing concentration of Sr²⁺, which is due to the contribution of Cd²⁺ ions in addition to Fe³⁺ and Fe²⁺ ions to interfacial polarization.     

The characterisation of the protective film formed by benzotriazole on the 90/10 copper-nickel alloy surface in H2SO4 media

The nature of the protective film formed by benzotriazole (BTAH) on the surface of the 90/10 CuNi alloy in deaerated 0.5 mol L⁻¹ H₂SO₄ solution containing Fe(III) ions as oxidant was investigated by weight-loss, calorimetric measurements, and by surface-enhanced Raman spectroscopy (SERS). The SERS measurements show that the protective film is composed by the [Cu(I)BTA]_n polymeric complex and that the BTAH molecules are also adsorbed on the electrode surface. A modification of the BET isotherm for adsorption of gases in solids is proposed to describe the experimental results obtained from weight-loss experiments that suggest an adsorption in multilayers. Electrochemical studies of copper and nickel in 0.5 mol L⁻¹ H₂SO₄ in presence and absence of BTAH have also been made as an aid to interpret the results. The calculated adsorption free energy of the cuprous benzotriazolate on the surface of the alloy is in accordance with the value for pure copper.     

Synthesis and characterization of in situ carbon-coated Li2FeSiO4 cathode materials for lithium ion battery

Li₂FeSiO₄/C composites with in situ carbon coating were synthesized via sol-gel method based on acid-catalyzed hydrolysis/condensation of tetraethoxysilane (TEOS) with sucrose and l-ascorbic acid as carbon additives, respectively. As-obtained Li₂FeSiO₄/C composites prepared with l-ascorbic acid as a carbon additive are composed of nanoparticulate Li₂FeSiO₄ in an intimate contact with a continuous thin layer of residual carbon and exhibit large specific surface area up to 395.7 m² g⁻¹. The results indicate that structure of the residual carbon is graphene-rich with obviously lower disordered/graphene (D/G) ratio. These as-obtained Li₂FeSiO₄/C composites exhibit first discharge capacity of 135.3 mAh g⁻¹ at C/16 and perform cycling stability, which are superior to those of Li₂FeSiO₄/C composites synthesized with sucrose as a carbon additive.     

Luminescence and energy transfer of Mn and Tb in Y3Al5O12 phosphors

Mn²⁺ is an excellent luminescent ion with variable color from green, yellow to red in different hosts and has been widely utilized in recent years. The luminescent intensity of Mn²⁺ in many hosts is so low that the correlative application is restricted. In the present paper, two methods, i.e. employing a charge compensator and introducing a sensitizer, were adopted to enhance the luminescence of Mn²⁺ in Y₃Al₅O₁₂ (YAG). By employing Si⁴⁺ as a charge compensator, the doping content of Mn²⁺ (x) in Y₃Mn_xAl_5−2xSi_xO₁₂ can be lifted up to 0.4. Mn²⁺ in YAG emits orange light in a broad band. The peak wavelength shifts from 586 to 593 nm with the increasing x. The luminescent intensity of Mn²⁺ reaches its maximum when x = 0.1. Co-doping Tb³⁺ into Mn²⁺ doped YAG, the sensitization effect of Tb³⁺ on Mn²⁺ was observed clearly. The resonance energy transfer from Tb³⁺ to Mn²⁺ occurs because there is a well overlapping between emission spectrum of Tb³⁺ and excitation spectrum of Mn²⁺. A reasonable explanation for the sensitization effect of Tb³⁺ on the luminescence of Mn²⁺ was brought forward.     

Sorption of copper,nickel and cadmium on bone char

The sorption capacity of bone char was tested on the removal of copper, nickel and cadmium ions, from aqueous solutions. The Freundlich and Langmuir models were applied to the adsorption isotherms. The equilibrium data fitted well with the Langmuir model and the maximum loading capacities showed the following affinity order: Cu²⁺ (1.093 mmol g^–1 at pH _i 3, and 0.884 mmol g^–1 at pH _i 4) > Cd²⁺ (0.760 mmol g^–1 at pH _i 3, and 0.690 mmol g^–1 at pH _i 4) > Ni²⁺ (0.453 mmol g^–1 at pH _i 3, and 0.225 mmol g^–1 at pH _i 4). The kinetic data follow a diffusion model in the film and inside particles. A sorption mechanism based on ion exchange, attack by protons of the carbonate and hydroxide positions in the apatite lattice, and also on the adsorption of protons on the basic active sites of carbon, is proposed to explain the heavy metals removal and the pH decreasing in solution.     

可见光和Cd2+对黄铜矿生物浸出的催化作用(英文)

利用扫描电镜(SEM)、同步辐射X射线衍射(SR-XRD)和X射线光电子能谱(XPS)研究在酸性氧化亚铁硫杆菌存在下,可见光和镉离子(Cd²⁺)对黄铜矿生物浸出的影响。生物浸出28天后的结果表明,光照下铜的溶解提高4.96%;Cd²⁺单独存在对黄铜矿的浸出有轻微的抑制作用;可见光和50mg/LCd²⁺同时存在时,溶解铜的浓度提高14.70%。化学浸出结果表明,可见光能促进体系中铁元素的循环。SEM结果显示,Cd²⁺在可见光下促进酸性氧化亚铁杆菌在黄铜矿表面的附着。综合SR-XRD和XPS结果可知,可见光和Cd²⁺促进黄铜矿的浸出,但不会抑制钝化物的形成。提出可见光和Cd²⁺对黄铜矿生物浸出协同催化作用机制的模型。     

Effect of acidic surface functional groups on Cr（VI） removal by activated carbon from aqueous solution

The activated carbon with high surface area was prepared by KOH activation. It was further modified by H2SO4 and HNO3 to introduce more surface functional groups. The pore structure of the activated carbons before and after modification was analyzed based on the nitrogen ad-sorption isotherms. The morphology of those activated carbons was characterized using scanning electronic microscopy (SEM). The surface functional groups were determined by Fourier transform infrared spectroscopy (FTIR). The quantity of those groups was measured by the Boehm titration method. Cr(Ⅵ) removal by the activated carbons from aqueous solution was investigated at different pH values. The results show that compared with H2SO4, HNO3 destructs the original pore of the activated carbon more seriously and induces more acidic surface functional groups on the activated carbon. The pH value of the solution plays a key role in the Cr(Ⅵ) removal. The ability of reducing Cr(Ⅵ) to Cr(Ⅲ) by the activated carbons is relative to the acidic surface functional groups. At higher pH values, the Cr(Ⅵ) removal ratio is im-proved by increasing the acidic surface functional groups of the activated carbons. At lower pH values, however, the acidic surface functional groups almost have no effect on the Cr(Ⅵ) removal by the activated carbon from aqueous solution.     

Role of Cr ions on the microstructure development, and magnetic phase evolution of Ni0.7Zn0.3Fe2O4 ferrite nanoparticles

A series of ferrite samples with the chemical formula Ni_0.7Zn_0.3Cr_xFe_2−xO₄ (x = 0.0-0.5) were prepared by a sol-gel auto-combustion method and annealed at 600 °C for 4 h. The resultant powders were investigated by various techniques, including X-ray diffractometry (XRD), vibrating sample magnetometry (VSM), and permeability studies. The prepared samples have a cubic spinel structure with no impurity phase. As the Cr³⁺ content x increases, bulk density and crystallite size decrease, whereas porosity increases. The saturation magnetization decreases linearly from 58.31 to 42.90 emu/g with increasing Cr³⁺ content. However, coercivity increases with increasing Cr³⁺ substitution. The magnetic moments calculated from Neel's molecular-field model are in agreement in the experiment results. The initial permeability (μ_i) decreases with increasing Cr³⁺ substitution. The decrease in initial permeability (μ_i) is attributed to decrease in magnetization on addition of Cr³⁺. The real part of the permeability decreases gradually with increasing frequency in accordance with Snoek's law. The Curie temperature decreases linearly with increasing Cr³⁺ content.     

Preparation and luminescent characteristics of Sr3RE2(BO3)4:Dy (RE = Y, La, Gd) phosphors for white LED

Dysprosium-activated Sr₃RE₂(BO₃)₄ (RE = Y, La, Gd) phosphors were synthesized by a high temperature solid-state reaction method. The phase uniformity of the phosphors was characterized by X-ray powder diffraction (XRD) and the luminescence characteristics were investigated. The excitation spectra at 575 nm emission show strong spectral bands in the region of 300-500 nm. The emission spectra of the phosphors with 365 nm excitation show three bands centered at 484 nm, 575 nm and 680 nm, which originate from the transitions of ⁴F_9/2 → ⁶H_15/2, ⁴F_9/2 → ⁶H_13/2 and ⁴F_9/2 → ⁶H_11/2 of Dy³⁺, respectively. The effect of Dy³⁺ concentration on the emission intensity of the phosphors was investigated. The fluorescence decay curves for ⁴F_9/2 → ⁶H_13/2 excited at 365 nm and monitored at λ_em of 575 nm were measured. The decay times decreased slowly with increasing Dy³⁺ doping concentration due to a trap capturing to resonance fluorescence transfer of the activated ions and due to the exchange interactions between activated ion pairs. In order to determine the type of interaction between activated ions, the concentration dependence curves (lg(I/x) versus lg x) of Sr₃RE₂(BO₃)₄:Dy³⁺ (RE = Y, La, Gd) were plotted. The concentration quenching mechanism of the ⁴F_9/2 → ⁶H_13/2 (575 nm) transition of Dy³⁺ is the d-d interaction. All results indicate these phosphors are promising white-color luminescent materials.     

Preparation of Ni0.5Zn0.5Fe2O4/SiO2 nanocomposites and their adsorption of bovine serum albumin

The magnetic nanocomposites of (1 − x)Ni_0.5Zn_0.5Fe₂O₄/xSiO₂ (x = 0-0.2) were synthesized by the citrate-gel process and their absorption behavior of bovine serum albumin (BSA) was investigated by UV spectroscopy at room temperature. The gel precursor and resultant nanocomposites were characterized by FTIR, XRD, TEM and BET techniques. The results show that the single ferrite phase of Ni_0.5Zn_0.5Fe₂O₄ is formed at 400 °C, with high saturation magnetization and small coercivity. A porous, amorphous silica layer is located at the ferrite nanograin boundaries, with the silica content increasing from 0 to 0.20, the average grain size of Ni_0.5Zn_0.5Fe₂O₄ calcined at 400 °C reduced from about 18-8 nm. Consequently, the specific surface area of the nanocomposites ascends clearly with the increase of silica content, which is largely contributed by the increase in the thickness of the porous silica layer. The Ni_0.5Zn_0.5Fe₂O₄/SiO₂ nanocomposites demonstrate a better adsorption capability than the bare Ni_0.5Zn_0.5Fe₂O₄ nanoparticles for BSA. With the increase of the silica content from 0 to 0.05 and the specific surface area from about 49-57 m²/g, the BSA adsorption capability of the Ni_0.5Zn_0.5Fe₂O₄/SiO₂ nanocomposites calcined at 400 °C improve dramatically from 22 to 49 mg/g. However, with a further increase of the silica content from 0.05 to 0.2, the specific surface area increase from about 57-120 m²/g, the BSA adsorption for the nanocomposites remains around 49 mg/g, owing to the pores in the porous silica layer which are too small to let the BSA protein molecules in.     

Mixed cerium valence and unusual Ce–Ru bonding in Ce23Ru7Cd4

The rare earth-rich compounds Ce₂₃Ru₇Cd₄ and Pr₂₃Ru₇Cd₄ were synthesized from the elements in sealed tantalum ampoules in an induction furnace. Both structures were refined on the basis of diffractometer data: P6₃mc, Z = 2, a = 988.7(3), c = 2241.6(5) pm, wR2 = 0.0439, 1976 F² values for Ce₂₃Ru₇Cd₄ and a = 992.7(2), c = 2236.4(7) pm, wR2 = 0.0466, 2528 F² values for Pr₂₃Ru₇Cd₄ with 74 variables per refinement. Striking structural motifs are ruthenium centered trigonal prisms RuCe₆ and RuPr₆ which are condensed via common edges and corners, building rigid three-dimensional networks. Larger voids within these networks are filled by slightly elongated Cd₄ tetrahedra. Five of the nine crystallographically independent cerium sites in Ce₂₃Ru₇Cd₄ show Ce–Ru distances which are shorter than the Pr–Ru distances in Pr₂₃Ru₇Cd₄. This strong hint for mixed cerium valence is supported by the magnetic behavior. Pr₂₃Ru₇Cd₄ shows Curie–Weiss behavior above 50 K with an experimental magnetic moment of 3.62 μ_B/Pr atom, indicating stable trivalent praseodymium. Complex magnetic ordering sets in at 13 K. Ce₂₃Ru₇Cd₄ shows a reduced magnetic moment of 2.05 μ_B/Ce atom. The trivalent cerium atoms show ferro- or ferrimagnetic ordering below T_C = 3.6 K.     

室温下介孔MnO2降解低浓度甲醛的研究

本文以KMnO₄和P123为原料采用溶胶-凝胶法在不同条件下制备了介孔MnO₂。研究了反应物比和pH对催化剂结构和催化降解性能的影响。溶胶-凝胶法制备介孔MnO₂的最佳条件为：原料配比为10：1,pH值为7。合成材料的结构和性能采用XRD、N₂吸脱附、FT-IR的测试方法表征,结果表明P123和KMnO₄合成的介孔MnO₂具有较大的比表面积和孔径,且有良好的HCHO催化降解性能。最后讨论了介孔MnO₂催化氧化HCHO的影响因素,发现在pH7 的情况下最有利于介孔MnO₂的活性稳定;在原料比为10：1情况下生成的介孔MnO₂比表面积较大,催化降解性能较强,在10h内保持在对甲醛的降解率为95%以上。     

The formation of 1T and 2H titanium disulfide by deintercalation of NaxTiS2

The topochemical reaction of Na_xTiS₂ solid phases with I₂ in acetonitrile leads to several modifications of TiS₂. The 1T-TiS₂ modification, Cd(OH)₂ type, is found by deintercalation of the rhombohedral phases 3R(I)-Na_xTiS₂ and 3R(II)-Na_xTiS₂. Deintercalation of the hexagonal phase 2H(I)-Na_xTiS₂ leads to a strongly disordered 2H-TiS₂ phase with a chch stacking of sulfur. The structure is in agreement with a mechanism of deintercalation consisting of parallel displacements of TiS₂ sandwiches.The observed magnetic susceptibility of powder 2H-TiS₂ is discussed in terms of a nearly temperature-independent intrinsic contribution of about 14 × 10^?6 emu per mole and a Curie-like tail contribution due to about 3 × 10^?4 mole of localized paramagnetic Ti²⁺ (3d²).     

Sintering of BaZrO3 and SrZrO3 perovskites: Role of substitutions by yttrium or ytterbium

The modification of perovskite sintering oxides A^IIB^IVO₃ was studied. The alkaline earth metal plays a role in the densification of perovskite. The effect of the substitution of Zr⁴⁺ by a lanthanide Yb³⁺ in barium zirconate (BZYb) increases its density and impedes BaO evaporation independently of the thermal cycle. A substitution of Zr⁴⁺ by Y³⁺ increases the density of barium zirconate (BZ) only after 4 h at 1650 °C. In all cases, the substitutions of Zr⁴⁺ by Y³⁺or Yb^{2+ or 3+} in the zirconate inhibit grain growth. The substitution in B site by a Ln³⁺ leads to the creation of vacancies (A^IIB^IV_(1−x)Ln^III_x O_3−x/2). To determine the vacancies’ role, three different controlled atmospheres were tested. Argon, dry air, and oxygen were used to study the impact on the linear shrinkage of barium zirconate when some Zr⁴⁺ are replaced by yttrium or ytterbium (BZY, BZYb) or not substituted (BZ). Strontium zirconate (SZ) is not as chemically stable as barium zirconate (BZ) during the thermal cycle when Yb is used as a substitution element. In effect, the presence of the secondary phase Zr₃Yb₄O₁₂ associated with the release of oxygen proves the bivalence of ytterbium (Yb²⁺ or Yb³⁺). Therefore, ytterbium can be substituted in either A or/and B sites. The study of reactive sintering between lanthanum strontium zirconate (SZYb) and Yb₂O₃ shows that a slight excess of Yb₂O₃ around SZYb grains stabilizes the chemical composition of SZYb. Perovskite symmetry and stability were determined by two factors, i.e., tolerance (t) and octahedral factors (r_B/r_O). It was demonstrated that the distortion of the perovskite unit cell increases the density of pellets.     

Synthesis and characteristics of poly(3-pyrrol-1-ylpropanoic acid) (PPyAA)-Fe3O4 nanocomposite

Poly(3-pyrrol-1-ylpropanoic acid) (PPyAA)-Fe₃O₄ nanocomposite was successfully synthesized by an in situ polymerization of 1-(2-carboxyethyl) pyrrole in the presence of synthesized Fe₃O₄ nanoparticles. Evaluation of structural, morphological, electrical and magnetic properties of the nanocomposite was performed by XRD, FT-IR, TEM, TGA, magnetization and conductivity measurements, respectively. XRD analysis reveals the inorganic phase as Fe₃O₄ and TGA shows about 90 wt% loading of Fe₃O₄ in the nanocomposite. FT-IR analysis indicates a successful conjugation of Fe₃O₄ particles with polypyrrole acetic acid. Magnetization measurements show that polypyrrole acetic acid coating decreases the saturation magnetization of Fe₃O₄ significantly. This reduction has been explained by the pinning of the surface spins by the possible adsorption of non-magnetic ions during the polymerization process. The conductivity and dielectric permittivity measurements strongly depend on the thermally activated polarization mechanism and thermal transition of PPyAA in the nanocomposite structure. Large value of dielectric permittivity (?′) of the nanocomposite at lower frequency is attributed to the predominance of species like Fe²⁺ ions and grain boundary defects (interfacial polarization).     

Controllable synthesis of bifunctional NaYF4:Yb/Ho@SiO2/Au nanoparticles with upconversion luminescence and high X-ray attenuation

A novel type of bifunctional water-soluble NaYF₄:Yb³⁺/Ho³⁺@SiO₂/Au nanocomposite is fabricated by a facile layer-by-layer technology in which the mercapto-silica shell is used as the functional layer coating on the central NaYF₄:Yb³⁺/Ho³⁺ nanocrystals. Then by adjusting the mole ratio of the Au nanoparticles to the NaYF₄:Yb³⁺/Ho³⁺@SiO₂ nanoparticles, control of the gold loading on the upconversion nanocrystal surface is achieved. The fabricated nanocomposites inherit the excellent physical and chemical properties from their building blocks, simultaneously exhibiting upconversion luminescence and high X-ray attenuation and as well are easily modified with various molecules. These properties render the synthesized NaYF₄:Yb³⁺/Ho³⁺@SiO₂/Au nanocomposite not only useful as a multimodality contrast agent to increase the efficiency of molecular imaging but also has the potential of in situ curing of diseases.     

MoO42-与 Zn2+对镁合金在 NaCl 溶液中的协同缓蚀作用

采用动电位极化曲线法,结合腐蚀后的表面微观形貌及EDS能谱分析,研究了MoO42-与Zn2+对AZ31镁合金在3.5%NaCl溶液中的协同缓蚀性能。结果表明:0.005 mol/L Zn2+与0.05 mol/L钼酸钠联合作用,可有效抑制镁合金在NaCl溶液中的腐蚀,Zn2+促进MoO42-在合金表面的吸附,缓蚀效果优于单一的钼酸盐缓蚀剂。缓蚀机制是:钼酸盐与Zn2+协同作用,使镁合金表面形成更为致密的钝化膜,从而抑制镁合金的腐蚀。     

Spectroscopic and crystal field analysis of absorption and photoluminescence properties of red phosphor CaAl12O19:Mn modified by MgO

The spectroscopic properties of a series of red phosphors with general composition of CaAl₁₂O₁₉:yMn⁴⁺ and (Ca_1−xAl₁₂O₁₉, xMgO):yMn⁴⁺ (x = 0-1, y = 0.001-1.5%) synthesized by a modified solid state method in air have been investigated in detail. Addition of MgO is necessary for Mn⁴⁺ charge compensation and leads to the formation of separate crystal phases of Al₂O₃ and MgAl₂O₄, which was confirmed by the XRD studies. Enhancement of Mn⁴⁺ luminescence with increasing content of MgO was observed and a mechanism for explanation of this phenomenon is suggested. For an analysis of the crystal phases and luminescent efficiency of the phosphors in the prepared series, crystal field calculations of the Mn⁴⁺ energy levels have been performed. This theoretical approach allowed for assigning the observed excitation and emission spectra. Red shift of the Mn⁴⁺ luminescence with increasing concentration of Mg ions is explained from the point of view of enhanced nephelauxetic effect after doping.