Bond covalency and electronic structure of CaB2O4(III) crystal

The electronic structure of CaB₂O₄(III) crystal obtained by using SIESTA program is reported in this article. It is observed that the band gap values are, respectively, 5.39 and 5.89 eV from our LDA and GGA calculations. The bond covalency and bond valence are calculated with a simplified method. For both Ca–O and B–O types of bond, the bond covalency has a decreasing trend with the increasing bond length. The result of bond covalency in explaining the interaction between atoms has been shown in good agreement with that of Mulliken population analysis. The ionic configuration for CaB₂O₄(III) in the fundamental state is estimated to be Ca^+1.808B^−0.68O^−0.112. A summary of B–O distances for the four phases of CaB₂O₄ crystal from several works is also presented.     

掺杂Fe2O3对吸附相反应技术制备TiO2的形貌和光催化性能的影响

利用吸附相反应技术制备得到了掺杂不同浓度的Fe₂O₃的TiO₂复合光催化剂。通过透射电子显微镜(TEM)、紫外可见光谱和X射线衍射(XRD)研究不同掺杂浓度对TiO₂形貌和结晶过程的影响,并利用3种波长光源下的甲基橙光降解实验考评了各个复合光催化剂的催化活性。结果表明,掺杂后复合光催化剂中Fe₂O₃分散性较好较均匀。在TiO₂紫外可见吸收光谱中由于Fe₂O₃的掺杂而出现了红移,而且随着掺杂浓度增加红移越来越明显,复合光催化剂的禁带宽度也越来越小。在焙烧过程中无定形Fe₂O₃或Fe³⁺进入了TiO₂的晶格结构,从而抑制了TiO₂的结晶过程。半导体禁带宽度的减少以及TiO₂结晶过程的抑制作用,都导致紫外光下复合光催化剂催化活性的降低。但Fe₂O₃的掺杂也使得复合光催化剂在可见光区出现了一定的光催化活性。     

固溶体Bi_2Mo_(1-x)W_xO_6的水热合成及光催化性能

采用水热法,在较低温度下合成了系列Bi2Mo1-xWxO6固溶体。结果表明,W的替代抑制了固溶体的晶粒生长,导致了较小的晶粒尺寸。随着x的增加,红外光谱中840cm-1处M-O键的振动频率νM-O有规律地向低频率方向移动,表明Mo6+离子逐步被W6+替代,生成了无限互溶的固溶体。光吸收性能研究表明,随着W6+逐步替代Mo6+,带隙出现了先降后升的趋势,x=0.4时带隙最小。而固溶体的光催化性能随着x的增加,出现了先增后减的趋势,x=0.4时光催化活性最高。此外,含W样品的光催化活性高于Bi2MoO6。这与固溶体的带隙、带结构和晶粒尺寸变化有关。     

Preparation of a new pyrochlore-type compound Na0.32Bi1.68Ti2O6.46(OH)0.44 by hydrothermal reaction

A new pyrochlore-type Na_0.32Bi_1.68Ti₂O_6.46(OH)_0.44 with the cubic cell of a=10.339(5) Å was prepared by hydrothermal reaction using TiO₂ (anatase) and Bi₂O₃ in NaOH solution. This compound was obtained when the molar ratio of NaOH/TiO₂ was above 2 and the reaction temperature was above 240 °C. The TG-curve of as-prepared sample showed a mass loss of 0.8 mass% which was caused by release of OH group. This compound decomposed to a pyrochlore-type compound and a layered-type Na_0.5Bi_4.5Ti₄O₁₅ above 800 °C. The optical band gap of Na_0.32Bi_1.68Ti₂O_6.46(OH)_0.44 was estimated to be 2.5 eV.     

纳米复合固体超强酸SO42-/CoFe2O4的制备和表征

采用纳米化学制备技术合成了新型的纳米复合固体超强酸催化剂ＳＯ４＾２－／ＣｏＦｅ２Ｏ４。用ＸＲＤ、ＴＥＭ、ＸＰＳ、红外光谱和比表面测定等技术研究了该催化剂的结构形态,结果表明：所研制的ＳＯ４＾２－／ＣｏＦｅ２Ｏ４２催化剂为晶态纳米粒子（〈５０ｎｍ）,比表面积很大（１５７ｍ＾２．ｇ＾－１）,ＳＯ４＾２－与氧化物的金属离子呈无机齿螯合状配位化合物的结合形式。以乙酸乙酯合成为模型反应考究了该催化剂的催化活     

Evolution and characterization of fluorite-like nano-SrBi2Nb2O9 phase in the SrO-Bi2O3-Nb2O5-Li2B4O7 glass system

Transparent glasses of various compositions in the system (100−x)Li₂B₄O₇−x(SrO-Bi₂O₃-Nb₂O₅) (where x=10, 20, 30, 40, 50 and 60, in molar ratio) were fabricated via splat quenching technique. The glassy nature of the as-quenched samples was established by differential thermal analyses. X-ray powder diffraction (XRD) and transmission electron microscopic studies confirmed the amorphous nature of the as-quenched and crystallinity in the heat-treated samples. Fluorite phase formation prior to the perovskite SrBi₂Nb₂O₉ phase was analyzed by both the XRD and high-resolution transmission electron microscopy. Dielectric and the optical properties (transmission, optical band gap and Urbach energy) of these samples have been found to be compositional dependent. Refractive index was measured and compared with the values predicted by Wemple-Didomemenico and Gladstone-Dale relations. The glass nanocomposites comprising nanometer-sized crystallites of fluorite phase were found to be nonlinear optic active.     

Reduction of Eu to Eu in MAl2Si2O8 (M=Ca, Sr, Ba) in air condition

In general, the reduction of Eu³⁺ to Eu²⁺ in solids needs an annealing process in a reducing atmosphere. In this paper, it is of great interest and importance to find that the reduction of Eu³⁺ to Eu²⁺ can be realized in a series of alkaline-earth metal aluminum silicates MAl₂Si₂O₈ (M=Ca, Sr, Ba) just in air condition. The Eu²⁺-doped MAl₂Si₂O₈ (M=Ca, Sr, Ba) powder samples were prepared in air atmosphere by Pechini-type sol-gel process. It was found that the strong band emissions of 4f⁶5d¹-4f⁷ from Eu²⁺ were observed at 417, 404 and 373 nm in air-annealed CaAl₂Si₂O₈, SrAl₂Si₂O₈ and BaAl₂Si₂O₈, respectively, under ultraviolet excitation although the Eu³⁺ precursors were employed. In addition, under low-voltage electron beam excitation, Eu²⁺-doped MAl₂Si₂O₈ also shows strong blue or ultraviolet emission corresponding to 4f⁶5d¹-4f⁷ transition. The reduction mechanism from Eu³⁺ to Eu²⁺ in these compounds has been discussed in detail.     

SiO2负载氮掺杂TiO2可见光响应光催化剂的制备及性能

以四氯化钛为钛源,尿素为氮源,采用液相水解-沉淀法制得SiO2负载N掺杂TiO2可见光响应TiO2-xNy/SiO2光催化剂(TSN)。以苯酚为模型物,考察了TSN在可见光区、紫外光区及太阳光下的光催化活性,以及催化剂的使用寿命、分离性能。采用XPS、FTIR、UV-Vis DRS、XRD、TEM和低温氮物理吸附等对催化剂的结构进行表征。结果表明,N以阴离子形式进入TiO2体相并置换晶格中的O,适量N掺杂的TSN在紫外光区、可见光区及太阳光下均表现出较高的活性。SiO2与TiO2界面间有Ti-O-Si键形成,结合牢固。N掺杂在TiO2表面生成Ti-O-N键,形成新的能级结构,使催化剂的吸收红移至450~500 nm,诱发TiO2可见光催化活性。SiO2负载可减小TiO2颗粒平均尺寸,增加催化剂比表面积;同时SiO2负载还可改善催化剂的分离性能,提高催化剂使用寿命。     

Magnetic diphase nanostructure of ZnFe2O4/γ-Fe2O3

Magnetic diphase nanostructures of ZnFe₂O₄/γ-Fe₂O₃ were synthesized by a solvothermal method. The formation reactions were optimized by tuning the initial molar ratios of Fe/Zn. All samples were characterized by X-ray diffraction, thermogravimetric analysis, infrared spectroscopy, and Raman spectra. It is found that when the initial molar ratio of Fe/Zn is larger than 2, a diphase magnetic nanostructure of ZnFe₂O₄/γ-Fe₂O₃ was formed, in which the presence of ZnFe₂O₄ enhanced the thermal stability of γ-Fe₂O₃. Further increasing the initial molar ratio of Fe/Zn larger than 6 destabilized the diphase nanostructure and yielded traces of secondary phase α-Fe₂O₃. The grain surfaces of diphase nanostructure exhibited a spin-glass-like structure. At room temperature, all diphase nanostructures are superparamagnetic with saturation magnetization being increased with γ-Fe₂O₃ content.     

偏硼酸锶催化剂光催化还原CO2合成CH4

采用溶胶-凝胶法制备出偏硼酸锶(SrB₂O₄)光催化剂. 紫外光催化还原CO₂合成CH₄(在液相水中)的实验证明: SrB₂O₄催化剂的光催化活性略高于TiO₂(P25). 利用X射线电子衍射谱(XRD)、傅里叶变换红外(FTIR)光谱、X射线光电子能谱(XPS)、透射电子显微镜(TEM)、荧光(PL)光谱和紫外-可见(UV-Vis)漫反射吸收光谱等技术, 研究了SrB₂O₄ 催化剂的晶体结构、形貌和能带结构. 结果表明: SrB₂O₄ 的价带为2.07 V (vs normalhydrogen electrode (NHE)), 低于(H₂O/H⁺)的氧化还原电位E_redox^o (0.82 V (vs NHE)); 而导带为-1.47 V (vsNHE), 高于(CO₂/CH₄)的氧化还原电位E_redox^o (-0.24 V (vs NHE)). 因此, SrB₂O₄催化剂可以有效地光催化还原CO₂生成CH₄. 与TiO₂(P25)相比, SrB₂O₄催化剂具有相对较高导带, 光生电子的还原能力强于TiO₂(P25), 更有利于CH₄的生成, 从而决定了SrB₂O₄催化剂光催化还原CO₂合成CH₄具有较高的光催化活性.     

Synthesis, structural characterization and optical properties of a new cesium aluminum borate, Cs2Al2B2O7

A new borate, Cs₂Al₂B₂O₇, was synthesized by solid-state reaction. It crystallizes in the monoclinic space group P2₁/c with a=6.719(1) Å, b=7.121(1) Å, c=9.626(3) Å, β=115.3(1)°, and Z=2. In the structure, two AlO₄ tetrahedra and two BO₃ planar triangles are connected alternately by corner-sharing to from nearly planar [Al₂B₂O₁₀] rings, which are further linked via common O1 atom to generate layers in the bc plane. These layers then share the O3 atoms lying on a center of inversion to form a three-dimensional framework with Cs atoms residing in the channels. The IR spectrum confirms the presence of both BO₃ and AlO₄ groups and the UV-vis-IR diffuse reflectance spectrum indicates a band gap of about 4.13(2) eV.     

Visible-light photocatalytic activity of the metastable Bi20TiO32 synthesized by a high-temperature quenching method

Metastable Bi₂₀TiO₃₂ samples were synthesized by a high-temperature quenching method using α-Bi₂O₃ and anatase TiO₂ as raw materials. The photocatalytic activity of the as-prepared samples was measured with the photodegradation of methyl orange at room temperature under visible light irradiation. The Bi₂₀TiO₃₂ samples exhibited good absorption in the visible light region with a band gap of about 2.38 eV and the band structure of Bi₂₀TiO₃₂ was studied. Photodegradation against methyl orange was much better than α-Bi₂O₃ prepared by the same way. The photocatalytic activity of Bi₂₀TiO₃₂ samples is supposed to be associated with the hybridized Bi 6s and O 2p orbitals. In addition, the dispersive characteristic of Bi 6s orbital in the hybridized valence band facilitates the mobility of the photogenerated carriers and hampers their recombination.     

A new structure type of phosphate: Crystal structure of Na2Zn5(PO4)4

A new compound, Na₂Zn₅(PO₄)₄, was identified in the system ZnONa₂OP₂O₅ and high-quality crystal was obtained by the melt method. The crystal structure of this compound was solved by direct method from single crystal X-ray diffraction data. The structure was then refined anisotropically using a full-matrix least square refinement on F² and the refinement converged to R₁=0.0233 and wR₂=0.0544. This compound crystallizes in the orthorhombic system with space group Pbcn, lattice parameters a=10.381(2) Å, b=8.507(1) Å, c=16.568(3) Å and Z=4. The structure is made up of 3D [Zn₅P₄O₁₆]_n²ⁿ⁻ covalent framework consisting of [Zn₄P₄O₁₆]_n⁴ⁿ⁻ layers. The powder diffraction pattern of Na₉Zn₂₁(PO₄)₁₇ is explained by simulating a theoretical pattern with NaZnPO₄ and Na₂Zn₅(PO₄)₄ in the molar ratio of 1:4 and then by Rietveld refinement of experimental pattern. Na₂Zn₅(PO₄)₄ melts congruently at 855 °C and its conductivity is 5.63×10⁻⁹ S/cm.     

一锅法制备S型异质结光催化剂Fe2O3/Fe2TiO5及其高效降解有机污染物性能

首次采用简单的一锅法制备了Fe₂O₃/Fe₂TiO₅异质结纳米材料。构建S型异质结后,与纯的Fe₂O₃和Fe₂TiO₅相比,Fe₂O₃/Fe₂TiO₅复合材料表现出更高的光催化降解速率和效率。经过2.5 h的光照后,Fe₂O₃/Fe₂TiO₅可以降解接近100%的亚甲基蓝（MB）。在Fe₂O₃/Fe₂TiO₅复合材料中,Fe₂O₃和Fe₂TiO₅之间形成了内建电场,可以促进光生电子-空穴对的分离。因此,具有更高能量的Fe₂TiO₅导带中的电子和具有更高能量的Fe₂O₃价带中的空穴可以得到有效的保留,从而使它们更加有效地扩散到催化剂表面,并参加降解反应。此外,Fe₂O₃/Fe₂TiO₅复合材料具有很好的光催化稳定性。     

Electrochemical properties and synthesis of LiAl0.05Mn1.95O3.95F0.05 by a solution-based gel method for lithium secondary battery

The cathode materials, LiMn₂O₄, LiAl_0.05Mn_1.95O₄ and LiAl_0.05Mn_1.95O_3.95F_0.05 were firstly prepared by a simple solution-based gel method using the mixture of acetate and ethanol as the chelating agent. The synthesized samples were investigated by X-ray diffraction, scanning electronic microscope and differential and thermal analysis. The as-prepared powders were used as positive materials for lithium-ion battery, whose discharge capacity and cycle voltammogram properties were examined. The results revealed that LiAl_0.05Mn_1.95O_3.95F_0.05 synthesized by the solution-based gel method had higher initial capacity than LiAl_0.05Mn_1.95O₄ and better capacity retention rate (92%) than that of LiAl_0.05Mn_1.95O₄ and LiMn₂O₄, which revealed that Al and F dual-doped LiMn₂O₄ could gain better electrochemical properties of LiMn₂O₄ than only the Al-doped LiMn₂O₄.     

Syntheses and characterization of two oxoborates, (Pb3O)2(BO3)2MO4 (M=Cr, Mo)

Two oxoborates, (Pb₃O)₂(BO₃)₂MO₄ (M=Cr, Mo), have been prepared by solid-state reactions below 700 °C. Single-crystal XRD analyses showed that the Cr compound crystallizes in the orthorhombic group Pnma with a=6.4160(13) Å, b=11.635(2) Å, c=18.164(4) Å, Z=4 and the Mo analog in the group Cmcm with a=18.446(4) Å, b=6.3557(13) Å, c=11.657(2) Å, Z=4. Both compounds are characterized by one-dimensional chains formed by corner-sharing OPb₄ tetrahedra. BO₃ and CrO₄ (MoO₄) groups are located around the chains to hold them together via Pb–O bonds. The IR spectra further confirmed the presence of BO₃ groups in both structures and UV–vis diffuse reflectance spectra showed band gaps of about 1.8 and 2.9 eV for the Cr and Mo compounds, respectively. Band structure calculations indicated that (Pb₃O)₂(BO₃)₂MoO₄ is a direct semiconductor with the calculated energy gap of about 2.4 eV.     

Fluorescence and phosphorescence properties of the low temperature forms of the MAl2Si2O8:Eu (M=Ca, Sr, Ba) compounds

The fluorescence and phosphorescence properties of Europium-doped MAl₂Si₂O₈ (M=Ca, Sr, Ba) are reinvestigated and discussed on the basis of the propensity of an activator to agglomerate with an oxygen vacancy. Due to a stronger attraction of the anion vacancy towards Eu²⁺ cations going from BaAl₂Si₂O₈ to SrAl₂Si₂O₈ and CaAl₂Si₂O₈ host lattices, the interpretation of the fluorescence spectra turns out to be less trivial in the Ca and Sr host lattices than in the Ba one and requests the account for Eu²⁺ cations lying at alkaline-earth sites with or without vacancy in their neighborhood. Phosphorescence in these compounds is highlighted.     

Li2O-TiO2-SiO2-P2O5和Li2O-TiO2-Al2O3-P2O5体系锂离子固体电解质的制备及性能研究

一些具有NASICON型网格结构的固体电解质具有高的电导率和好的稳定性,NASICON的意思是Na Super Ionic Conductor[1]。当NaZr2(PO4)3中P5 被Si4 部分取代时便可以得到具有NASICON结构的Na1 xZr2SixP3-xO12体系,其具有高的钠离子电导率。然而有相同结构的Li1 xZr2SixP3-xO12体系的离子电导率却很低,这是因为Li 半径太小,而NASICON三维网格结构的离子通道太大,两者不匹配而使电导率下降[2]。但当LiZr2(PO4)3中Zr4 被离子半径小些的Ti4 取代,所得LiTi2(PO4)3的通道就与Li 半径相匹配,适合于锂离子的迁移,从而使其电导率…     

Structure Study of Bi2.5Na0.5Ta2O9 and Bi2.5Nam−1.5NbmO3m+3 (m=2-4) by Neutron Powder Diffraction and Electron Microscopy

The crystal structures of Bi_2.5Na_0.5Ta₂O₉ and Bi_2.5Na_m-1.5Nb_mO_3m+3 (m=3,4) have been investigated by the Rietveld analysis of their neutron powder diffraction patterns (λ=1.470 Å). These compounds belong to the Aurivillius phase family and are built up by (Bi₂O₂)²⁺ fluorite layers and (A_m-1B_mO_3m+1)^2- (m=2-4) pseudo-perovskite slabs. Bi_2.5Na_0.5Ta₂O₉ (m=2) and Bi_2.5Na_2.5Nb₄O₁₅ (m=4) crystallize in the orthorhombic space group A2₁am, Z=4, with lattice constants of a=5.4763(4), b=5.4478(4), c=24.9710 (15) and a=5.5095(5), b=5.4783(5), c=40.553(3) Å, respectively. Bi_2.5Na_1.5Nb₃O₁₂ (m=3) has been refined in the orthorhombic space group B2cb, Z=4, with the unit-cell parameters a=5.5024(7), b=5.4622(7), and c=32.735(4) Å. In comparison with its isostructural Nb analogue, the structure of Bi_2.5Na_0.5Ta₂O₉ is less distorted and bond valence sum calculations indicate that the Ta-O bonds are somewhat stronger than the Nb-O bonds. The cell parameters a and b increase with increasing m for the compounds Bi_2.5Na_m-1.5Nb_mO_3m+3 (m=2-4), causing a greater strain in the structure. Electron microscopy studies verify that the intergrowth of mixed perovskite layers, caused by stacking faults, also increases with increasing m.     

Synthesis, crystal structure, infrared and Raman spectra of Sr4Cu3(AsO4)2(AsO3OH)4·3H2O and Ba2Cu4(AsO4)2(AsO3OH)3

The two new compounds, Sr₄Cu₃(AsO₄)₂(AsO₃OH)₄·3H₂O (1) and Ba₂Cu₄(AsO₄)₂(AsO₃OH)₃(2), were synthesized under hydrothermal conditions. They represent previously unknown structure types and are the first compounds synthesized in the systems SrO/BaO-CuO-As₂O₅-H₂O. Their crystal structures were determined by single-crystal X-ray diffraction [space group C2/c, a=18.536(4) Å, b=5.179(1) Å, c=24.898(5) Å, β=93.67(3)°, V=2344.0(8) Å³, Z=4 for 1; space group P4₂/n, a=7.775(1) Å, c=13.698(3) Å, V=828.1(2) Å³, Z=2 for 2]. The crystal structure of 1 is related to a group of compounds formed by Cu²⁺-(XO₄)³⁻ layers (X=P⁵⁺, As⁵⁺) linked by M cations (M=alkali, alkaline earth, Pb²⁺, or Ag⁺) and partly by hydrogen bonds. In 1, worth mentioning is the very short hydrogen bond length, D···A=2.477(3) Å. It is one of the examples of extremely short hydrogen bonds, where the donor and acceptor are crystallographically different. Compound 2 represents a layered structure consisting of Cu₂O₈ centrosymmetric dimers crosslinked by As1φ₄ tetrahedra, where φ is O or OH, which are interconnected by Ba, As2 and hydrogen bonds to form a three-dimensional network. The layers are formed by Cu₂O₈ centrosymmetric dimers of CuO₅ edge-sharing polyhedra, crosslinked by As1O₄ tetrahedra. Vibrational spectra (FTIR and Raman) of both compounds are described. The spectroscopic manifestation of the very short hydrogen bond in 1, and ABC-like spectra in 2 were discussed.