共沉淀法制备六方相ITO纳米粉体及其光电性能

以金属In、SnCl_4·5H_2O为原料、尿素为沉淀剂,采用共沉淀法加入(NH_4)_2SO_4,制备出六方相ITO纳米粉体。通过XRD、TEM、四探针电阻仪、荧光光谱仪以及XPS,研究了ITO粉体的晶型、颗粒形貌、电性能以及光性能。结果表明:加入(NH_4)_2SO_4后,ITO粉体形貌由类菱面体和类球形混合体转变为类球形;不加(NH_4)_2SO_4时晶型为立方相结构,当(NH_4)_2SO_4与铟的物质的量之比为1∶3.45和1∶1.73时粉体晶型转变为六方相结构,继续添加(NH_4)_2SO_4晶型又转变为立方相结构。立方相ITO粉体的电阻率较低为0.64Ω·cm,六方相ITO粉体在相同激发波长下,发射光强度相对较高。     

具有不同形貌和择优取向的MxWO3·xH2O粉晶的制备与表征

采用沉淀结合渗析的方法，以钨酸钠、钨酸铵为原料，制备了不同形貌、具有择优取向的M_xWO₃·xH₂O(M=Na⁺，NH₄⁺，x<1)粉晶，利用SEM、XRD、TG、IR、XPS等手段对粉体进行表征，考察了不同渗析时间和焙烧温度对粉晶形貌、晶化程度及结构转变的影响。结果表明，长时间渗析后粉体的晶化程度明显提高，并沿(010)晶面方向择优生长，形貌由不规则形变为梭形和蝴蝶形。经空气气氛400 ℃焙烧后，Na_xWO₃·xH₂O和(NH₄)_xWO₃·xH₂O粉晶均转变为沿(200)晶面方向择优生长的立方青铜相，且形貌也发生改变。     

Na4Ca(SO4)3复盐高温合成及温度对晶体形貌的影响

用高温合成法制备出硫酸钙复盐Na₄Ca(SO₄)₃，利用差热分析、X射线衍射、扫描电子显微分析等现代测试仪器研究了该复盐的反应历程。研究结果表明，其反应过程按CaSO₄+Na₂SO₄→(Na_0.8Ca_0.1)₂SO₄→Na₄Ca(SO₄)₃进行。Na₄Ca(SO₄)₃为高温稳定相，其最佳合成温度为800 ℃～1 100 ℃。育晶温度及时间对复盐形貌有明显影响，在1 000 ℃保温2 h后转到945 ℃育晶5 h,晶体生长较好。     

Ba2SbInO6双钙钛矿的水热合成和表征

利用水热晶化法制备了Ba₂SbInO₆纯相，并通过XRD、SEM、IR、XPS和ICP等方法，对产物的物相、形貌、结构和组成进行了表征。初步结构表征结果表明，产物可能为B位离子无序排列的立方钙钛矿结构，空间群为Pm3m，晶胞参数为a=0.4132 mm。产物粉末呈现立方晶型，粒度约为0.5～2 μm。     

水热重结晶法制备四方相纳米Ba0.9Ca0.1TiO3晶体的研究

采用水热重结晶法对低温液相法制备的Ba_0.9Ca_0.1TiO₃(B_0.9C_0.1T)浆料进行220 ℃, 3 h的水热处理, 成功制备了四方相B_0.9C_0.1T纳米粉体. 并对水热重结晶和未水热处理的两种粉体进行了TEM, XRD, Raman, FT-IR, TG和介电性能的表征. 研究表明, 经水热重结晶后的B_0.9C_0.1T粉体体系发生从顺电立方相向铁电四方相的转变, 羟基缺陷以及CO₃^2－杂质显著减少, 粉体形貌由外边缘毛躁的球形转变为四边形. 并发现羟基缺陷的减少是影响体系相转变的关键因素.     

水热重结晶法制备四方相纳米Ba0.9Ca0.1TiO3晶体的研究

采用水热重结晶法对低温液相法制备的Ba_0.9Ca_0.1TiO₃(B_0.9C_0.1T)浆料进行220 ℃, 3 h的水热处理, 成功制备了四方相B_0.9C_0.1T纳米粉体. 并对水热重结晶和未水热处理的两种粉体进行了TEM, XRD, Raman, FT-IR, TG和介电性能的表征. 研究表明, 经水热重结晶后的B_0.9C_0.1T粉体体系发生从顺电立方相向铁电四方相的转变, 羟基缺陷以及CO₃^2－杂质显著减少, 粉体形貌由外边缘毛躁的球形转变为四边形. 并发现羟基缺陷的减少是影响体系相转变的关键因素.     

一种SO2固定及用于制备BaSO3或BaSO4的方法

在常温常压下,由乙二胺（EDA）和乙二醇及其衍生物（EGs）组成的混合体系可捕集SO₂并转化为一种SO₂储集材料（SO₂SM）。EDA+EGs体系呈现了强的捕集性能（0.364~0.662 g_SO2·gabsorbent^-1）。FTIR,XPS和XRD结果确证了SO₂SM为一种烷基亚硫酸盐。以EG-SO₂SM为原料制备具有多种形貌的BaSO₃或BaSO₄,在此过程中,EG-SO₂SM不仅提供了原材料,而且可以释放EDA和EG用作表面活性剂,调控晶体的结晶化过程。     

一种SO2固定及用于制备BaSO3或BaSO4的方法

在常温常压下,由乙二胺（EDA）和乙二醇及其衍生物（EGs）组成的混合体系可捕集SO₂并转化为一种SO₂储集材料（SO₂SM）。EDA+EGs体系呈现了强的捕集性能（0.364~0.662 g_SO2·g_absorbent^-1）。FTIR,XPS和XRD结果确证了SO₂SM为一种烷基亚硫酸盐。以EG-SO₂SM为原料制备具有多种形貌的BaSO₃或BaSO₄,在此过程中,EG-SO₂SM不仅提供了原材料,而且可以释放EDA和EG用作表面活性剂,调控晶体的结晶化过程。     

H2SO4处理的Nb2O5/γ -Al2O3催化剂表面酸性与催化性能研究

用Hammett指示剂法、红外光谱（IR）、示差扫描量热-热重法（DSC-TG）和微型催化反应装置等研究了H₂SO₄处理的负载型Nb₂O₅/γ-Al₂O₃催化剂表面酸性和催化异丁烯（IB）与异丁醛（IBA）反应生成2，5-二甲基-2，4-己二烯（DMHD）的催化性能。结果表明随所用H₂SO₄浓度增加，Nb₂O₅/γ-Al₂O₃催化剂表面酸性增强，B酸量增加，L酸量先增加后下降。经H₂SO₄处理的Nb₂O₅/γ-Al₂O₃催化剂的催化活性明显增加，但当H₂SO₄浓度超过0.05 mol·L^-1时催化活性又急剧下降，这可能是因为在H₂SO₄处理的催化剂表面形成的强酸中心上，产物分子进一步转化为积炭且封闭催化剂活性表面，导致催化活性下降。     

自生核壳结构MnO2的电磁性能及其生长机理研究

采用水热合成法,以(NH₄)₂S₂O₈作氧化剂,以MnSO₄·H₂O为锰源,制备了自生核壳结构MnO₂粉体。利用X射线粉末衍射、扫描电子显微镜、透射电子显微镜、振动样品磁强计和热重分析对产物进行成分、晶型、形貌、磁性能和热稳定性分析,并通过电磁参数的测试对产物的电磁特性以及电磁波损耗机制进行阐述。结果表明：所制得粉体是直径3～5 μm的核壳结构海胆球形MnO₂,其复介电常数实部在8.40～5.35,虚部在2.66～2.07;复磁导率实部和虚部都很小,分别在1.04～1.14和0.03～0.21范围内。最后分析了核壳结构MnO₂的电磁波损耗机制以及热稳定性能。     

Singlet-triplet energy separations in divalent five-membered cyclic conjugated C5H3X, C4H3SiX, C4H3GeX, C4H3SnX, and C4H3PbX (X = H, F, Cl, and Br)

Singlet-triplet energy gaps in cyclopenta-2,4-dienylidene, as well as its 2- or 3-halogenated derivatives, are compared and contrasted with their sila, germa, stana, and plumba analogues; at HF/6-31G* and B3LYP/ 6-311++G(3df, 2p) levels of theory. Energy gaps (ΔG_t-s), between triplet (t) and singlet (s) states, appear linearly proportional to: (i) the size of the group 14 divalent element (M = C, Si, Ge, Sn and Pb), (ii) the angle ∠C-M-C, and (iii) the ΔG_(LUMO-HOMO) of the singlet state involved. The magnitude of ΔG_t-s, for each 2- and/or 3-substituted species studied, increases with an order of: carbenes < silylenes < germylenes < stanylenes < plumbylenes. This order reverses for the barriers of the ring puckering. The puckering occurs with more ease for every singlet, compared to its corresponding triplet form.Regardless of the group 14 element (M) employed, every 3-halo-substituted species is more stable than the corresponding 2-halo-substituted isomer. For M = Pb, Sn and/or Ge; 3-halo-substituted species have higher ΔG_t-s than their corresponding 2-halo-substituted analogues. For M = Si, similar ΔG_t-s are found for 2- and 3-halogenated isomers. For M = C, 3-halo-substituted species have lower ΔG_t-s than their corresponding 2-halo-substituted analogues.Every cyclic singlet has a larger ∠C-M-C angle, than its corresponding cyclic triplet state, except for 3-halosilacyclopenta-2,4-dienylidenes where triplet has a larger ∠C-M-C angle than its corresponding singlet state.     

Electronic structures of the boron cage molecules B4H4, B4Cl4 and B4F4

Ab initio calculations have been performed on B₄H₄, B₄Cl₄ and B₄F₄ in order to aid our understanding of the bonding in these compounds, which is presumably based on a tetrahedral boron cage. This cage has only 8 electrons and so is less than that expected on the basis of the usual framework electron counting rules. Basis sets with polarisation functions were used at the SCF, CI and CPF levels of theory to confirm that the T _d structures are indeed more stable than the D _4h ones. Davidson-Roby population analyses were able to show that many factors, including 3-centre 2-electron bonding and backbonding from the ligand to the boron cage, are of importance in determining the relative stability of the three compounds, of which B₄Cl₄ is the only one that has yet been observed experimentally.     

On the crystal chemistry of three copper(II)-arsenates: Cu3(AsO4)2-III,Na4Cu(AsO4)2, and KCu4(AsO4)3

The three copper(II)-arsenates were synthesized under hydrothermal conditions; their crystal structures were determined by single-crystal X-ray diffraction methods:Cu₃(AsO₄)₂-III:a=5.046(2) Å,b=5.417(2) Å,c=6.354(2) Å, =70.61(2)°, =86.52(2)°, =68.43(2)°,Z=1, space group ,R=0.035 for 1674 reflections with sin / 0.90 Å^–1.Na₄Cu(AsO₄)₂:a=4.882(2) Å,b=5.870(2) Å,c=6.958(3) Å, =98.51(2)°, =90.76(2)°, =105.97(2)°,Z=1, space group ,R=0.028 for 2157 reflections with sin / 0.90 Å^–1.KCu₄(AsO₄)₃:a=12.234(5) Å,b=12.438(5) Å,c=7.307(3) Å, =118.17(2)°,Z=4, space group C2/c,R=0.029 for 1896 reflections with sin / 0.80 Å^–1.Within these three compounds the Cu atoms are square planar [4], tetragonal pyramidal [4+1], and tetragonal bipyramidal [4+2] coordinated by O atoms; an exception is the Cu(2)^[4+1] atom in Cu₃(AsO₄)₂-III: the coordination polyhedron is a representative for the transition from a tetragonal pyramid towards a trigonal bipyramid. In KCu₄(AsO₄)₃ the Cu(1)^[4]O₄ square and the As(1)O₄ tetrahedron share a common O—O edge of 2.428(5) Å, resulting in distortions of both the CuO₄ square and the AsO₄ tetrahedron. The two Na atoms in Na₄Cu(AsO₄)₂ are [6] coordinated, the K atom in KCu₄(AsO₄)₃ is [8] coordinated by O atoms.Die drei Kupfer(II)-Arsenate wurden unter Hydrothermalbedingungen gezüchtet und ihre Kristallstrukturen mittels Einkristall-Röntgenbeugungsmethoden ermittelt:Cu₃(AsO₄)₂-III:a = 5.046(2) Å,b = 5.417(2) Å,c = 6.354(2) Å, = 70.61 (2)°, = 86.52(2)°, = 68.43(2)°,Z = 1, Raumgruppe ,R = 0.035 für 1674 Reflexe mit sin / 0.90 Å^–1.Na₄Cu(AsO₄)₂:a = 4.882(2) Å,b = 5.870(2) Å,c = 6.958(3) Å, = 98.51(2)°, = 90.76(2)°, = 105.97(2)°,Z = 1, Raumgruppe ,R = 0.028 für 2157 Reflexe mit sin / 0.90 Å^–1.KCu₄(AsO₄)₃:a = 12.234(5) Å,b = 12.438(5) Å,c = 7.307(3) Å, = 118.17(2)°,Z = 4, Raumgruppe C2/c,R = 0.029 für 1896 Reflexe mit sin / 0.80 Å^–1.Die Cu-Atome in diesen drei Verbindungen sind durch O-Atome quadratisch planar [4], tetragonal pyramidal [4 + 1] und tetragonal dipyramidal [4 + 2]-koordiniert; eine Ausnahme ist das Cu(2)^{[4 + 1]}-Atom in Cu₃(AsO₄)₂-III: Das Koordinationspolyeder stellt einen Vertreter des Übergangs von einer tetragonalen Pyramide zu einer trigonalen Dipyramide dar. In KCu₄(AsO₄)₃ haben das Cu(1)^[4]O₄-Quadrat und das As(1)O₄-Tetraeder eine gemeinsame O—O-Kante von 2.428(5) Å, was eine Verzerrung der beiden Koordinationsfiguren CuO₄-Quadrat und AsO₄-Tetraeder bedingt. Die zwei Na-Atome in Na₄Cu(AsO₄)₃ sind durch O-Atome [6]-koordiniert, das K-Atom in KCu₄(AsO₄)₃ ist [8]-koordiniert.

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Zur Kristallchemie dreier Kupfer (II)-Arsenate: Cu₃(AsO₄)₂-III, Na₄Cu(AsO₄)₂ und KCu₄(AsO₄)₃

     

Energetics of formation of alkali and ammonium cobalt and zinc phosphate frameworks

Alkali and ammonium cobalt and zinc phosphates show extensive polymorphism. Thermal behavior, relative stabilities, and enthalpies of formation of KCoPO₄, RbCoPO₄, NH₄CoPO₄, and NH₄ZnPO₄ polymorphs are studied by differential scanning calorimetry, high-temperature oxide melt solution calorimetry, and acid solution calorimetry.α-KCoPO₄ and γ-KCoPO₄ are very similar in enthalpy. γ-KCoPO₄ slowly transforms to α-KCoPO₄ near 673 K. The high-temperature phase, β-KCoPO₄, is 5-7 kJ mol⁻¹ higher in enthalpy than α-KCoPO₄ and γ-KCoPO₄. HEX phases of NH₄CoPO₄ and NH₄ZnPO₄ are about 3 kJ mol⁻¹ lower in enthalpy than the corresponding ABW phases. There is a strong relationship between enthalpy of formation from oxides and acid-base interaction for cobalt and zinc phosphates and also for aluminosilicates with related frameworks. Cobalt and zinc phosphates exhibit similar trends in enthalpies of formation from oxides as aluminosilicates, but their enthalpies of formation from oxides are more exothermic because of their stronger acid-base interactions. Enthalpies of formation from ammonia and oxides of NH₄CoPO₄ and NH₄ZnPO₄ are similar, reflecting the similar basicity of CoO and ZnO.     

The compounds KAs4O6 X (X=Cl,Br, I) and NH4As4O6 X (X=Br,I): Hydrothermal syntheses and structure determinations

The crystal structures of five isotypic hexagonal compounds with general formulaMAs₄O₆ X [M=K, NH₄;X=Cl, Br, I; space group: P622;Z=1] were determined from 370 single crystal X-ray data and refined toR values <0.05. The structure type is characterized by neutral charged [As₂O₃] sheets arranged parallel (00.1). The As atoms of neighbouring two sheets point to each other and the sheets are combined by interlayeredM andX atoms, respectively. TheM atoms are coordinated to twelve oxygen atoms, theX atoms are coordinated to twelve arsenic atoms. In both cases the coordination polyhedron is a hexagonal prism. The compounds were synthesized by thermal treatments of cubic As₂O₃ and potassium or ammonium haloids in a saturated aqueous solution of potassium acetate resp. ammonia [500 K, saturation vapour pressure].

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Die Verbindungen KAs₄O₆ X (X=Cl, Br, I) und NH₄As₄O₆ X (X=Br, I): Hydrothermalsynthese und Strukturbestimmung

Zusammenfassung Die Kristallstrukturen der fünf isotypen hexagonalen Verbindungen mit der allgemeinen FormelMAs₄O₆ X [M=K, NH₄;X=Cl, Br, I; Raumgruppe: P622;Z=1] wurden anhand von 370 Einkristall-Röntgendaten bestimmt und aufR-Werte <0.05 verfeinert. Der Strukturtyp ist ausgezeichnet durch neutrale [As₂O₃]-Schichten, die parallel (00.1) angeordnet sind. Die As-Atome zweier benachbarter Schichten weisen jeweils aufeinander zu, und die Schichten selbst werden durch zwischengelagerteM- bzw.X-Atome verbunden. DieM-Atome werden jeweils von zwölf O-Atomen, dieX-Atome von zwölf As-Atomen umgeben. Das Koordinationspolyeder ist in beiden Fällen ein hexagonales Primsa. Die einzelnen Verbindungen wurden unter Hydrothermalbedingungen aus kubischem As₂O₃ und dem jeweiligen Kalium- oder Ammoniumhalogenid in einer gesättigten wäßrigen Lösung von Kaliumacetat bzw. Ammoniak synthetisiert (500 K, Sättigungsdampfdruck).

     

Near infrared study of aqueous lanthanide perchlorates

The near infrared spectra of water in aqueous solutions of La(ClO₄)₃, Pr(ClO₄)₃, Nd(ClO₄)₃, Gd(ClO₄)₃, Er(ClO₄)₃, Yb(ClO₄)₃, Lu(ClO₄)₃, and NaClO₄ have been measured in the concentration range from 0.3 to 2.5 mol-dm^–3, at 25°C. The relative contents of free OH groups in the 1.0, 1.6, and 2.2M solutions have been calculated from extinction coefficients for water at 1160 nm. They increase with increasing salt concentration and are greater in solutions of the lighter lanthanide perchlorates at any fixed molarity. The results are discussed in terms of the stoichiometry and structure of hydrated cations of trivalent lanthanides.     

Correlation between thermodynamic properties and coordination states of aqueous bivalent transition metal sulfates

The osmotic coefficients for CoSO₄, NiSO₄, CuSO₄, MnSO₄, and ZnSO₄ have been found to be approximately the same up to very highest concentrations, while they are significantly higher for MgSO₄. Negligible changes in the visible spectra of CoSO₄ and NiSO₄ induced by increasing concentration indicate little, if any, coordination of the sulfate anion, while the UV spectral effects indicate outer-sphere association. More distinct spectral effects are observed for CuSO₄. However, the free sulfate anion concentration is found to be the same in equimolal solutions of CoSO₄, NiSO₄, and ZnSO₄, and probably also in CuSO₄, while it is higher in the solutions of MgSO₄. The conclusion is drawn that the four isopiestic transition metal sulfates at any given molality are in corresponding coordination states. The general problem of correlation between thermodynamic properties of solutions and the coordination states of the dissolved salts is discussed.     

The synthesis and structural characterization of the new ternary nitrides: Ca4TiN4 and Ca5NbN5

The ternary nitrides, Ca₄TiN₄ and Ca₅NbN₅, were synthesized in sealed niobium tubes using lithium nitride as a flux at 900 and 1050 °C, respectively. The structures of both compounds were solved from single-crystal X-ray diffraction data. Ca₄TiN₄ is the first example of a calcium group IV nitride; it crystallizes in the triclinic space group (No. 2) with cell parameters a=5.9757(5) Å, b=6.0129(5) Å, c=6.0116(12) Å, α=71.565(4)°, β=79.471(4)°, γ=68.258(4)° and Z=2. Ca₄TiN₄ is isostructural with Na₄TiO₄ and contains tetrahedral TiN₄ units connected through edges and corners to CaN₄ tetrahedra and CaN₅ square pyramids. Ca₅NbN₅ crystallizes in the monoclinic space group C2/m (No. 12) with cell parameters a=11.922(7) Å, b=6.878(5) Å, c=8.936(7) Å, β=101.22(3)° and Z=4. Ca₅NbN₅ is isostructural with Ba₅NbN₅; the structure contains NbN₄ tetrahedra that share vertices with CaN₅ trigonal bipyramids.     

Interaction Between Two Similar Plane Parallel Double Layers for (NH4)2Fe(SO4)2 or (NH4)2Cu(SO4)2 Type Complex Salt Electrolytes at Positive Surface Potential

Interaction energies between two similar plane parallel double layers for (NH₄)₂Fe(SO₄)₂ or (NH₄)₂Cu(SO₄)₂ type complex salt electrolytes at positive surface potential were expanded in a power series and accurate numeral results were given for 0.1 ≤ y _e  < y ₀ ≤ 20. The general expressions were given for the interaction energies of A _ν +B _ν′ +C_ν? type complex salt electrolytes at y > 0. The interaction energies for simple salts NaCl, CaCl₂, Na₂SO₄, FeCl₃, Na₃PO₄, Mg₃(PO₄)₂, Al₂(SO₄)₃, and complex salts (NH₄)₂Fe(SO₄)₂ or (NH₄)₂Cu(SO₄)₂ at y ₀ = 1 were compared. There was hardly difference between these simple salts and this complex salt for the interaction energies. The interaction energy for complex salt (NH₄)₂Fe(SO₄)₂ was close to that for simple salt Na₃PO₄.

Supplemental files are available for this article. Go to the publisher's online edition of the Journal of Dispersion Science and Technology to view the free supplemental file.     

Molecular orbitals studies on two limiting structures of conjugated vinyl cation,C4H4F+

Nonempirical LCAO-MO-SCF calculations employing STO-3G minimal basis set have been carried out to examine the two limiting, open and bridged, structures of a conjugative fluorovinyl cation system and the interconversion of these two structures. The bridged ion is found to be 37.6 kcal/mole higher in energy than the open ion. Three pathways of converting the open ion to bridged ion were investigated. The pathway in which conjugation is preserved along the reaction profile gives the lowest energy barrier and depicts the bridged ion as a transition state.