Redox equilibrium U(IV) + 2Fe(CN) 63? ? U(VI) + 2Fe(CN) 64? in solutions of unsaturated heteropoly anions: Potentials of redox couples, stability of U(IV) complexes, reaction mechanism

The kinetics and equilibria of the reactions UO₂²⁺ + 2L + 2Fe(CN)₆⁴⁻ ⇄ UL₀ + 2Fe(CN)₆³⁻ in 0.1–1.0 M HCl solutions (ionic strength 1.0), where L is heteropoly anion of the composition P₂W₁₇O₆₁¹⁰⁻ or SiW₁₁O₃₉⁸⁻, were studied speelrophotometrically. Measurement of the redox potential of the ferri/rerrocyanide couple in acid solutions allowed estimation of the stability constants of the complxes U^IV(P₂W₁₇O₆₁)₂¹⁶⁻ and U^IV(SiW₁₁O₃₉)₂¹²⁻, equal in 1 M H⁺ solutions to 10^18.6 and 10^21.O, respectively. Accumulation of U^IVL₂ formed by reduction of UO₂²⁺ follows a first-order rate law, i.e., it involves the formation of UO₂⁺ which slowly reacts with L. The arising complex rapidly reacts with UO₂⁺. The loss of UL₂ occurs via formation of the complex of nonoxygenated U(V) with the heleropoly anion. Original Russian Text ? V.P. Shihv, A.B. Yusov. M.N. Sokolova, A.M. Fedoseev, 2008, published in Radiokhimiya, 2008, Vol. 50, No. 3, pp. 209–214.     

Influence of conditions on the potential of the couple of nonoxygenated U5+/U4+ ions bound in complexes with the P2W17O 6110? and SiW11O 398? anions

The formal potential of the couple of nonoxygenated U⁵⁺/U⁴⁺ ions bound in complexes with unsaturated heteropoly anions (HPAs) P₂W₁₇O₆₁¹⁰⁻ (I) and SiW_{11 O39}⁸⁻ (II) in 0–1 M NaNO₃ and 1 M (NaCl + HCl) in the range of pH 0.7–4.7 was measured. In 1 M NaNO₃ solutions at pH 4.7–3.0 for I and 4.3–3.9 for II, the formal potentials are constant: 0.820 and 0.730 V, respectively. They preserve approximately the same value with a decrease in pH to 0.7 in 1 M (NaCl + HCl). The potential noticeably decreases with a decrease in the NaNO₃ or NaCl concentration from 1 M to 0 (pH 4.1–4.7): to 0.09 and 0.05–0.06 V for I and II, respectively. Approximate constancy of the potential of the U⁵⁺/U⁴⁺ couple with a decrease in pH to 1 and lower distinguishes this couple from the M⁴⁺/M³⁺ couples (M = Ce, Am, Bk) whose potential appreciably grows with increasing acidity. This is due to the fact that the U⁵⁺ and M⁴⁺ ions in acid solutions remain in the form of complexes with the ratio M: HPA = 1: 2, whereas the M³⁺ ions pass into the form of 1: 1 complexes. Thus, variation of the formal potentials of all the M ^{n + 1}/M ⁿ⁺ couples in the presence of H⁺ and Na⁺ ions is associated with variation of the stability constants of the complexes M(HPA)₂, which, in turn, is caused by interaction of single-charged ions with HPA. However, the H⁺ and Na⁺ ions interact with HPA by different mechanisms and therefore affect the potential of the U⁵⁺/U⁴⁺ couple differently. Original Russian Text ? V.P. Shilov, A.B. Yusov, A.M. Fedoseev, Ph. Moisy, 2008, published in Radiokhimiya, 2008, Vol. 50, No. 5, pp. 393–396.     

Heterogeneous equilibria in aqueous solutions of uranophosphates MII(PUO6)2·nH2O (MII = Mg2+, Ca2+, Sr2+, Ba2+)

The stability of uranophosphates M^II(PUO₆)₂·nH₂O (M^II = Mg, Ca, Sr, Ba) in aqueous solutions at pH from 0 to 14 was studied. These compounds preserve their composition and structure in the interval of pH 1–11 and congruently pass into the solution within the limits of their solubility. In strongly acidic media (pH < 1), alkaline-earth metal uranophosphates transform into uranophosphoric acid HPUO₆·4H₂O. In alkaline solutions at pH > 11, the uranophosphates MII(PUO₆)₂·nH₂O irreversibly transform into diuranates. Using the methods of equilibrium thermodynamics, the solubility products and Gibbs functions of formation of alkalineearth metal uranophosphates were calculated, the solubility curves were calculated and experimentally confirmed, and the speciation diagrams of U(VI) and P(V) in solutions and in equilibrium solid phases were constructed.     

Crystal structure of a double Np(V) and Co(NH3)63+ maleate, Co(NH3)6[NpO2(HL)2(H2O)3](HL)2?H2O [L = OOC(HC)2COO]

Crystal structure of a double Np(V) and Co(NH₃) ₆ ³⁺ maleate Co(NH₃)₆[NpO₂(HL)₂(H₂O)₃](HL)₂H₂O [L = OOC(HC)₂COO] was studied. The crystal structure consists of complex anions [NpO₂(HL)₂(H₂O)₃]^–, HL^– anions, [Co(NH₃)₆]³⁺ cations, and water molecules of crystallization. Hydrogen bonds in which proton donors are water molecules and hexaamminecobalt cations link structural fragments to form a 3D network. The coordination polyhedra of the Np(V) atoms are pentagonal bipyramids whose equatorial planes are formed by oxygen atoms of two HL^– anions and three water molecules. Four crystallographically independent maleate anions were identified in the structure. Two of these anions enter into the Np(V) surrounding, and their coordination capacity is 1.Translated from Radiokhimiya, Vol. 46, No. 6, 2004, pp. 521–523.Original Russian Text Copyright © 2004 by Charushnikova, Krot, Starikova.     

State of difficultly soluble uranosilicates MIHSiUO6 ? nH2O (M + = Li+, Na+, K+, Rb+, Cs+, NH4+) in saturated aqueous solutions

The solubility of uranosilicates M^IHSiUO₆ nH₂O (M^I = Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, NH ₄ ⁺ ) in aqueous solutions at 25°C was studied experimentally. The equilibrium constants of reactions that occur at dissolution of uranosilicates in acidic and neutral solutions were calculated. The composition of the equilibrium solutions was studied. The standard Gibbs energies of formation of the compounds were calculated from the solubility data. The behavior of the uranosilicates under various conditions was predicted on the basis of the previously suggested quantitative physicochemical model of the state of the heterogeneous system crystalline uranosilicate-aqueous solution.Translated from Radiokhimiya, Vol. 46, No. 5, 2004, pp. 418–422.Original Russian Text Copyright © 2004 by Chernorukov, Nipruk, Knyazev, Pegeeva.     

Evidence for High T C Superconducting Transitions in Isolated Al 45? and Al 47? Nanoclusters

Heat capacities measured for Al₄₅⁻ and Al₄₇⁻ nanoclusters have reproducible jumps at ∼200 K. These jumps are consistent with theoretical predictions that some clusters with highly degenerate electronic states near the Fermi level will undergo a transition into a high T _C superconducting state. An analysis based on a theoretical treatment of pairing in Al₄₅⁻ and Al₄₇⁻ agrees well with the experimental data in both the value of the critical temperature and in the size and width of the jumps in the heat capacity.     

Crystal structure of uranyl μ3-oxoacetate [(UO2)3(μ3-O)2(OOCCH3)2(H2O)2]

The crystal structure of [(UO₂)₃(₃-O)₂(OOCCH₃)₂(H₂O)₂] consists of uranium coordination polyhedra (CPs) combined via common equatorial edges into ribbons, with ₃-O atoms being common for three CPs. The structure was compared with that of known complexes with ₃-oxo atoms.Translated from Radiokhimiya, Vol. 46, No. 5, 2004, pp. 396–400.Original Russian Text Copyright © 2004 by Charushnikova, Krot, Starikova.     

Optical conductivity of a superconductor withdx2?y2 symmetry

Using a simplified Eliashberg formulation in which we keep only that part of the susceptibility which is separable and of symmetry in the pairing channel and keep the isotropic part in the renormalization channel, we have calculated the ac conductivity in the superconducting state. At zero temperature, in the clean limit, we find a finite amount of absorption at any frequency, however small, although it is substantially reduced over its normal-state value. Besides this boson-assisted absorption, when impurities are added a new channel is opened up in which momentum is given up to the impurity system and absorption proceeds directly through the creation of a hole-particle pair. Born and unitary impurity scattering are considered.This research was supported in part by the Canadian Institute for Advanced Research (CIASR), by the Ontario Centre for Materials Research (OCMR), and by the Natural Sciences and Engineering Research Council o f Canada (NSERC).     

Er3+/Yb3+掺杂NaGd(WO4)2粉体的制备与发光性能

采用水热法成功制备了Er~(3+)/Yb~(3+)双掺杂的NaGd(WO_4)_2纳米粉体,研究了不同络合剂、水热温度对样品形貌和结构的影响。测量了不同Er~(3+)掺杂浓度样品的可见上转换和近红外发射光谱。结果表明:在980nm LD激发下,可观测到样品强烈的绿色上转换发光,对应Er~(3+)的~2H_(11/2)→~4I_(15/2)(530nm)和~4S_(3/2)→~4I_(15/2)(552nm)跃迁,以及较弱的红色上转换和近红外发光,分别对应Er~(3+)的~4F_(9/2)→4I15/2(656nm)和~4I_(13/2)→~4I_(15/2)(1 532nm)跃迁。且随着Er~(3+)掺杂浓度的增加,样品的上转换红绿光和1.54μm附近的近红外光均呈现出先增大后减小的趋势。样品的激发和发射光谱显示,在378nm处的激发峰最强,对应Er~(3+)的~4I_(15/2)→~4 G_(11/2)能级跃迁,最强发射峰位于552nm。根据泵浦功率与发光强度的关系可以得出,红光和绿光的发射主要为双光子吸收过程,但红光还包含了一定的单光子吸收成分。     

Effect of SiO 32? /OH? on plasma electrolytic oxidation of Ti-5Mo-4V-3Al

Plasma electrolyte oxidation (PEO) was utilized to produce thick films on titanium and Ti-5Mo-4V-3Al alloys by immersing them in various solutions of Na₂SiO₃ and KOH with different concentrations to investigate the effect of SiO₃²⁻/OH⁻ relations on the morphology and formed phases by utilizing SEM and XRD. Corrosion resistance is evaluated by open circuit potential (OCP) variation of samples in NaCl 3.5% and potentiodynamic polarization. The results show that the unstable film is formed by using more aggressive PEO electrolyte. By increasing this ratio, pore size varied from fine to coarse and the rate of corrosion decreased and OCP became more positive. The best protective film was formed in SiO₃²⁻/OH⁻ ratio of 1.     

Thermodynamic properties of (TeO2)0.95 ? n ? z(ZnO)z(Na2O)n(Bi2O3)0.05 glasses

The heat capacity (C _p ⁰) of the tellurite glasses

Reducing ultra-low thermal expansion of β-Zr2O(PO4)2 by substitutions?

The ultra-low thermal expansion of β-Zr₂O(PO₄)₂ could still be reduced by chemical modifications, according to previous works on uranium and thorium IV homologues that evidenced a contracting effect of big cations. However, the present study shows that the only isovalent cations likely to substitute for Zr^IV or P^V are either harmful, or unstable, chemically or thermally. Furthermore, aliovalent modifications seem to be forbidden by the crystal structure of the material, leaving probably very few perspectives of improvement. Vanadium however improves significantly the crystallinity of the material and lowers the α-β transition temperature.     

过渡金属(Mn2+、Ni2+、Fe3+、Cu2+)掺杂ZnO基稀磁半导体的制备及性质

利用溶液腐蚀法制备了Mn2+、Ni2+、Fe3+、Cu2+离子掺杂的ZnO基稀磁半导体。XRD表明掺杂后的ZnO仍然保持单一的纤锌矿结构,没有任何杂质相产生。由紫外-可见光反射谱可知掺杂后吸收边发生了红移。掺杂前ZnO的带隙为3.20eV,对样品分别掺入Mn、Ni、Fe和Cu后的带隙分别为3.19eV、3.15eV、3.08eV和3.17eV。掺杂后样品的室温PL谱除了紫外发射峰外,对于Mn掺杂的样品还在蓝光区域出现了2个分别位于424nm和443nm的发射峰,Fe掺杂的样品出现了一个位于468nm的微弱发射峰,Cu掺杂的样品出现了位于469nm及535nm的很宽的发射峰。室温磁滞回线显示掺杂后样品有明显的铁磁性,掺入Mn、Ni、Fe和Cu样品的剩余磁化强度(Ms)分别为0.3902×10-3emu/cm3、0.454emu/cm3、0.372emu/cm3和0.962×10-3emu/cm3,矫顽力分别为47Oe、115.92Oe、99.33Oe和23Oe。经分析室温铁磁性来源于缺陷调制的Mn2+-Mn2+长程铁磁交换相互作用。     

FeVO4/Cu3(BTC)2(H2O)3异质结制备及光催化性能

以Cu片和1, 3, 5-苯三甲酸为原料,电化学法制备经典Cu-MOF材料Cu₃(BTC)₂(H₂O)₃,即HKUST-1,作为基底金属有机框架材料(MOFs),采用室温沉积法制备FeVO₄/HKUST-1异质结复合材料,通过XRD、SEM、BET、UV-Vis DRS等对其晶体结构、形貌、比表面积、光吸收性能等进行了表征。结果表明:FeVO₄与HKUST-1复合形成异质结后,有利于光生电子-空穴的产生和转移,对目标染料污染物罗丹明B(RhB)的降解性能显著增强。可见光照射120 min后,异质结体系中RhB的降解率可达93%,而单一FeVO₄或HKUST-1体系中仅为12%和5%。此外,对材料的组成比例进行了优化,当FeVO₄与HKUST-1摩尔比为1∶1时,制备的FeVO₄/HKUST-1复合材料具有最佳的光催化性能。进一步,考察了其循环使用的稳定性,循环5次后对RhB的降解效率仍保持在90%以上,稳定性良好。      

Ln(Ln=Gd3+,Cu+,Sm3+,Dy3+)助激活的Ca8Mg（SiO4）4Cl2∶Eu2+荧光粉的光谱特性和Eu2+的格位计算

采用高温固相法合成了掺杂Ln(Ln=Gd3+,Cu+,Sm3+,Dy3+)作助激活离子的氯硅酸镁钙荧光粉。通过X射线衍射(XRD)对Ca8Mg(SiO4)4Cl2∶Eu2+,Ln进行了表征,结果表明Ln的共掺杂并没有影响基质晶体的面心立方结构。所合成的荧光粉发射峰值位于507nm的绿光区,激发光谱在330~430nm之间均有较强吸收,与紫光InGaN芯片(395nm)相匹配。掺杂Ln作助激活剂增强了荧光粉的发光强度。借助Uitert经验公式计算出Eu2+在Ca8Mg(SiO4)4Cl2基质中占据八配位Ca(Ⅱ)格位。     

CaF2:Yb3+/Er3+/X(X= Li+, Na+, K+)近红外二区发光性能研究

利用热分解法制备了CaF₂:Yb³⁺/Er³⁺纳米颗粒,通过改变Yb³⁺和Er³⁺的掺杂浓度对其近红外二区(NIR-II)发光性能进行调节,研究结果表明,当Yb³⁺掺杂浓度为20%,Er³⁺掺杂浓度为2%时,在980 nm光源激发下,NIR-II发光性能最强,且纳米颗粒分散性良好,尺寸均匀。然后,进一步研究了不同的碱金属离子(Li⁺、Na⁺、K⁺)共掺杂对其NIR-II发光性能的影响,研究结果表明,Li⁺掺杂因不利于纳米颗粒成核导致NIR-II发光性能降低,Na⁺和K⁺掺杂均有利于NIR-II发光性能提升。相比而言,K⁺离子半径更大,更有利于破坏晶体场的局部对称性,因此,在K⁺共掺杂的情况下NIR-II发光性能最强。     

Interaction of methanesulfonic acid with actinide ions. The new complexes HImid[Np(C2O4)(CH3SO3)3(H2O)2], [NpO2(Terpy)(CH3SO3)(H2O)]·2H2O, and [UO2(CH3SO3)2(H2O)]

Complexation of methanesulfonic acid with Np(IV), Np(V), and U(VI) ions in aqueous solutions was studied. New crystalline compounds HImid[Np(C₂O₄)(CH₃SO₃)₃(H₂O)₂] (I), [NpO₂(Terpy)(CH₃SO₃)·(H₂O)]·2H₂O (II), and [UO₂(CH₃SO₃)₂(H₂O)] (III) were isolated. The absorption spectra of all the compounds in the IR, visible, and UV ranges were examined. The relationship between the composition, crystal structure, and IR and electronic absorption spectra of the complexes is discussed. Original Russian Text ? G.B. Andreev, N.A. Budantseva, I.G. Tananaev, B.F. Myasoedov, 2009, published in Radiokhimiya, 2009, vol. 51, no. 3, pp. 197–201.     

Eu3+对Na3Gd2(BO3)3∶Tb3+发光性能的影响及其能量传递

采用高温固相法制备了Na_3Gd_2(BO_3)_3∶Tb~(3+),Eu~(3+)荧光粉,并对样品的物相组成、微观形貌、发光性能和能量传递进行了分析。结果表明,Na_3Gd_(2-x)(BO_3)_3∶xTb~(3+)荧光粉在紫外和近紫外区域有较强的激发峰,在368nm波长激发下,发射光呈绿色,Tb~(3+)最佳掺杂量为x=0.04。随着在Na_3Gd_(1.96)(BO_3)_3∶0.04Tb~(3+)中掺入Eu~(3+),Tb~(3+)对Eu~(3+)产生了以电偶极-电偶极相互作用为主的能量传递,且传递效率随Eu~(3+)掺杂量的增加而逐渐增大。发射光谱中Tb~(3+)的发射峰强度逐渐减弱,而Eu~(3+)的发射峰强度逐渐增强,导致Na_3Gd_(1.96-y)(BO_3)_3∶0.04Tb~(3+),yEu~(3+)荧光粉发光颜色由绿色向橙色变化。     

Er3+/Yb3+共掺杂Ca0.5Gd(WO4)2荧光粉的发光性能和温度特性

上转换发光材料由于具备独特的热敏特性而被应用于非接触式光学温度传感技术,其中Ca_0.5Gd(WO₄)₂具有良好的热稳定性和光学特性,非常适合作为温度传感器的基质材料。本工作采用高温固相法成功制备了Er³⁺、Yb³⁺共掺杂Ca_0.5Gd(WO₄)₂荧光粉,研究了不同Yb³⁺掺杂浓度对样品物相结构、微观形貌和发光性能的影响。随着Yb³⁺掺杂浓度的增加,Ca_0.5Gd(WO₄)₂∶Er³⁺/Yb³⁺荧光粉的上转换和近红外发光强度先增加后减小,在Yb³⁺掺杂浓度为10%(摩尔分数,下同)时,发光强度均出现最大值。根据泵浦功率与发光强度的依赖关系可以得出,Er³⁺的上转换发光属于双光子吸收过程。此外,测量了样品Ca_0....