Structure and kinetic studies of U(VI)-benzamidoxime complex in non-aqueous solutions by H- and C-NMR

The structural and kinetic studies of U(VI) complex with benzamidoxime(Hba) as ligand in CD₃COCD₃ have been studied by means of ¹H and ¹³C NMR. The Hba molecule was found to coordinate to UO₂²⁺ in the form of anionic benzamidoximate (ba), and the number of ba coordinated to UO₂²⁺ was determined to be 3 by analyzing the chemical shift of ¹³C NMR signal for Hba in the presence of UO₂²⁺. The exchange rate constants(k_ex) of ba in [UO₂(ba)₃] were determined by the NMR line-broadening method. The kinetic parameters were obtained as follows: k_ex(25°C) = 3.1 × 10³s⁻¹, ΔH^≠ = 35.8 ± 3.5 KJ mol⁻¹, and ΔS^≠ = −65 ± 13.7 J K⁻¹ mol⁻¹. The UV-visible absorption spectra of solutions containing UO₂²⁺ and Hba were also measured. The molar extinction coefficient of the complex was found to be extremely large compared with those of UO₂(L)₅²⁺ (L = unidentate oxygen donor ligands) complexes. This is due to the strong electron withdrawing of UO₂²⁺ from Hba and suggests that an interaction between UO₂²⁺ and Hba is very strong. Such a high affinity of monomeric amidoxime to UO₂²⁺ reasonably explains the high adsorptibility of amidoxime resin to U(VI) species, and is considered to result in the high recovery of U(VI) species from sea water using amidoxime resin.     

Volume added surface barrier discharge plasma excited by bipolar nanosecond pulse power in atmospheric air: optical emission spectra influenced by gap distance

In this paper, volume barrier discharge with different gap distances is added on the discharge border of high-voltage electrode of annular surface barrier discharge for generating volume added surface barrier discharge (V-SBD) excited by bipolar nanosecond high-voltage pulse power in atmospheric air. The excited V-SBDs consist of surface barrier discharge (d=0 mm) and volume added surface barrier discharges (d=2 mm and 3 mm). The optical emission spectra are recorded for calculating emission intensities of N₂ (C ³Ⅱ_u →B³Π_g ) and N₂⁺ (B ²Σ_u⁺ → X ²Σ_g⁺ ), and simulating rotational and vibrational temperatures. The influences of gap distance of V-SBD on emission intensity and plasma temperature are also investigated and analyzed. The results show that d=0 mm structure can excite the largest emission intensity of N ₂ (C ³ Π_u →B ³Π_g ), while the existence of volume barrier discharge can delay the occurrence of the peak value of the emission intensity ratio of N₂⁺ (B ²Σ_u⁺ → X ²Σ_g⁺ )/N ₂(C³Π_u →B³Π_g ) during the rising period of the applied voltage pulse and weaken it during the end period. The increasing factor of emission intensity is effected by the pulse repetition rate. The d=3 mm structure has the highest threshold voltage while it can maintain more emission intensity of N₂(C³ Π _u →B ³Π_g ) than that of d=2 mm structure. The structure of d=2 mm can maintain more increasing factor than that of the d=3 mm structure with varying pulse repetition rate. Besides, the rotational temperatures of three V-SBD structures are slightly affected when the gap distance and pulse repetition rate vary. The vibrational temperatures have decaying tendencies of all three structures with the increasing pulse repetition rate.     

Structural study on uranyl ion in 1-butyl-3-methylimidazolium nonafluorobutanesulfonate ionic liquid

The structure of uranyl ion in 1-butyl-3-methylimidazolium nonafluorobutanesulfonate ionic liquid (BMINfO) has been studied with ¹H- and ³⁵Cl-NMR, Raman, and UV-visible spectroscopy. In the ¹H-NMR spectrum of the BMINfO solution prepared by dissolving UO₂(ClO₄)₂·5 6H₂O, the signal of H₂O coordinated to UO₂²⁺ was observed at 6.64 ppm at 50°C (free H₂O in BMINfO: 3.1 ppm at 50°C), suggesting that the uranyl species exists as the aquo complex, [UO₂(H₂O)_n]²⁺. The signal of the coordinated H₂O disappears with heating at 120°C for 3 h under vacuum. This indicates the dehydration from [UO₂(H₂O)_n]²⁺. On the other hand, the ³⁵Cl-NMR signal of ClO₄⁻ as the counter anion of UO₂²⁺ was observed at 1011 ppm (vs. Cl⁻ in D₂O) regardless of heating. This indicates that no ClO₄⁻ ion is in the first coordination sphere of UO₂²⁺. Furthermore, the UV-visible absorption spectra showed that the characteristic absorption bands due to UO₂²⁺ were sharpened with the dehydration. This means the simplification of the structure around UO₂²⁺. These results described above suggest that UO₂²⁺ in BMINfO has no ligand in its equatorial plane after the dehydration, i.e. UO₂²⁺ exists as a bare cation in this system.     

Et-Ph-BCTABipy的合成及其对Pd2+的萃取性能

合成了N,N′-二乙基-N,N′-二苯基-［2,2′-联吡啶］-6,6′-二硫代酰胺(Et-Ph-BCTABipy)萃取剂,并利用¹³C NMR和¹H NMR对其进行了表征;研究了相接触时间、萃取剂浓度、水相初始酸度和Pd²⁺浓度等因素对Et-Ph-BCTABipy萃取Pd²⁺性能的影响,利用摩尔比法确定了Et-Ph-BCTABipy与Pd²⁺所形成的配合物组成;同时,在Ln(Ⅲ)与Pd²⁺共存体系中研究了Et-Ph-BCTABipy对Pd²⁺的萃取选择性。结果表明：Et-Ph-BCTABipy在HNO₃体系中对Pd²⁺具有较强的萃取性能和较高的萃取选择性;萃取过程中Et-Ph-BCTABipy与Pd²⁺以1∶2的比例结合,其萃取平衡常数K_ex=3.42×10⁶。     

Et-Ph-BCTABipy的合成及其对Pd2+的萃取性能

合成了N，N′-二乙基-N，N′-二苯基-［2，2′-联吡啶］-6，6′-二硫代酰胺(Et-Ph-BCTABipy)萃取剂，并利用¹³C NMR和¹H NMR对其进行了表征；研究了相接触时间、萃取剂浓度、水相初始酸度和Pd²⁺浓度等因素对Et-Ph-BCTABipy萃取Pd²⁺性能的影响，利用摩尔比法确定了Et-Ph-BCTABipy与Pd²⁺所形成的配合物组成；同时，在Ln(Ⅲ)与Pd²⁺共存体系中研究了Et-Ph-BCTABipy对Pd²⁺的萃取选择性。结果表明：Et-Ph-BCTABipy在HNO₃体系中对Pd²⁺具有较强的萃取性能和较高的萃取选择性；萃取过程中Et-Ph-BCTABipy与Pd²⁺以1∶2的比例结合，其萃取平衡常数K_ex=3.42×10⁶。     

新型铯选择性吸附剂的合成及性能

在金属镍粉表面原位合成了与金属基体紧密结合的亚铁氰化镍钾(KNiFC/Ni)吸附剂。经分析,其表面为面心立方晶系的亚铁氰化镍钾(KNiFC),厚度约为40~80nm,晶格参数为0.996 0nm,化学组成可表示为K1.4Ni1.3Fe(CN)6。结果表明:该吸附剂不水解,对137 Cs具有较高的吸附容量,非常快的吸附速率,很高的选择性,Cs的吸附分配系数(Kd)可达105 mL/g,即使在1.0mol/L NaNO3溶液中,Kd值也大于103 mL/g;该吸附剂吸附137 Cs为典型的离子交换机制,NH+4由于具有和Cs+相近的离子半径所以竞争最为强烈。本吸附剂有望用于含铯废液的处理及137 Cs的分离或提取。     

锕系金属（铀和锔）内嵌硼球烯的理论研究

最近发现的全硼富勒烯（硼球烯,D_2d B^-/0₄₀）,开启了硼球烯化学研究的新篇章。类似于富勒烯,金属掺杂也是硼球烯修饰和功能化重要途径。本工作采用密度泛函理论预测了一系列锕系金属掺杂硼球烯［An@B₃₉］ⁿ⁺（An=U,n=3;An=Cm,n=2）。理论计算表明,这些硼球烯均为稳定的金属内嵌硼球烯,其中［U@B₃₉］³⁺的能量最低,结构具有C₃对称性,而［Cm@B39］²⁺为C₁结构。成键性质分析表明,［U@B₃₉］³⁺和［Cm@B₃₉］²⁺均存在σ和π离域键。另外［An@B₃₉］ⁿ⁺中U-B键的共价相互作用强于Cm-B键,且［U@B₃₉］³⁺较［Cm@B₃₉］²⁺更稳定。因此,An-B键的共价特征对于这些锕系金属内嵌硼球烯的形成是必不可少的。本工作扩展了硼球烯体系,并为新型稳定金属内嵌硼球烯的设计提供了理论线索。     

螯合剂对铀在小鼠体内分布的影响研究

铀在生物体内的化学形态及分布是评价铀毒性的基础。文章通过尾静脉注射给药方式研究螯合剂对染铀小鼠体内铀分布的影响。通过建立包含主要体液金属离子、小分子配体及UO₂²⁺与螯合剂的热力学平衡模型,采用数值模拟方法研究UO₂²⁺在血液中的形态。实验结果表明：DTPA易与UO₂²⁺形成［(UO₂)₂(OH)DTPA］^2-,对小鼠血液中的UO₂²⁺有明显的促排作用,但在促排的同时对小鼠的肾脏和骨骼有损伤;抗坏血酸对小鼠体内各组织器官的铀促排几乎无作用,但形成的［(UO₂)₂(OH)Ascorbate］²⁺会阻碍肾脏中U(Ⅵ)的代谢;NTA对小鼠体内各组织器官铀的促排作用小,并会促使体内出现固相(UO₂)₃(PO₄)₂·4H₂O,对骨骼有较强的损伤作用,不适合作为铀的促排剂。     

无机锶吸附剂的制备及其应用

为了去除放射性溶液中的90Sr,采用高锰酸钾和氯化锰的水溶液在pH=10~12、60℃的水浴中反应制备了一种MnO2吸附材料,并用X射线衍射法对其进行了初步分析和表征,该样品为α-MnO2和γ-MnO2的混合晶相。采用静态实验对该吸附剂进行研究,并将其与9种常见的天然锶吸附材料进行比较。结果表明:该吸附剂对90Sr的吸附效果明显好于常用天然吸附材料;其对90Sr的吸附速率非常快,约20min即可吸附平衡,且具有较高的理论饱和吸附容量(Q≈0.52mmol/g)和吸附分配系数(Kd),其典型Kd≈104 mL/g;随着硝酸浓度增加90Sr的Kd值迅速降低,当c(HNO3)=0.01mol/L时,Kd≈6×103 mL/g,而当c(HNO3)=0.1mol/L时,Kd值仅为6mL/g,降低了3个数量级;Na+、K+的含量对Kd值的影响较小,随其浓度增加Kd值缓慢降低,但Co2+、Ca2+对锶的Kd值具有较大的影响,随离子浓度增加Kd值快速减小。该吸附剂对模拟和真实放射性废液的90Sr动态去除实验结果表明,其对锶具有很好的吸附性能,可用于去除放射性废水中的90Sr。     

探索碱金属阳离子在钍基硫酸盐配合物自组装过程中的作用

配体通常会直接影响钍配合物的自组装模型,但是碱金属阳离子在其自组装过程中的潜在作用还有待进一步研究。本工作中,通过添加不同碱金属阳离子,可以获得一系列四价钍的硫酸盐结构配合物,说明了碱金属阳离子对于整个拓扑结构以及四价钍水解聚合方式的影响。四价钍硫酸盐的结构分析表明,引入K⁺、Cs⁺可以改变晶体骨架的维度,形成一维链状、二维层状或三维框架的钍硫酸盐结构,较大的Cs⁺可促进二维层状低聚物的形成,同时形成了罕见的［Th₃(μ₃-O)］¹⁰⁺三聚体中心。过去认为抗衡离子在配合物形成过程中扮演无关紧要的角色,而这一工作表明碱金属抗衡离子影响了结构的整体堆积方式。     

Effect of N_2 and O_2 on OH radical production in an atmospheric helium microwave plasma jet

UV-pulsed laser cavity ringdown spectroscopy of the hydroxyl radical OH(A–X)(0–0)band in the wavelength range of 306–310 nm was employed to determine absolute number densities of OH in the atmospheric helium plasma jets generated by a 2.45 GHz microwave plasma source.The effect of the addition of molecular gases N_2 and O_2 to He plasma jets on OH generation was studied.Optical emission spectroscopy was simultaneously employed to monitor reactive plasma species.Stark broadening of the hydrogen Balmer emission line(H_β)was used to estimate the electron density nein the jets.For both He/N_2 and He/O_2 jets, newas estimated to be on the order of 10~(15)cm~(-3).The effects of plasma power and gas flow rate were also studied.With increase in N_2 and O_2 flow rates, netended to decrease.Gas temperature in the He/O_2 plasma jets was elevated compared to the temperatures in the pure He and He/N_2 plasma jets.The highest OH densities in the He/N_2 and He/O_2 plasma jets were determined to be 1.0?×10~(16)molecules/cm~3 at x?=?4 mm(from the jet orifice)and 1.8?×?10~(16)molecules/cm~3 at x=3 mm, respectively.Electron impact dissociation of water and water ion dissociative recombination were the dominant reaction pathways, respectively, for OH formation within the jet column and in the downstream and far downstream regions.The presence of strong emissions of the N_2~+ bands in both He/N_2 and He/O_2 plasma jets, as against the absence of the N_2~+ emissions in the Ar plasma jets, suggests that the Penning ionization process is a key reaction channel leading to the formation of N_2~+ in these He plasma jets.     

Characterization of extended defects in SiGe alloys formed by high dose Ge implantation into Si

The synthesis of SiGe/Si heterostructures by Ge⁺ ion implantation is reported. 400 keV Ge⁺ ions were implanted at doses ranging from 3 × 10¹⁶ to 10 × 10¹⁶ ions/cm² into (001) Si wafers, followed by Si⁺ amorphisation and low temperature Solid Phase Epitaxial Regrowth (SPER). TEM investigations show that strained alloys can be fabricated if the elastic strain energy (E_el) of the SiGe layer does not exceed a critical value (E′_el) of about 300 mJ/m², which is independent of the implantation energy. Our analysis also suggests that “hairpin” dislocations are formed as strain relieving defects in relaxed structures. A “strain relaxation” model is proposed to explain their formation.     

强碱性阴离子交换树脂用于90YCl3溶液金属杂质的纯化

从⁹⁰Sr/⁹⁰Y放射性衰变平衡体系中分离获得的90Y溶液具有无载体、金属杂质含量高等特点,需要进一步纯化才能应用于⁹⁰Y放射性药物的制备。本工作研究了AE4强碱性阴离子交换树脂在盐酸溶液中对Y³⁺、Fe³⁺、Al³⁺、Zn²⁺、Mg²⁺的吸附性能。结果表明：AE4树脂在盐酸溶液中不吸附Al³⁺、Zn²⁺、Mg²⁺;在3 mol/L以上的盐酸溶液中对Fe³⁺吸附性能较好;在7 mol/L以上的盐酸溶液中对Y³⁺的吸附性能较好。含有Y³⁺、Al³⁺、Zn²⁺、Mg²⁺等元素的混合溶液在3 mol/L HCl溶液通过AE4树脂柱后,Fe³⁺基本被全部吸附在树脂柱上;吸附余液调节盐酸浓度至7 mol/L,通过另一根AE4树脂柱,Y³⁺基本被吸附在树脂柱上。最后用0.01 mol/L HCl洗脱吸附在树脂柱上的Y³⁺,得到纯化后的YCl₃溶液。稳定核素和90Y示踪的研究结果表明,采用AE4树脂纯化⁹⁰YCl₃溶液的工艺可行,AE4树脂可用于90YCl3溶液中Fe、Al、Zn、Mg等主要杂质金属元素的去除。     

钙-铀-碳酸络合物对红土吸附铀性能的影响

采用静态实验法研究了钙-铀-碳酸络合物对红土吸附铀性能的影响。结果表明:溶液的pH值、总碳酸和钙离子浓度增大会抑制红土对铀的吸附,当pH=7.0,红土投加量为1g/L,钙离子、总碳酸根和初始铀浓度分别为0.4mmol/L、3.8mmol/L和50mg/L时,红土对铀的最大吸附容量约为4.20mg/g。铀在红土上的吸附形态为UO2(CO3)2-2、UO2(CO3)4-3和UO2CO3(aq)。利用铀-碳酸络合物总量c(UCO3)T可预测红土吸附铀的容量qe,c(U-CO3)T与qe呈非线性关系,其方程为qe=18.2(c(UO2+2)·c(CO2-3)(K1+K2c(CO2-3)+K3c2(CO2-3)))0.36。该研究成果可为铀污染土壤的修复和治理提供技术和理论参考。     

Isomer separation of Cu and Cu with a resonance ionization laser ion source

Radioactive copper isotopes were ionized with the resonance ionization laser ion source (RILIS) at the on-line isotope separator ISOLDE (CERN). Using the different hyperfine structure in the 3d¹⁰ 4s  ²S_1/2 – 3d¹⁰ 4p  ²P⁰_1/2 transition the low- and high-spin isomers of ⁷⁰Cu were selectively enhanced by tuning the laser wavelength. The light was provided by a narrow-bandwidth dye laser pumped by copper vapor lasers (CVL) and frequency doubled in a BBO crystal. The ground state to isomeric state intensity ratio could be varied by a factor of 30, allowing to assign gamma transitions unambiguously to the decay of the individual isomers. It is shown that the method can also be used to determine magnetic moments. In a first experiment for the 1⁺ ground state of ⁷⁰Cu a magnetic moment of (+)1.8(3) μ_N and for the high-spin isomer of ⁷⁰Cu a magnetic moment of (±)1.2(3) μ_N could be deduced.     

Ion implantation doping and electrical conductivity enhancement of C60 films

Pristine C₆₀ films sublimed onto sheet mica were implanted with 20 keV K⁺ ions and I⁺ ions at doses of 1.0 × 10¹⁶/cm², 3.0 × 10¹⁶/cm² and 5.0 × 10¹⁶/cm², and with 20 keV Ar⁺ ions at a dose of 5.0 × 10¹⁶/cm². The distributions of dopants were studied using Rutherford backscattering spectrometry (RBS). The temperature dependence of sheet resistivity of the films was investigated applying a four-probe system. It was proposed that the conductivity enhancement of K⁺ implanted C₆₀ films was due to the implanted ions in the films, while for I⁺ implanted C₆₀ films, both implanted I⁺ ions and irradiation effects of the ions contributed to the enhancement of conductivity.     

不同离子浓度对~(239)Pu在高庙子膨润土上的吸附影响

采用静态吸附法研究了239 Pu在CO2-3、HCO-3、SO2-4、Mg2+、Ca2+、Fe3+等不同离子浓度下在膨润土上的吸附。实验结果表明:随着CO2-3、HCO-3、Mg2+、Ca2+、Fe3+浓度的增大,239Pu在膨润土上的吸附分配系数Kd值逐渐减小,而随着SO2-4浓度的增加,Kd值先增加后减小,其中CO2-3、Fe3+浓度对Kd值影响较大。     

Heavy ion irradiation effects in the rare-earth sesquioxide Dy2O3

Polycrystalline pellets of the rare-earth sesquioxide Dy₂O₃ with cubic C-type rare-earth structure were irradiated with 300 keV Kr²⁺ ions at fluences up to 5 × 10²⁰ Kr/m² at cryogenic temperature. Irradiation-induced microstructural evolution is characterized using grazing incidence X-ray diffraction (GIXRD) and transmission electron microscopy (TEM). In previous work, we found a phase transformation from a cubic, C-type to a monoclinic, B-type (C2/m) rare-earth structure in Dy₂O₃ during Kr²⁺ ion irradiation at a fluence of less than 1 × 10²⁰ Kr/m². In this study, we find that the crystal structure of the top and middle regions of the implanted layer transform to a hexagonal, H-type (P6₃/mmc) rare-earth structure when the irradiation fluence is increased to 5 × 10²⁰ Kr/m²; the bottom of the implanted layer, on the other hand, remains in a monoclinic phase. The irradiation dose dependence of the C-to-B-to-H phase transformation observed in Dy₂O₃ appears to be closely related to the temperature and pressure dependence of the phases observed in the phase diagram. These transformations are also accompanied by a decrease in molecular volume (or density increase) of approximately 9% and 8%, respectively, which is an unusual radiation damage behavior.     

Argon irradiation damage at a Cu/Al2O3 interface for different alumina structures

The evolution of damages at a Cu/Al₂O₃ device interface after Ar⁺ irradiation, depending on alumina structure, and the effect of surface roughness on sputtering have been studied. A polycrystalline Cu/Al₂O₃ bilayer and polycrystalline Cu on amorphous alumina were irradiated with 400 keV Ar⁺ ion beam at doses ranging from 5 × 10¹⁶ to 10¹⁷ Ar⁺/cm² at room temperature. The copper layer thicknesses were between 100 and 200 nm. RBS analysis was used to characterize the interface modification and to deduce the sputtering yield of copper. The SEM technique was used to control the surface topography. A RBS computer simulation program was used to reproduce experimental spectra and to follow the concentration profile evolutions of different elements before and after ion irradiation. A modified TRIM calculation program which takes into account the sputtering yield evolution as well as the concentration variation versus dose gives a satisfactory reproduction of the experimental argon distribution. The surface roughness effect on sputtering and the alumina structure influence at the interface on mixing mechanisms are discussed.