掺铝的α型氢氧化镍的合成及其电化学性能

目前使用的碱性二次电池中,镍系列电池占有很重要的地位,其中镍电极是其核心.镍电极的研究集中于掺杂离子对电极过程的作用机理、具有优良的电化学性能的稳定的α-Ni(OH)2和纳米Ni(OH)2的制备等三个热点上.由于NiOOH/Ni(OH)2电化学储能所涉及的活性物质在碱性介质中具有不溶解性及长寿命的优点,所以氢氧化镍特别适宜作为碱性蓄电池的正极活性物质.

PREPARATION AND PROPERTIES OF THREAD-THROUGH COPOLYMERS OF POLYETHYLENE WITH POLYISOPRENE

Graft copolymers of polyethylene (PE) with polyisoprene (PI) were synthesized through polymerization of ethylene in toluene solution of PI (cis-1,4-: 95%; 3,4-: 5%) using a homogeneous V(acac)3/Et3Al2Cl3 catalyst. Copolymers are formed when the growing po

微孔配位聚合物的合成与表征

微孔配位聚合物是近年来被广泛研究的领域之一，这类材料在储气材料等领域的应用前景逐步被开发出来。作为良好的储气材料，配位聚合物必须具有规则的孔道结构和良好的稳定性。本论文以合成多维孔道新化合物为目标，成功合成并解析出13个微孔配位聚合物。对化合物的元素分析、红外和TGA等进行了表征，同时对部分化合物的紫外和荧光性质进行了测定。 首先，对微孔配位聚合物的最新研究动态进行了简要介绍，并对一些代表性化合物的结构类型、性能以及应用等进行了归纳总结。然后介绍了合成配位聚合物晶体的实验原理，化合物的表征方法。 本论文在水热条件下，成功合成了13个新化合物分别为：(C19H15N4)2(NO3)2∙3H2O (3-3)，(C19H15N4)2[CdCl4] (3-4)，2Ag(tta)∙AgNO3 (3-5)，Cu8(tta)15(H2O)Cl (3-6)，[Zn(5-CH3-tta)2(isoH)2] (BDC) (3-7)，Pb[(PO3)2C(OH) CH3]•H2O (4-1)，Ni(C5H4NCOO)2∙4H2O (5-2)，Co(C5H4NCOO)2(H2O)2∙2H2O (5-3)，[CdCl2(C13H12N2O)2] (5-4)，{C6H4(COOH)S}2 (5-5)，(Deta)(ClO4)NO3 (5-6)，(NH4)2[-Mo8O26] (6-1) 和 (NH4)2[Mo4O13] (6-2)。其中化合物3-5，3-6和3-7是由四氮唑和金属构筑的纳米孔道三维化合物；化合物3-3，3-4，5-2，5-3，5-4，5-5和5-6均具有超分子网络结构；4-1是有机膦酸为配体的二维层状化合物，是首例(5,5)连接的(47•63) (48•62)拓扑网络。化合物6-1是一维无限链骨架的钼酸盐，6-2是二维层状的钼酸盐，显示了不寻常的(32•4)(32•53•8)(3•42•54•6•82)(34•43•54•64) 拓扑网络。最后对论文进行概括总结，并展望了下一阶段的工作安排。

Assessment of metal contamination in surface sediments of Jiaozhou Bay, Qingdao, China

An assessment of metal contamination in surface sediments of the Jiaozhou Bay, Qingdao, one of the rapidly developing coastal economic zones in China, is provided. Sediments were collected from 10 stations and a total of 15 heavy metals were analyzed. Concentrations of metals show significant variability and range from 210 to 620 ppm for Ti, 2.7 to 23 ppm for Ni, 4.2 to 28 ppm for Cu, 5.2 to 18 ppm for Pb, 12 to 58 ppm for Zn, 0.03 to 0.11 ppm for Cd, 5 to 51 ppm for Cr, 1.5 to 9.9 ppm for Co, 5.3 to 19 ppm for As, 12 to 32 ppm for Se, and 19 to 97 ppm for Sr. Based on concentration relationships and enrichment factor (EF) analyses, the results indicate that sediment grain size and organic matter played important roles in controlling the distribution of the heavy metals in surface sediments of the Jiaozhou Bay. The study shows that the sediment of the Jiaozhou Bay has been contaminated by heavy metals to various degrees, with prominent arsenic contributing the most to the contamination. The analysis suggests that the major sources of metal contamination in the Jiaozhou Bay are land-based anthropogenic ones, such as discharge of industrial waste water and municipal sewage and run-off. Notably, the elevated heavy metal concentrations of the Jiaozhou Bay sediments could have a significant impact on the bay's ecosystem. With the rapid economic development and urbanization around the Jiaozhou Bay, coastal management and pollution control should focus on these contaminant sources, as well as provide ongoing monitoring studies of heavy metal contamination within the bay.

甘肃金川II号岩体岩浆演化及铜镍硫化物成矿过程探讨

金川矿床是超大型岩浆 Ni-Cu-PGE 硫化物矿床，它赋存有世界第三的镍储量（5.45×106 t，Ni 的平均品位为 1.2%）。该矿床位于华北板块西侧阿拉善地块西南边缘龙首山隆起中。本论文以金川矿区的 II 号岩体为研究对象，在系统整理前人工作的基础上，通过深入细致的野外地质考察和系统采样，选取有代表性的样品，进行详细的显微镜鉴定，并运用元素地球化学等手段，对 II 号岩体的源区特征、岩浆演化过程及其赋存的⑴、⑵号矿体的成矿机制等主要矿床学问题进行了系统成因研究，并尝试提出了二次硫化物熔离成矿模式。本论文主要取得以下几点结论性成果： 1）岩浆起源：起源于上地幔尖晶石－石榴石二辉橄榄岩过渡地带的下部。通过上地幔源岩的柱状部分熔融模式（≥25%）或三角部分熔融模式（10～15%），形成富PGE的S不饱和原始岩浆。 2）地壳同化混染：地壳物质的同化混染主要是由早期下地壳物质的同化混染和晚期上地壳物质的同化混染组成的多阶段同化混染，并且其成分为富钙质围岩。 3）结晶分异演化：金川II号岩体作为橄榄石堆积相，其橄榄石的结晶主要发生在上地壳深部岩浆房，而橄榄石与熔浆的反应及辉石和斜长石的结晶则主要发生在浅部岩浆房，既现今岩体所在位置。 4）S 的饱和机制：岩浆通道内下地壳物质的同化混染，导致岩浆硫饱和，并于岩浆通道中发生了第一次硫化物熔离；上地壳深部岩浆房中地壳物质的同化混染和橄榄石的分离结晶，促使硫饱和的母岩浆发生了第二次硫化物熔离。 5）深部岩浆房的演化：上地壳深部岩浆房中橄榄石分离结晶与硫化物熔离之后，在重力分异作用下，形成了自上而下的硅酸盐岩浆、橄榄石“晶粥”、含硫化物熔体的橄榄石“晶粥”以及矿浆的四层分层格局。同时，底部部分硫化物熔体发生了Pt合金（Pt-Fe）的脱离。 6）侵入期次：上地壳深部岩浆房中，母岩浆分异演化早期，其顶部含有尚未完全成长橄榄石颗粒的“晶粥”在构造应力挤压下首先上侵、成岩形成金川II号岩体顶部、呈“上悬体”的中细粒含辉橄榄岩；分层格局形成之后，橄榄石“晶 VI 粥”、含硫化物熔体的橄榄石“晶粥”以及矿浆依次上侵成岩、成矿，分别形成金川 II 号岩体上部的二辉橄榄岩相、⑴、⑵号矿体的主体以及⑵号矿体底部的块状矿石。

土壤中重金属活动性的唐南膜测定、模型模拟与污染的原位控制

土壤是自然环境的重要组成部分，是人类赖以生存与发展的宝贵资源。但是近年来我国土壤重金属污染日益严重，重金属污染物与其它类型的污染物相比具有隐蔽性、长期性与不可逆性等一系列特殊性，成为土壤中永久的污染物，最终通过食物链的传递进入人体，对人类的健康造成潜在的危害。因此，研究土壤重金属污染与控制具有很重要的意义。本论文首次将唐南膜平衡法（DonnanMembraneTechnique）和EcosAT（EquilibriumCalculationOfSpeciationAndTransport）模型引入我国土壤重金属活动性研究，并将两种方法获得的结果进行比较，互相验证，取得了较好的结果。还将两种方法结合探讨了贵州铝厂生产的赤泥对土壤中的游离重金属离子浓度的影响。土壤样品采于贵州都匀福锌矿地区，一个位于锅锌矿选厂尾矿坝下农田中的水稻土，以下简称坝下土，为重污染土；另一个位于锅锌矿上游桥边农田中的水稻土，以下简称桥边土，为轻污染土，本研究取得的主要结论与认识包括：1．作者对唐南膜平衡法进行了部分改进，用国内生产的JAM一I型均相离子交换膜替换Brwin等所用的BDH膜，既降低了实验的平衡时间，又经济实惠。另外还用KNO3溶液代替KNO3和Ca（NO3）2混合溶液作为实验的介质溶液，就可以避免由于国内土壤中Ca2+含量差异较大可能造成的误差。其它实验条件为：蠕动泵的流速为2.0ml／min，平衡时间为48小时。2．用柠檬酸体系（液一液体系）和土壤一水体系（固一液体系）检验了唐南膜平衡法，它可以在不扰动体系平衡的基础上同时测定同一体系中的多个游离金属离子浓度，而且各金属离子之间互不干扰。3．桥边土中的游离重金属离子浓度与其中2mol／LHNO3提取的重金属总含量成很好的直线关系，其中Cu和Zn游离离子浓度与其中的总金属含量呈现较好的正比关系，随着重金属总含量的降低，即土液比的降低，游离重金属离子浓度随之降低；而其中的Ni和Cd却相反，随着重金属总含量的降低，游离重金属离子浓度反而增加。添加赤泥后随着土液比的降低各重金属的游离离羲?子浓度的变化趋势与添加赤泥前一样。桥边土中的重金属游离离子浓度在添加联合法赤泥后有所增加，而拜尔法赤泥的加入降低了其中的游离重金属离子浓度，加入的比例越大，变化的量越多，而且其中Ni和cd的变化幅度比Cu和Zn的要大。4．坝下土中Cu、Zn、Ni和Cd元素的游离离子浓度与它们在土壤中Zmol／LHNo3提取的重金属总含量呈很夯的正比关系，随着重金属总含量的降低，游离重金属离子浓度随之降低。添加赤泥后其中Cu和Zn元素的变化趋势与添加赤泥前一样，Ni和Cd元素出现了异常，Ni在赤泥添加比例为0.50％时变化趋势一样，但添加比例为2.00％时其离子浓度先增加，但在土液比为1:100时反而有较大幅度的降低。而其中Cd离子浓度先增加，在土液比为1:100时反而有较大幅度的降低。坝下土中Cu和Zn的游离离子浓度在添加赤泥以后改变很小，赤泥添加比例为2.00％的土壤中的游离离子浓度相对较低一点，而添加比例为0.50％的与未加赤泥的土壤基本上一样；其中Ni和Cd的变化相对来说较大，赤泥添加比例为2.00％的土壤中的游离离子浓度降低得比较明显，拜尔法赤泥添加比例为0.50％的土壤也得到了较大的改善，而联合法赤泥添加比例为0.50％的却比未加赤泥的土壤中的还要高一点。5．利用ECOSAT模型模拟了本论文所涉及的实验中的游离重金属离子浓度，测量值与模拟值取得了较好的一致，除了Zn的误差较大以外，其它三个元素符合的很好，从而表明EC0sAT在土壤一水系统中的模拟取得了较好的结果。6．模拟了不同土液比土壤中各重金属元素在有机质、铁氧化物、粘土和唐南凝胶体这四种吸附相中的分配。发现在所研究的土壤样品中所有元素在粘土相中所占的比例很小，可以忽略不计，Cu主要分布在有机质相中，占80％左右，随着土液比的降低，其在有机质和唐南凝胶体相中的分配比例慢慢变小，而在铁氧化物中的比例越来越大；Zn主要分布在有机质和铁氧化物相中，各占40％左右；随着土液比的降低，Zn在有机质相中的比例增大，铁氧化物比例几乎不变，而唐南凝胶体所占比例逐渐减小；Ni基本上只分布在有机质和铁”氧化物相中，Cd则几乎只存在于有机质相中，它们的分布比例几乎不随土液比的改变而变化。7．无论在桥边土和坝下土中添加何种赤泥，添加的比例是多少，在添加赤泥前后土壤中重金属元素在各吸附相中的分配比变化很小，主要是有机质相所占比例稍微变小，而铁氧化物相相应的有一点增加。而对于不同的土液比，其变化趋势相同，只是变化幅度相对来说较大。

A practical approach to the degradation of polychlorinated biphenyls in transformer oil

A practical and efficient disposal method for hydrodechlormation of polychlorinated biphenyls (PCBs) in transformer oil is reported. Transformer oil containing PCBs was treated by nanometric sodium hydride (nano-NaH) and transition metal catalysts. High destruction and removal efficiency (89.8%) can be attained by nano-NaH alone under mild conditions. The process exhibits apparent characteristics of a first order reaction. The reductive ability of nano-NaH was enhanced by the addition of transition metal catalysts. In the presence of TiCl4, 99.9% PCBs was hydrodechlorinated. The complex reducing reagents, Ni(OAc)(2) + i-PrONa, show extra hydrodechlorinating activity for di-chlorinated biphenyls. (c) 2004 Elsevier Ltd. All rights reserved.

Single-crystal X-ray structure and properties of K-10[Ni-4(H2O)(2)(AsW9O34)(2)]center dot 4H(2)O

The rational synthesis and the structural and magnetic characterization of a nickel cluster are presented. The compound comprises a rhomblike Ni4O16 group encapsulated between two-heptadentate tungstoarsenate ligands [AsW9O34](9-). The crystal structure of K-10[Ni-4(H2O)(2)(AsW9O34)(2)](.)4H(2)O was solved in monoclinic, P2(1)/n symmetry, with a = 12.258(3) Angstrom, b = 21.232(4) Angstrom, c = 15.837(3) Angstrom, beta = 92.05(3)degrees, V = 4119.1(14) Angstrom(3), Z = 2, and R = 0.0862. The crystal structure of the Ni(II) derivative was compared with that of the Cu(II), Zn(II), Co(II) and Mn(II) derivatives. The Ni4O14(H2O)(2) unit in the compound shows no Jahn-Teller distortion. On the other hand, the Ni(II) derivative shows ferromagnetic exchange interactions within the Ni4O16 group (J = 7.8 cm(-1), J' = 13.7 cm(-1)) and an S = 4 ground state, the highest spin state reported in a heteropoly complex. Its redox electrochemistry has been studied in acid buffer solutions using cyclic voltammetry. It exhibited two steps of one-electron redox waves attributed to redox processes of the tungsten-oxo framework. The new catalyst showed an electrocatalytic effect on the reduction of NO2-.

Partial oxidation of methane to synthesize gas over Ni/alpha-Al2O3 catalyst promoted by noble metals

The production of synthesis gas by partial oxidation bf methane in oxygen has been examined over Ni/alpha-Al2O3 catalyst promoted by noble metals(Rh, Ru, Pt and Pd), especially with Pt. The reactivity is considered in conjunction with the result of H-2-TPR, CO-TPD, SEM and XRD. It is found that small amount of Pt results in a great improvement of activity for the Ni/alpha-Al2O3 catalyst. The activity order is : Rh-Ni>Pt-Ni approximate to Ru-Ni>Pd-Ni, meantime the Pt improves the stability of Ni/alpha-Al2O3 catalyst except for Pd which is easy to he deactivated by carbon deposition. The results of TPD, SEM and XRD indicate that there is an interaction between Ni and Pt metals in the catalyst. The interaction increases the dispersions of Pt and Nit the presence of Pt suppresses the growth and the migration of Ni grains over the surface of the catalyst.

Studies on the adsorption property of NO on the Ni-based mixed oxide catalysts with Perovskite-like (ABO(3) and A(2)BO(4)) structure

The mixed oxides LaNiO3, La0.1Sr0.9NiO3, La2NiO4 and LaSrNiO4 with perovskite (ABO(3)) and related(A(2)BO(4)) structures were prepared and the adsorption property for NO and the catalytic activity for NO decomposition over these oxidse were also tested. The catalysts were characterized by means of BET surface measurement, chemical analysis, NO-TPD etc.. It was shown that the adsorption amount of NO is correlated with the concentration of oxygen vacancy formed and the adsorption type and strength of NO are related to the valence of metallic ion. Generally there are three kinds of adsorption species, NO-, NO+ and NO on the mixed oxides, among them the negative adsorpion species (NO-) are active for NO decomposition. The weaker the adsorption of oxygen on the catalyst is, the faster the mobility of oxygen is and the easier the redox process takes place in reproducing the active sites in which the oxygen species (O-, O2-) would participate.

Ni^2＋掺杂透明ZnO-Al2O3-SiO2系微晶玻璃的光学性质

采用传统熔融冷却的方法制备了透明Ni^2＋掺杂ZnO-Al2O3-SiO2系玻璃，结合X-射线、吸收和荧光等测试手段，研究了不同热处理温度对Ni^2＋掺杂透明ZnO-Al2O3-SiO2系微晶玻璃光学性质的影响。由X-射线衍射谱鉴定出微晶玻璃中析出的晶相为ZnAl2O4微晶，其尺寸在13nm以下。玻璃中没有发现近红外发光，而在微晶玻璃中存在宽带近红外发光，其可归属为八面体六配位Ni^2＋离子的^3T2g（^3F）激发态向^3A2g（^3F）基态的跃迁。随热处理温度升高发光强度增强，而发射峰位则发生蓝移；荧

Upgrading of liquid fuel from the vacuum pyrolysis of biomass over the Mo-Ni/gamma-Al2O3 catalysts

High amounts of acid compounds in bio-oil not only lead to the deleterious properties such as corrosiveness and high acidity, but also set up many obstacles to its wide applications. By hydrotreating the bio-oil under mild conditions, some carboxylic acid compounds could be converted to alcohols which would esterify with the unconverted acids in the bio-oil to produce esters. The properties of the bio-oil could be improved by this method. In the paper, the raw bio-oil was produced by vacuum pyrolysis of pine sawdust. The optimal production conditions were investigated. A series of nickel-based catalysts were prepared. Their catalytic activities were evaluated by upgrading of model compound (glacial acetic acid). Results showed that the reduced Mo-10Ni/gamma-Al2O3 catalyst had the highest activity with the acetic acid conversion of 33.2%. Upgrading of the raw bio-oil was investigated over reduced Mo-10Ni/gamma-Al2O3 catalyst. After the upgrading process, the pH value of the bio-oil increased from 2.16 to 2.84. The water content increased from 46.2 wt.% to 58.99 wt.%. The H element content in the bio-oil increased from 6.61 wt.% to 6.93 wt.%. The dynamic viscosity decreased a little. The results of GC-MS spectrometry analysis showed that the ester compounds in the upgraded bio-oil increased by 3 times. it is possible to improve the properties of bio-oil by hydrotreating and esterifying carboxyl group compounds in the bio-oil.