茜素红-S螯合形成树脂吸附测定地质样品的金、铂和钯

以茜素红-S(1,2-二羟基蒽醌-3-磺酸钠)为螯合剂,与大孔强碱性阴离子树脂D296-R合成茜素红-S螯合形成树脂,能够在酸性介质中使螯合形成树脂中的-OH离解出H⁺,变成-O-,与大体积的贵金属碘络阴离子[MeI4]^2-相遇形成稳定的螯合物。在较宽的酸度范围内使Au、Pt、Pd与贱金属有效分离,并抑制NO3^-对贵金属吸附的影响。与高压密闭溶矿方式相结合,Au、Pt、Pd的回收率均大于92%,检出限:Au 0.047 ng/g、Pt 0.082 ng/g、Pd 0.051 ng/g。应用于铂族元素地球化学成分分析一级标准物质中Au、Pt、Pd的测定,结果与认定值的相对误差(RE)为-7.58% ~10.9%,相对标准偏差(RSD)均小于9.86%。     

New Sorption Materials Based on Organosilicon Derivatives of Thiosemicarbazides

The synthesis of organosilicon derivative monomers and polymers characterized with sorption properties has been performed. The synthesized organosilicon polymers have been investigated as sorbents for heavy (Hg(II)) and noble (Ag(I), Au(III), Rh(II), Pd(II), and Pt(IV)) metals. The coefficients of the interphase metal distribution have been estimated.     

合成亚砜BSO萃取分离钯铂的性能研究

对合成亚砜BSO萃取Pd(Ⅱ)、Pt(Ⅳ)性能的研究表明,在不同酸度下BSO对Pd(Ⅱ)均有优异的萃取性能,而只有在高酸度介质里BSO对Pt(Ⅳ)有较高的萃取能力.在低酸度下利用BSO对Pd(Ⅱ)、Pt(Ⅳ)萃取性能的差异,能很好地萃取分离Pd(Ⅱ)、Pt(Ⅳ);也可以在高酸度下共萃Pd(Ⅱ)、Pt(Ⅳ),再利用水反萃Pt(Ⅳ),达到分离Pd(Ⅱ)、Pt(Ⅳ)的目的.     

铑(III)离子印迹聚合物的制备及其作为吸附材料的应用探索

以RhCl63-为模板,丙稀酰胺(AM)为功能单体,甲基丙烯酸乙二醇酯(EGDMA)为交联剂,采用分子印迹技术合成了一系列铑离子印迹聚合物(ⅡPs);研究了聚合条件和聚合方法对ⅡPs吸附性能的影响。结果发现,在模板、功能单体和交联剂的加入摩尔比为1:2:40时,用沉淀聚合法制备的铑离子印迹聚合物(ⅡP2)具有较高的吸附容量和最好的印迹效果。该印迹聚合物不仅可重复多次使用,而且在Rh(Ⅲ)与Pd(Ⅱ)、Pt(Ⅳ)、Ru(Ⅲ)、Ir(Ⅳ)、Cu(Ⅱ)、Ni(Ⅱ)及Fe(Ⅲ)之间的吸附选择性系数均在10以上,将其作为吸附材料用于分离富集添加了Rh(Ⅲ)的河水样品中的Rh(Ⅲ),回收率在90%左右,相对标准偏差在5.0%以下。     

Adsorption properties of Ag（Ⅰ）, Au（Ⅲ）, Pd（Ⅱ） and Pt（Ⅳ） ions on commercial 717 anion-exchange resin

The adsorption properties of the four precious metal ions (Ag(I), Au(II), Pd(III) and Pt(IV)) on the commercial Cl^?-form 717 strongly basic anion-exchange resin were studied in detail. The effects of the contact time, solution acidity, and concentrations of Cl^? and Pb²⁺ ions on the adsorption properties were studied by the batch method. Then, the column method was conducted under the optimized adsorption conditions (pH=3.0). The effects of the sample loading flow rate and the length-to-diameter ratios of the columns were investigated. The precious metal ions adsorbed could not be eluted completely after the saturated adsorption because the precious metal ions were found to be reduced to their metallic states during the adsorption process. So, it is recommended that the commercial Cl^?-form 717 strongly basic anion-exchange resin should be decomposed directly to recovery the precious metals after the saturated adsorption.     

活性炭吸附-电感耦合等离子体发射光谱法测定化探样品中痕量金铂钯

对于大量化探样品的测定，方法必须尽量操作简便、程序快捷、成本经济和结果可靠。本方法采用酸溶分解样品，活性炭吸附分离富集Au,Pt,Pb，结合电感耦合等离子体发射光谱法进行测定。方法的检出限为0．2ng/g(Au,Pb)-0.5ng/g(Pt)，用于化探样品的测定，结果与推荐值吻合较好，5次平行测定的RSD在6．5％－13．5％。方法简便快速，能适合大量化探样品的实际分析。     

硫化镍试金预富集-ICP-AES测定矿石中的Pt、Pd、Ir、Au

详细研究了硫化镍试金预富集－ICP－AES测定矿石中的Pt,Pd,Ir,Au的多种影响因素，结果表明硫化镍扣用盐酸溶解，多孔玻砂坩埚过滤溶液，盐酸和双氧水溶解残渣是比较理想的分析方案，硫化镍扣溶解过程中，Pt,Pd的损失可忽略。Au的损失相当高，仅能半定量，对于μg/g级的样品，Pt,Pd,Ir,Au的平均回收率在96－99％之间，相对标准偏差为1．7％－6．8％（n=5)，拟定的方法已用于矿石、精矿的分析。     

流动注射化学发光法分析Au、Ag、Pt、Pd的进展

介绍了流动注射化学发光法(FI—CL)的基本原理及其测定痕量Au、Ag、Pt和Pd方面的应用。评述了FI—CL仪器的研制、新分析方法的建立、与其它技术联用等方面的最新进展情况。展望了FI—CL法测定痕量Au、Ag、Pt和Pd的发展方向和研究热点。引用56篇参考文献。     

普罗维登斯菌和希瓦氏菌对Pt(IV)的吸附特性

研究了普罗维登斯菌和希瓦氏菌两种微生物对Pt(IV)的吸附特性。pH和离子强度条件优化实验结果表明,pH=2.0时吸附效果较好,吸附量分别为58.62和72.20 mg/g;随着离子强度的增加,普罗维登斯菌对Pt(IV)的吸附量增加而希瓦氏菌却降低;Pt(IV)和Pd(II)共存时,两种微生物吸附剂均优先吸附Pd(II)。动力学和等温吸附实验结果表明,普罗维登斯菌吸附Pt(IV)的过程更符合拟二级动力学模型和Langmuir等温模型,说明化学吸附是该过程的限速步骤,且为单分子层吸附,其理论最大吸附量为136.10 mg/g。因此,以上研究结果表明,普罗维登斯菌和希瓦氏菌可以吸附回收溶液中的Pt(IV)离子。     

金核/铂壳纳米粒子的光化学合成及电催化活性

在含不同摩尔比的Au(Ⅲ)和Pt(Ⅳ)离子的PEG(聚乙二醇)-丙酮溶液中,采用光化学共还原法合成了一组Au@Pt复合纳米粒子,并以炭黑分别对其负载制成Au@Pt/C催化剂。借助于UV-Vis、TEM和HR-TEM的表征,证实复合纳米粒子为球形的核/壳结构;分别以XPS、EDS和电化学方法分析了复合粒子的化学状态、结构特点和Au@Pt/C催化剂的催化性质。结果表明,不同Au:Pt摩尔比的Au@Pt/C催化剂对甲醇氧化反应具有良好的催化活性和稳定性,其中Au:Pt=1:1时形成的Au@Pt/C催化剂电催化活性最高,约为商品Pt/C催化剂的4倍。简要讨论了核/壳结构产生高催化活性的主要原因。     

溶剂萃取分离金川料液中的金钯铂

阐述了石油亚砜（ＰＳＯ）选择性萃取分离Ｐｄ的基本原理，并以此为基础研究了用ＤＢＣ萃Ａｕ、ＰＳＯ萃Ｐｄ及Ｎ２３５萃Ｐｔ，从金川蒸馏Ｏｓ、Ｒｕ之后的脱胶液中萃取分离金、钯、铂的工艺过程     

碱性条件下M/C(M=Pt, Pd, Ni, Ag, Au)对甲醇氧化电催化活性的对比研究

用化学还原法制备了M/C(M=Pt, Pd, Ni, Ag, Au) 5种纳米金属碳截催化剂,用XRD、XPS分别表征活性物的晶相结构、表面组成和价态形式,用TEM观察催化剂微观形貌,用循环伏安法测定不同催化剂对甲醇氧化的电催化活性。结果表明,催化剂中的纳米金属粒径在3~11 nm之间,纯度较高,在载体表面的分布较为均匀;Pd/C催化剂对甲醇氧化有较好的催化作用,Ni/C对甲醇氧化有一定的活性,而Ag/C和Au/C几乎没有活性。在1 mol·L-1CH3OH+1 mol·L-1NaOH条件下,Pd/C对甲醇氧化最高峰电流密度为890 mA·mg-1,约为Pt/C的66%,Ni/C对甲醇氧化最高峰电流密度为6.3 mA·mg-1,仅为Pt/C的0.46%。     

Rare earth—platinum group mixed metal oxide systems

The phase development in rare earth—platinum group oxide (RE---PG---O) systems has been investigated by reacting selected compositions in sealed evacuated silica vials and characterizing the products using X-ray diffraction. PG(II), PG(III), PG(IV) and PG(V) species, where PG Ru, Ir, Rh, Pd and Pt, have been stabilized in these systems in various structure types. For PG(II) these include the Nd₂CuO₄-type structure and other fluorite-related derivatives; for PG(III), orthorhombically distorted perovskite; for PG(IV), the pyrochlore structure; for PG(V), - and γ-A₃BO₇ types, which are also ordered fluorite derivative structures. The rare earth has a secondary effect on RE---PG---O phase development, with the half-filled 4f shell of the Gd representing a transition point for structural stability in the RE series. Systems containing La and Ce exhibit anomalous behaviour with respect to other RE---PG---O systems. In the course of the present study 28 new phases including a new polymorphic type, designated γ-RE₃PGO₇, have been synthesized.     

白云岩和石英岩型铂族矿床中铂钯金的相态分析

以四川大岩子铂钯矿为研究对象,在岩矿鉴定的基础上,将白云岩、石英岩型铂族矿床中铂、钯和金的赋存状态划分为碳酸盐赋存相、硫化物赋存相、金属互化物相和残渣相。研究制定了各相态的浸取剂及浸取条件,并采用ICP-MS测定各相态中铂、钯和金的含量。结果表明,各元素各相态浸取量之和与样品各元素的总量之比分别为:铂94.3%~96.8%、钯99.9%~108%、金91.0%~99.1%;矿物中铂、钯和金主要分布在硫化物赋存相、金属互化物相中。     

硫代硫酸盐浸出脱铜阳极泥中金、银和钯的研究

密度泛函计算和热力学分析表明,相较于Au(I)和Ag(I)离子,Pd(II)离子更容易与S2O3^2-发生配位反应,3种元素均可被氨性硫代硫酸盐溶液浸出。脱铜阳极泥中高含量的锡和锑对硫代硫酸盐浸出贵金属无明显影响,但铅以PbO形态存在时会覆盖在贵金属表面抑制浸出。硫代硫酸盐对脱铜阳极泥中贵金属的直接浸出率低;阳极泥先经氢氧化钠预处理去除部分铅后浸出率有所提高;经碳酸盐转化-醋酸预处理可去除阳极泥中93.8%的铅,硫代硫酸盐对金、银和钯的浸出率达到88.0%、93.4%和80.7%。X射线衍射(XRD)和X射线光电子能谱(XPS)分析表明,醋酸预处理后阳极泥颗粒表面没有出现PbO钝化层。     

合成亚砜BSO萃取钯铂机理研究

研究了合成亚砜BSO萃取Pd、Pt、Cu、Fe和Ni的性能.结果表明低酸度时,Pd2 几乎完全被萃取,其它金属的萃取率极低.钯易于从Pt、Cu、Fe和Ni金属中分离出来,且反萃容易.利用红外光谱研究了BSO萃取Pd和Pt的机理.低酸度时,在钯萃合物的红外光谱中,出现2个新的吸收峰(1122和931cm-1),表明BSO通过硫和氧原子以中性配位机理萃取钯;高酸度时,没有新的红外吸收峰出现,表明BSO以离子缔合机理萃取钯.BSO以离子缔合方式萃取铂.     

Gold based bimetallic catalysts for liquid phase applications

The liquid phase oxidation of D-Sorbitol has been carried out in water using oxygen as the oxidant in the presence of gold based catalyst. Au/C, Pt/C and Pd/C monometallic systems were compared to bimetallic Au/Pd and Au/Pt on carbon. A strong synergistic effect was observed producing a significant increase of reaction rate. Moreover, the addition of gold to Pd or Pt catalyst produced a system more resistant to oxygen poisoning allowing it to work also under a moderate pressure. The effect of varying the molar ratio of the metals has also been studied.     

ICP-AES法测定废催化剂不溶渣中的铂、钯和铑

采用碱熔-碲共沉淀分离富集,用电感-耦合等离子体发射光谱法(ICP-AES)测定精细化工废催化剂不溶渣中的铂、钯、铑含量。系统考察了碱熔解和碲共沉淀富集分离的条件,研究了碲富集物中的主要元素和比例,确定了ICP-AES法测定铂、钯、铑的条件。结果表明,碱熔-共沉淀能够充分分离富集样品中的铂、钯、铑;测定催化剂不溶渣中653~3652 g/t铂、447~3804 g/t钯、539~6433g/t铑时,相对标准偏差(RSD)、样品加标回收率分别为铂0.84%~1.78%、97.0%~99.4%,钯1.05%~1.82%、97.0%~100.6%,铑1.00%~2.12%、98.2%~100.4%。方法分析快速、易于掌握,已用于生产分析中。     

吐温80-硫酸铵-水的固液体系萃取分离Pt(Ⅳ)、Pd(Ⅱ)、Ir(Ⅳ)碘络阴离子

报道了吐温（Ｔｗｅｅｎ）８０－（ＨＮ４）２ＳＯ４－水的固液萃取体系中Ｐｔ（Ⅳ）、Ｐｄ（Ⅱ）、Ｉｒ（Ⅳ）碘络阴离子的萃取行为,在ＨＣｌ－ＮＨ４Ｉ介质中,该体系可萃取Ｐｔ（Ⅳ）、Ｐｄ（Ⅱ）、Ｉｒ（Ⅳ）,而贱金属不被萃取,可用于Ｐｔ、Ｐｄ、Ｉｒ与贱金属的分离。对合成样进行了萃取分离,并初步探讨其机理。     

A new partitioning process for high-level liquid waste by extraction chromatography using silica-substrate chelating agent impregnated adsorbents

To separate the long-lived minor actinides (MA(III) = Am(III), Cm(III)) and some specific fission products (FP) such as Pd(II), Mo(VI), Cs(I) and Sr(II) from high-level liquid waste (HLLW), we have been studying a new partitioning process by extraction chromatography using several novel silica-based extraction resins. In this work, we examined the separation behavior of the elements contained in a simulated MA-effluent by the CMPO/SiO₂P packed column. In addition, as an attempt to further isolate Am(III) and Cm(III) from the heavy RE(III) such as Eu(III), Gd(III) and Dy(III) contained in the MA-effluent, we investigated the possibility of separation by using a silica-based cationic exchange resin. Furthermore, to isolate Sr(II) from the HLLW, adsorption and separation performances of Sr(II) and some other FP elements were studied by using a novel silica-based crown ether extraction resin, DtBuCH18C6/SiO₂P. The experimental results demonstrated that the elements in the simulated MA-effluent can be successfully separated to (1) Pd, (2) MA-hRE and (3) Zr–Mo, by CMPO/SiO₂P packed column using water and a dilute DTPA solution as eluents. Am(III) and Cm(III) are expected to be effectively separated from light RE(III) and Y(III) by the SiSCR cationic resin. However, more effective separation between Am(II), Cm(III) and heavy RE(III) such as Eu(III), Gd(III) and Dy(III) needs further approach. DtBuCH18C6/SiO₂P showed a highly selective adsorption for Sr(III) so that the Sr(II) could be completely separated from other FPs except a portion of Ba(II).