碘量法与电重法测定氧化铜矿中酸溶铜的方法比较

试料用含亚硫酸钠的硫酸(10%)溶液浸取,使铜的氧化物矿物选择溶解,过滤后加入溴饱和盐酸掩蔽砷和锑等金属,补加少量硫酸,蒸干后用硫酸溶解,用硫代硫酸钠标准溶液滴定测定氧化铜矿中酸溶铜的含量,此方法快速、稳定、准确。选取14个日常分析的样品进行测定,其结果与电解重量法比对,结果令人满意。     

电解重量法测定混合铜矿中自由氧化铜

建立了用于混合铜矿石中自由氧化铜测定的方法。试样用含亚硫酸钠(6g/L)的硫酸(10%)溶液浸取2h,选择性溶解铜氧化物,过滤并煮沸滤液,用去离子水稀释后电解。溶液中的铜离子电积至阴极铂网上。用火焰原子吸收光谱法检测残余于电解后液中的铜离子;同时用硝酸(1+1)溶解铂网上的铜,并用火焰原子吸收光谱法检测与阴极铜共电积的杂质元素含量,用铂阴极差重加上电积后液残余铜含量并减去共电积的杂质元素含量可计算出氧化铜矿中酸溶铜含量。与碘量法相比,不用肉眼观察颜色变化确定终点,人为误差小,结果稳定、准确。通过对加拿大氧化铜矿标准物质AMIS0050进行测定(n=12),方法准确度可靠。并选取15批次的氧化铜矿检测,与经典碘量法比对,结果令人满意。     

Characterization of Copper and Aluminum AC Electrochemical Oxidation Products

Non-equilibrium electrochemical metal oxidation is one of the methods to obtain the power-saturated nanosized metal oxides. AC electrochemical separate copper and aluminum oxidation in an aqueous sodium chloride solution is performed. It results in the phase transformations of the obtained copper (I) oxide and boehmite during the storing in solution. Phase composition, pore structure characteristics and morphology of the products are considered. Their pore structure is preferably formed by mesopores. Carbonate ion adsorption of metal oxides/oxyhydroxides is due to their high affinity. The contamination of the power-saturated nanosized products of electrolysis with carbon-containing impurities is not a problem because some undesirable compounds may be removed by heat treatment, but others do not negatively affect the operating performance. Product of AC electrochemical copper oxidation is characterized by particle shape anisotropy (spindle-shaped particles of copper oxide and copper carbonate hydroxide wire bundles) that positively affects the some properties. The product of AC electrochemical aluminum oxidation has a flower-like structure.     

氧化铜转化法制备氢氧化钡

以硫化钡为原料,在水溶液中与氧化铜反应,生成氢氧化钡。副产物硫化铜经氧化焙烧生成氧化铜,循环使用于下一次合成中。放出的二氧化硫经石灰乳吸收用来制备亚硫酸氢钙。     

煤中溴的淋滤行为研究

在不同pH值条件下对来自重庆磨心坡矿煤样进行柱淋滤实验,用电感耦合等离子体质谱法( ICP-MS )测定煤中溴的含量及四种淋滤介质在不同时间段获取的淋出液中溴的浓度。结果表明,淋滤液的pH值、淋滤时间、煤中溴的赋存形态及在煤中赋存部位对溴的淋出有重要影响。淋滤液的酸性越强,煤中溴的最大淋出浓度越大,一定时间内溴的总淋出率也越高。 pH值为2的淋滤液,在淋滤前40h内淋出溴的量占总淋出量的80.65%;pH值为4的淋滤液,在淋滤前50h内淋出溴的量占总淋出量的89.42%。在酸性淋滤液作用下,首先被淋出的是存在煤颗粒表面的碳酸盐态和铁锰结合态溴,然后煤基质内部的水溶态和离子交换态溴才被淋出。柱淋滤实验表明,煤中溴在风化过程中,会被酸性雨水淋溶出来进入周围土壤或地表水体,造成周围环境溴的富集。     

金矿石化学物相分析选择性溶剂实验探索

运用碘-碘化钾氨性溶液作为裸露及半裸露包裹金的选择性溶剂,硫代硫酸钠-亚硫酸钠溶液作碳酸盐包裹金的选择性溶剂,以及溴素-氯化钠溶液作硫化矿包裹金的选择性溶剂进行实验探索.使用国家标准物质GBW07190对方法进行评价,并对该标准物质中其他矿物中金(AAu)的这一相态做了更详细的分离,测定了其中的碳酸盐包裹金、褐铁矿包裹金、黄铁矿包裹金,石英和硅酸盐包裹金的含量.火焰原子吸收法测定金的检出限是0.05×10-6;石墨炉原子吸收法测定金的检出限是0.30×10-9.RSD为0.29%~11.6%,RE为0.11%~8.40%.方法适用于各种金矿物的相态分离,进一步细化了金的各种赋存状态,所得结果令人满意.完全满足矿床划带、选矿试验和成矿规律研究的实际需要.     

AC Electrochemical Copper and Aluminum Oxidation in Sodium Acetate Solutions

Electrochemical copper and aluminum oxidation using alternating current of industrial frequency was carried out in an aqueous sodium acetate solution. Simultaneous oxidation of metals accelerates copper oxidation, but does not significantly influence the aluminium oxidation rate. It results in the preparation of the copper-aluminum oxide system with a high content of copper oxide (up to 70 wt %). High energy consumption due to the voltage loss to overcome the resistance of the oxidation product layer on the electrode surface considerably limits the process and its product application. Furthermore, the chemical aluminum oxidation in alkaline medium of an aqueous sodium acetate solution instead of electrochemical one does not result in the power-saturated, nanosized metal oxide formation. The results obtained do not only underline the new technology of nanomaterial production, but also allow scientists to consider the mechanisms of the metal oxidation AC-process.     

Modulation of the Aerobic Oxidative Polymerization in Phenylazomethine Dendrimers Assembling Copper Complexes

The aerobic oxidative polymerization of phenol derivatives can provide poly(phenylene oxide)s, which are known as engineering plastics. This oxidation can be carried out with atmospheric oxygen molecules as the oxidizing reagent in the presence of copper complexes as the catalyst; however, stoichiometric or excess amounts of bases are also generally required. By using a phenylazomethine dendrimer complexed with several equivalent amounts of copper chloride, the additive (base)‐free polymerization of 2,6‐difluorophenol was successful with a very small amount of the catalyst (0.7 mol % of copper for the monomer) because the dendrimer was composed of many Schiff base units, affording a base and catalyst (copper complex) condensed reaction field. The resulting polymer was nearly linear and the molecular weight was very high. When the equimolar amount of the copper complex in one dendrimer molecule was increased, the polymer obtained under this reaction condition was rather branched, resulting in a higher glass transition temperature.     

用于甲醇直接气相氧化羰基化的负载铜催化剂

 采用浸渍法制备了负载型铜基催化剂,并用其催化甲醇直接气相氧化羰基化合成碳酸二甲酯(DMC), 考察了浸渍溶剂、载体、助催化剂和铜含量的影响. 结果表明,以CuCl为活性组分原料、浓氨水为浸渍溶剂和活性炭为载体制得的负载铜催化剂显示出很高的催化活性,在特定的反应条件下,该催化剂上甲醇的转化率可达27.7%, DMC选择性可达95%. 分子筛负载的铜催化剂上甲醇的转化率低于1%, 但是生成DMC的选择性高达100%. 催化剂活性随着Cu负载量的增加而增大,但负载量过高可引起甲醇的过度氧化反应,导致DMC选择性下降. 催化剂中添加KOH或钯化合物,有利于提高以CuCl2为活性组分原料制得的铜催化剂的活性,但同时也促进了副反应的发生. 随着反应时间的延长,催化剂的活性组分流失,活性下降,但是生成DMC的选择性维持在95%左右.     

氧化铜-过氧化聚吡咯-还原氧化石墨烯复合膜修饰电极非酶检测葡萄糖

先以氧化石墨烯(Graphen oxide,GO)为阴离子掺杂剂,采用电化学聚合法制备了聚吡咯-氧化石墨烯复合膜(PPy-GO)。分别在0.10 mol/L Na Cl和0.10 mol/L NaOH溶液中对其进行还原和过氧化处理,制得过氧化聚吡咯-还原氧化石墨烯复合膜(OPPy-ERGO)。再以此OPPy-ERGO复合膜为载体,采用电化学沉积法制备了氧化铜-过氧化聚吡咯-还原氧化石墨烯复合膜修饰电极(CuO-OPPy-ERGO/CCE)。通过扫描电镜和电化学方法对此电极进行表征,研究了葡萄糖在此修饰电极上的电化学行为。结果表明,此电极对葡萄糖的电氧化过程表现出高的催化活性和良好的抗干扰能力。在0.20 mol/L NaOH溶液中,安培法检测葡萄糖的线性范围为5.0×10~(-7)~1.0×10~(-3)mol/L,检出限(3Sb)为2.0×10~(-7)mol/L,灵敏度为121.8μA/(mmol·L~(-1))。该电极用于血清中葡萄糖含量的测定,加标回收率为96.0%~110.1%。