制备多孔镍负载TiO2薄膜光催化降解喹啉和化工废水

为了获得具有高光催化活性和稳定性的TiO2薄膜,采用浸渍涂布法不加黏结剂将Deguessa P-25TiO2固定在泡沫镍基片上,制备成泡沫镍基负载TiO2薄膜,并以Ti-10薄膜为光催化组件制备了一种新型连续流内循环光催化反应器。表征结果显示:P-25薄膜呈混晶相,增大负载浓度会增加基片上结晶质(如锐钛矿相(101))数量、团聚颗粒数量、表面微裂痕以及比表面积;高温煅烧下泡沫镍基片上Ni元素以金属Ni和NiO形式扩散到薄膜表面,形成NiO-Ni体系,有助于提高薄膜的光催化活性;当负载P-25质量分数为10%时,薄膜表层Ni原子比为12.29%,此时薄膜具有最佳光催化活性。以Ti-10样品为光催化薄膜组件制备了一种连续流光催化反应装置,该装置降解化工废水的实验结果显示反应装置连续运行一周,出水可达到一级排放标准。     

SiO2-TiO2薄膜制备及其光催化性能研究

Sol-gel法制备SiO2-TiO2复合薄膜，进行甲醛的光催化降解实验，研究了SiO2掺杂量、薄膜焙烧温度、甲醛溶液pH值及初始浓度对光催化性能的影响。结果表明，500℃焙烧1h，掺杂质量SiO2：TiO2=12：100时，SiO2-TiO2薄膜的光催化活性最高，150min后甲醛降解率达76％，是单纯TiO2薄膜的1．3倍，该薄膜稳定性较好，经重复8次使用，最大降解率只下降4％。     

纳米TiO2光催化降解亚甲基蓝

在以钛酸丁酯为钛源,采用溶胶-凝胶法合成制备纳米TiO2催化剂样品的基础上,将其用于在紫外光照射和无光照射条件下进行亚甲基蓝降解的实验研究,并与P-25纳米TiO2进行光催化降解对比研究。对在不同条件下合成制备样品的光催化降解率的差异,通过X射线粉晶衍射、扫描电镜等从物相组成、微观结构等因素上进行了分析和探讨。结果表明,采用溶胶-凝胶法在450℃焙烧2 h所得到的纳米TiO2具有很好的光催化降解亚甲基蓝的能力,当催化剂样品质量浓度为2.5 g/L,亚甲基蓝初始浓度为5.0 mg/L时,室温下光催化反应3 h,其降解率达98%以上,其光催化降解率比P-25纳米TiO2高;光催化降解率与催化剂样品的制备条件、物相组成、颗粒尺寸等因素有关。     

镍酞菁修饰镍铝水滑石的制备及光催化性能研究

通过共沉淀法将水溶性四羧基镍酞菁(Ni Pc)负载到镍-铝碳酸根水滑石(Ni Al-LDHs)上,制备负载型催化剂(Ni Pc/Ni Al-LDHs)。采用XRD、FT-IR、UV-Vis、TG-DTA和SEM等技术对酞菁衍生物和Ni Pc/Ni Al-LDHs的结构进行表征。结果表明Ni Pc没有改变Ni Al-LDHs的晶型结构和热稳定性能。在10 mg/L、25 m L的甲基橙溶液、p H值为3、H2O2用量50μL的条件下,Ni Pc/Ni Al-LDHs协同H2O2光催化氧化降解甲基橙3 h后,甲基橙剩余率为16.33%。溶液p H值在3~7范围内,Ni Pc/Ni Al-LDHs/H2O2都能有效光催化氧化降解甲基橙,且光催化氧化降解过程涉及到羟基自由基反应。     

硅烷偶联剂改性TiO2/膨胀石墨复合材料的制备及其光催化性能研究

以硅烷偶联剂黏结剂,利用溶胶-凝胶法将TiO2（P25）负载在膨胀石墨上,利用XRD、EDS以及SEM等分析技术对TiO2/膨胀石墨复合材料进行表征;以橙黄Ⅱ为目标降解物,考察了TiO2/膨胀石墨复合材料光催化性能以及重复使用性能。结果表明：随着TiO2含量的增加,TiO2/膨胀石墨复合材料的光催化效率随之增加,对橙黄Ⅱ的光催化降解符合一级反应动力学方程,TiO2负载量为15%时,反应速率常数为0.387 h-1,高于P25的反应速率常数。TiO2/膨胀石墨复合物使用4次仍保持较高的光催化活性。     

二价铁活化过硫酸盐去除水中苯胺

零价铁和硝基苯反应后生成二价铁和苯胺,而苯胺也是地下水污染物。硫酸根自由基具有强氧化性,可以降解苯胺。而二价铁可以活化过硫酸盐产生硫酸根自由基,进而去除苯胺。本文研究了二价铁浓度、过硫酸盐浓度、苯胺初始浓度、体系初始pH、反应温度等因素对二价铁活化过硫酸盐去除水中苯胺处理效率的影响。结果表明:1)Fe2+活化过硫酸盐生成SO-4·能快速并有效氧化降解苯胺,对于目标浓度为1 000 mg/L的苯胺而言,Fe2+浓度为3.3 mmol/L,Na2S2O8浓度为4.4 mmol/L时,对苯胺有较佳降解效果,苯胺的降解率为86.33%。2体系对较低浓度的苯胺降解效果较好,当污染物初始浓度由1 000 mg/L降低到500 mg/L和100 mg/L时,苯胺降解率由86.33%升高为90.27%和97.16%。3初始pH对苯胺的降解率影响较大,中性条件下(pH=7左右)降解率较好,高初始pH(pH=9,11)和低初始pH条件(pH=3,5)下均低于中性条件下苯胺的降解效率。4体系的温度变化对降解率影响不明显。     

钛柱撑蒙脱石光催化降解亚甲基蓝的实验研究

采用TiCl4水解法制备钛柱化剂与钠蒙脱石离子交换后,自然风干、焙烧得到具有稳定层结构、大晶面间距(2.26 nm)和大比表面积(285.7 m2/g)的钛柱撑蒙脱石(Ti-PILM)。用制备的Ti-PILM对亚甲基蓝(MB)进行紫外光作用下的光催化降解实验,并与层结构不规则的Ti-PILM在相同条件下对MB的光催化效果进行对比,研究MB的初始浓度、Ti-PILM投放量、pH对光催化降解效果的影响。结果表明,室温条件下,降解时间120 min,当Ti-PILM投样量等于2 g/L,MB初始浓度为50 mg/L,pH为7时,Ti-PILM对MB降解速度最高。与纳米TiO2不同,Ti-PILM对MB的降解率和降解初速率与MB在其表面的吸附行为密切相关。     

N2气氛下煅烧的黄铁矿对As(Ⅲ)的吸附作用

微量As(Ⅲ)是水中较难去除的毒性物质,天然黄铁矿对水中As(Ⅲ)的去除能力低于磁黄铁矿.将黄铁矿在氮气下高温煅烧使其转变为由磁黄铁矿构成的多孔结构化材料,具有较高的比表面积和表面化学反应活性,在地下水As(Ⅲ)去除方面具有潜在的应用前景.考察了煅烧温度、煅烧时间、pH值以及溶解氧对去除水中As(Ⅲ)的影响.结果表明黄铁矿煅烧生成的单斜磁黄铁矿对As(Ⅲ)具有最佳去除效果,最佳煅烧条件为600℃煅烧1 h;在水溶液有溶解氧条件下煅烧黄铁矿去除As(Ⅲ)的适宜p H值范围较宽(4~10),而在水溶液缺少溶解氧条件下适宜pH值则变为7~10;煅烧黄铁矿在有氧水溶液中对As(Ⅲ)的吸附比缺氧水溶液中的吸附效果好.     

La0.5Sr0.5Co0.8Mn0.2O3-δ钙钛矿对过一硫酸盐降解水中四溴双酚A影响实验研究

研究了La_0.5 Sr_0.5 Co_0.8 Mn_0.2 O_3-δ钙钛矿活化过氧单硫酸盐对四溴双酚A(TBBPA)的降解作用,重点探讨不同的煅烧温度制备镧锶钴锰钙钛矿(LSCM82)的催化性能对过一硫酸盐降解TBBPA的影响,以及溶液的不同初始pH条件对优选材料体系降解效率的影响。结果发现,变价离子的氧化还原对Co3+/Co2+和(Mn4++Mn3+)/Mn2+是催化剂活性的主要贡献者。煅烧温度为950 ℃且具有适量间隙氧及比表面积的LSCM82-950催化反应速率较高。在中性pH环境条件下应用LSCM82-950活化过一硫酸盐降解水中TBBPA污染物,既可以使催化剂钴浸出很少,又能达到最大程度的TBBPA降解效果。     

粉末活性炭增强臭氧氧化去除铁锰

为了有效解决地下水中铁锰超标的问题,本文提出了一种新的粉末活性炭(PAC)和臭氧联用去除铁和锰的方法,并探索PAC在臭氧氧化处理水中铁和锰的作用机理。首先研究PAC和臭氧单独处理铁和锰的效果;然后研究PAC和臭氧联用处理铁和锰的效果,并探究不同条件(pH、温度、PAC用量、氧化剂质量浓度)对水中铁和锰去除效果的影响;最后研究PAC在臭氧氧化处理水中铁和锰的作用机理。结果表明：PAC在不同条件下都能强化铁和锰被臭氧氧化,在PAC用量为0.3 g/L、臭氧质量浓度为5 mg/L、pH值为7.0、室温的条件下,5 min内铁和锰混合溶液质量浓度由0.5 mg/L迅速降到0.1 mg/L以下,达到相应排放标准要求;随着PAC用量的增加,铁和锰的残留质量浓度逐渐降低,这说明反应高度依赖PAC表面的活性位点,进一步证实了PAC对水中铁和锰去除效果的影响。扫描电镜(SEM)和Mapping分析等表征结果表明,反应后在PAC表面形成了铁氧化物和锰氧化物涂层,而这些氧化物涂层会进一步加快水中游离铁和锰的去除。     

Modifications of the porous network of sandstone accompanying the formation of black varnish

Black varnish commonly develops on rain-washed fine-grained monument sandstone. Stone modifications are, to the naked eye, limited to 10-μm thick black film and underlying modified zone about 1-mm thick. Transfer properties (absorption and drying kinetics and permeability) are, however, modified several centimetres under the surface. The present study investigates the modifications of black-varnish covered siliceous sandstones taken from Alsatian monuments (East of France) and of fresh sandstone undergoing wetting–drying cycles in the laboratory. Double-coloured thin-sections revealed gradual changes in the porous network, up to 3 cm under the black varnish. SEM observations showed that the film was mainly composed of iron and phosphorus while the modified zone was rich in calcium and sulphur. Fifty capillary absorption–drying cycles were carried out on fresh sandstone. Absorption kinetics was measured at each cycle. A continuous decrease of sandstone absorption kinetics over the fifty cycles was interpreted as a reorganisation of the porous network, reducing the connectivity of the porous network although total porosity remained unchanged. Wetting–drying cycles carried out under an environmental microscope (ESEM) showed a displacement of the finest particles (clay clusters), filling the macroporosity and decreasing the connectivity.     

The selective removal of Co(II) from Ni(II) by coprecipitation with manganese in ammoniacal solutions

The coprecipitation of cobalt(II) and nickel(II) with manganese in ammoniacal solutions has been studied. It was found that cobalt and nickel were precipitated with the aid of manganese at pH 9.3–10.2. However, the rate of precipitation of manganese was about five times that of cobalt. The recovery of these divalent ions by precipitation increased as the pH of the solution increased, while the selectivity of cobalt against nickel decreased with the increase of pH. The partial pressure of oxygen had also an important role in the precipitation of manganese and cobalt but little effect on the up-take of nickel. As the oxygen pressure increased, manganese and cobalt oxidized at a fast rate and the rate of coprecipitation of cobalt with manganese increased. Typically, more than 90% of cobalt was recovered readily by coprecipitation with manganese, while very little nickel was removed from the solution.     

氨基膨润土对铜镍镉污染土壤的钝化修复研究

采集土壤,加入铜、镍和镉制成重金属污染土壤。以四乙烯五胺改性膨润土和膨润土原土作为修复剂,通过模拟酸雨和混合提取剂提取有效态重金属,评价膨润土和氨基膨润土对土壤中铜、镍、镉的钝化效果。结果表明:p H=3. 5的模拟酸雨对各污染土壤中重金属离子的提取率均在0. 1%以下。混合提取剂对污染土壤中有效态金属的提取能力比模拟酸雨强很多。添加膨润土原土和氨基膨润土均能钝化土壤中的铜、镍和镉,氨基膨润土上嫁接的氨基对金属有络合作用,因而比膨润土原土对铜、镍和镉具有更强的钝化能力。综合评价表明氨基膨润土是一种对铜、镍和镉污染土壤具有应用前景的钝化修复材料。     

铵盐镍基电镀金刚石钻头的电化学机理研究及应用

以微机控制电化学分析系统对铵盐镍基胎体镀层的电化学机理进行研究,试验了硫酸镍用量、氯化铵用量、镀液温度和镀液的pH值对镍沉积的影响,结果表明保持镀液适当高的pH值、略低的温度和加入氯化铵,可使镍沉积的极化增大,从而使镀层晶粒变小,结晶致密,且氯化铵的加入没有改变阴极过程的控制步骤。在N iSO4.6H2O 280 g/L,NH4Cl 19 g/L,H3BO335 g/L,十二烷基硫酸钠0.1 g/L;镀液温度45℃±1℃,pH值5.2,电流密度3.6 A/dm^2条件下电镀Φ41/27 mm室内钻头,钻进可钻性Ⅷ级的绢云母化含石英斜长石玢岩,钻进时效平均达到1.94 m/h,钻头的磨损约为0.092 mm/m,与普通镍-钴胎体钻头的使用寿命相差不大;但其钻进时效要比镍-钴胎体钻头高0.18 m/h,即约高10%,为野外生产试验提供了试制钻头的可靠资料和经验。     

Nettle ash as a low cost adsorbent for the removal of nickel and cadmium from wastewater

This study was focused on nettle ash as an alternative adsorbent for the removal of nickel (II) and cadmium (II) from wastewater. Batch experiments were conducted to determine the factors affecting adsorption of nickel (II) and cadmium (II). The adsorption process is affected by various parameters such as contact time, solution pH and adsorbent dose. The optimum pH required for maximum adsorption was found to be 6. The experimental data were tested using Langmuir, Freundlich and Tempkin equations. The data were fitted well to the Langmuir isotherm with monolayer adsorption capacity of 192.3 and 142.8 mg/g for nickel and cadmium, respectively. The adsorption kinetics were best described by the pseudo second order model. The cost of removal is expected to be quite low, as the adsorbent is cheap and easily available in large quantities. The present study showed that nettle ash was capable of removing nickel and cadmium ions from aqueous solution.     

Usable Values of Nickel Ore and Nickel Concentrate Certified Reference Materials

The preparation and characterisation of three nickel ores and two nickel concentrate certified reference materials are described in this paper. The samples of nickel ore and nickel concentrate were collected from the Hongqiling nickel deposit in Jilin province. The raw materials were crushed and passed through a 2.0‐mm sieve. The rough samples were then ground for 48 hr in a high‐alumina ball mill to a final size of < 0.074 mm. Homogeneity of the samples was tested by X‐ray fluorescence spectrometry (WD‐XRF) and inductively coupled plasma‐atomic emission spectrometry (ICP‐AES). The relative standard deviations (RSD) of results on mass fraction measurements by WD‐XRF were < 1.0% m/m for eighteen components. F‐tests showed that all five samples were homogeneous. Nineteen laboratories contributed with measurement results (2127 in total) for the certification of mass fractions for twenty‐three elements and compounds. Twenty‐three components in the nickel ores and twenty components in the nickel concentrates were characterised as certified values, while the Ni mass fractions ranges from 0.1 to 9.02% m/m in these certified reference materials. These five samples were approved as national certified reference materials by the National Organisation of Reference Materials of China in 2012.     

干旱高山区地电化学法寻找铜镍矿研究——以青海化隆拉水峡铜镍矿区为例

为解决干旱高山区的深部找矿问题和探索地电化学法在干旱高山区寻找隐伏铜镍矿产的可行性,在青海化隆拉水峡铜镍矿区开展了地电提取测量法、土壤离子电导率测量法寻找隐伏铜镍矿的试验研究,通过对已知矿体的地电化学法找矿试验,在隐伏铜镍矿体上测出了清晰的地电化学异常。对矿区的深部及外围的找矿预测中,在A区发现3个地电化学Ni、Cu及电导率异常,在B区发现3个地电化学Cu异常、1个Ni异常、3个电导率异常,在C区发现了3个地电化学Cu异常、2个地球化学Ni异常、3个电导率异常,推测在上述地电化学异常区内寻找隐伏铜镍矿会有新的突破。     

峨眉山玄武岩和白马层状岩体的铬镍地球化学

文章讨论了峨眉山玄武岩及白马基性、超基性岩体的微量元素地球化学特征。对Cr、Ni富集的地球化学条件进行了探讨,认为在母岩浆分离结晶早期形成的堆积层,即结晶度很小的橄榄岩有利于寻找富Cr、Ni层位。     

大洋多金属结核和深海沉积物标准物质中铂族元素的中子活化分析

采用镍锍试金预富集中子活化分析方法,测定了大洋多金属结核标准物质ＧＳＰＮ２、ＧＳＰＮ３和深海沉积物标准物质ＧＳＭＳ２、ＧＳＭＳ３中的铂族元素;根据大洋样品成分特征,对常规的镍锍试金配方和熔炼条件作了改善;计算了活化分析中的铂族元素干扰核反应,校正了Ａｕ对Ｐｔ的二级干扰;选用羰基化镍粉配料,降低了铂族元素空白值。用国家一级标准物质ＧＢＷ０７１０２作了对照分析,结果与标准值相符。