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。     

基于响应面的可见光催化材料制备与优化

为使TiO₂能在可见光作用下发挥光催化作用,并易于从水中分离,将掺有稀土金属离子Er³⁺的上转换发光剂Er³⁺:YAlO₃与TiO₂采用溶胶-凝胶法结合,再将其负载于聚氨酯海绵(PS)载体表面,制备Er³⁺:YAlO₃/TiO₂-PS光催化剂。利用响应面(RSM)方法对光催化材料制备条件进行优化,根据中心组合设计方法设计出3因素5水平析因实验,以光催化剂对苯酚的降解率作为响应值,得到最佳的催化剂制备条件:在水热处理温度110~114 ℃、光催化剂中TiO₂质量浓度60~65 mg/L、海绵/溶胶负载比20 g/L时苯酚降解率最佳,与实测结果相符。     

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。     

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。     

紫外光及日光下天然金红石光催化降解苯酚的研究

研究了山西代县天然金红石在紫外光和日光照射条件下对苯酚的光催化降解性能,考察了光照时间、pH值、苯酚初始浓度以及H2O2添加量对降解过程的影响。在紫外光照射下,酸性条件(pH=3.5)利于光催化降解,中性和碱性条件下降解效率较低;当初始浓度为60mg/L时,降解速率可达1.922mg/(L.h);H2O2作为电子捕获剂可提高苯酚降解速率,最佳投加量为2mL/L。在日光条件下,天然金红石对苯酚表现出良好的降解性能,照射7h后,降解率达87.68%,仅略低于P25型TiO2(99.72%),可在14h内完全降解。根据电子探针和X射线衍射分析结果,认为天然金红石晶格中的V、Fe等杂质可能是提高其可见光响应效果和光催化活性的主要原因。     

共存重金属离子对针铁矿活化过硫酸盐去除水中磺胺吡啶的影响

基于硫酸根自由基的高级氧化技术能有效降解水中磺胺类药物残留。由于在自然环境中共存重金属会对环境修复效果产生一定影响,文中重点研究了不同pH环境条件下不同重金属离子对针铁矿活化过硫酸盐(PS)去除水中磺胺吡啶(SPY)的影响。不同类型重金属离子(Cu^2+、Pb^2+、Cd^2+,0.2mmol/L)在反应体系(初始条件:针铁矿,1.0g/L;PS,4mmol/L;SPY,10mg/L;pH=8.2)中对SPY的降解对比研究发现:在无重金属共存的条件下,针铁矿/PS体系降解SPY的去除率为25.2%;Pb^2+和Cd^2+对针铁矿/PS体系的影响较弱,去除率分别为30.8%和34.8%;Cu^2+的促进作用很大,可以使SPY被完全降解(100%)。机理分析认为,在针铁矿/PS体系中Pb^2+和Cd^2+主要通过影响吸附作用导致磺胺吡啶被去除,而Cu^2+主要通过自身活化PS的作用。不同pH条件(3.0,8.0,12.0)实验证实弱碱性条件下,Cu^2+/针铁矿/PS能够发挥较高的活性从而降解SPY。本文结果为采用针铁矿活化过硫酸盐技术修复类似复合污染地下水环境提供了实验依据。     

热活化过硫酸盐降解氧氟沙星特性及响应面优化

为了探究热活化过硫酸盐（PS）技术对水中氧氟沙星（OFX）的氧化降解作用,考察了反应温度、体系的初始pH、PS的初始浓度、OFX的初始浓度对OFX降解效果的影响;并在单因素实验的基础上,选取反应时间、体系的初始pH、PS的初始浓度和OFX的初始浓度4个因素进行了响应面优化实验。结果表明：最佳降解条件为,反应温度60℃、PS初始浓度4.0 mmol/L、pH=4.7、OFX初始浓度0.03 mmol/L、反应时间60 min,此时OFX的降解率为81.29%;4个因素对热活化PS降解OFX均有影响,其影响显著性从大到小为反应时间、OFX的初始浓度、PS的初始浓度、初始pH。利用响应曲面法模拟出反应体系的最佳条件,经实验验证,OFX降解率为93.78%,与预测最佳结果95.00%基本相符,表明模型可靠有效。     

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.     

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。     

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.     

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。