Formation of CoAl layered double hydroxide on the boehmite surface and its role in tungstate sorption

Sorption of tungstate on boehmite(γ-Al OOH)is increased by co-sorption with Co~(2+)over the near-neutral p H range.Batch uptake experiments show up to a 3-fold increase in tungstate uptake over the range WO_4~(2-)=50–1000μmol/L compared to boehmite not treated with Co~(2+).Desorption experiments reveal a corresponding decrease in sorption reversibility for tungstate co-sorbed with Co~(2+).Reaction of boehmite with Co~(2+)results in the formation of Co Al layered double hydroxide(LDH),as confirmed by X-ray diffraction and X-ray absorption spectroscopy.Tungsten L_3-edge X-ray absorption near edge structure(XANES)reveals that W(VI)is octahedrally coordinated in all sorption samples,with polymeric tungstate species forming at higher tungstate concentrations.X-ray diffraction and X-ray absorption spectroscopy indicate that the mechanism for enhancement of tungstate uptake is the formation of surface complexes on boehmite at low tungstate concentrations,while exchange into the Co Al LDH becomes important at higher tungstate concentrations.The results provide a basis for developing strategies to enhance tungstate sorption and to limit its environmental mobility at near-neutral pH conditions.     

过渡金属元素掺杂改性SCR对零价汞的催化氧化性能

为提高商用SCR催化剂对Hg0(零价汞)的催化氧化活性,研究了过渡金属对其进行掺杂改性的方法,并利用固定床反应平台考察了不同试验条件下改性催化剂对Hg0的氧化效率. 结果表明:Y、Zn、Ni和Zr等过渡金属的掺杂可明显抑制SCR催化剂的催化活性,而Fe、Cu掺杂改性SCR催化剂对Hg0的催化氧化性能有显著提升. 在反应温度为350 ℃、空速比为370 000 h-1、φ(HCl)为1×10-5的条件下,Fe、Cu掺杂改性的SCR催化剂对Hg0的氧化效率均能达到90%以上,并且Fe掺杂改性后的SCR催化剂的脱硝性能也未受到明显影响. 借助XRD和XPS等表征手段,对反应前后Fe掺杂改性SCR催化剂进行了研究,表明Fe改性SCR催化剂遵循Mars-Maessen和Langmuir-Hinshelwood机制,可明显提高对Hg0的催化氧化效率,因此,应用前景较好.      

不同制备方法对Cu-SSZ-13催化性能的影响

为了考察制备方法对Cu-SSZ-13催化剂在氨选择性催化还原NO_x(NH_3-SCR)中催化性能的影响,使用不同的方法和载体,制备出理化性质有明显差异的3种催化剂(Cu_(3.9)-Na_(0.8)-SSZ-13、Cu_(5.1)-H-SSZ-13和Cu_(4.0)-Na_(4.0)-SSZ-13),并考察3种催化剂的水热稳定性和抗硫中毒性能.结果表明,由于具有适宜的Cu负载量,并且Cu物种的稳定性极高,一步合成法制备的Cu_(3.9)-Na_(0.8)-SSZ-13催化剂的水热稳定性优于液相离子交换法制备的两种催化剂.而以H-SSZ-13为载体,液相离子交换法负载Cu物种制备的Cu_(5.1)-H-SSZ-13催化剂具有最优的抗硫中毒能力,这与其较多的酸性位有关.因此,含有较多酸性位并且活性物种稳定性高是制备水热稳定性和抗硫中毒能力较优的Cu-SSZ-13催化剂的关键.     

城市污水厂污泥催化热水解制备聚合氯化铝铁

采用催化热水解分离城市污水厂污泥中的有机物和无机物,并将无机物制备成了聚合氯化铝铁。研究结果表明:在盐酸质量浓度为20%,反应时间为2 h,反应温度为90℃,固液比1∶3条件下,制备的液体聚合氯化铝铁的Al_2O_3含量为9.34%,Fe_2O_3含量为2.11%,盐基度为47.8%;制备的产品在城市污水处理中取得了较好处理效果。同时采用红外光谱(IR)技术对制备的聚合氯化铝铁的聚合形态进行表征。     

Cu-Mn-Zr复合催化剂制备及其催化氧化乙酸乙酯性能

采用溶胶凝胶法制备了4种不同金属摩尔比的Cu-Mn-Zr复合催化剂，利用BET、XRD和XPS对其进行了表征分析，通过固定床管式反应器评价了其对乙酸乙酯模拟气体的催化活性，定性测定了其催化反应降解产物.结果表明，Mn的加入增大了催化剂的比表面积和总孔容，催化剂的N₂吸附-解吸等温线为IV型.Cu-Zr（1：1）催化剂观察到氧化铜晶体和四方晶型氧化锆晶体，氧化铜晶体随着Cu比例的减小而降低，Mn的加入导致氧化锆晶体消失.催化剂无固定形态，呈现良好的分散性.增大Mn/Zr摩尔比能提高催化活性.Cu-Mn-Zr的适当组分比能提高其低温催化活性，其中Cu-Mn-Zr（1：1：1）催化剂的低温催化活性与CO₂的选择性较佳，在200℃时对CO₂的选择性达到96.7%.降解产物分析表明，乙酸乙酯降解中间产物有乙酸和乙醇，最终降解产物主要有CO₂和H₂O等.     

Photochemical degradation of methylparathion in the presence of humic acid

Photochemical degradation of methylparathion (O,O,-dimethyl O-4 nitrophenylphosphorothioate) in the presence of humic acid between pH 2 and 7 was monitored by differential pulse polarography. Humic acid was not electro-active under the experimental conditions used in this study. Only the pesticide and its main degradation product at pH 2 exhibited polarographic signals. Photolysis of methylparathion in acid media was sensitized by humic acid since the pesticide did not degrade in the absence of this compound. Methylparathion degradation in the presence of humic acid was observed at each of the studied pHs. The reaction was first-order with rate constant values ranging from 2 × 10^?3 to 6.3 × 10^?3 min^?1.     

纳米零价铁及其双金属体系对菲的降解研究

以实验室合成的纳米零价铁(n ZVI)及其双金属(n ZVI/Cu和n ZVI/Ni)为反应材料,对菲(Phenanthrene)的去除进行研究.表征结果表明:纳米颗粒平均粒径均为80~100 nm,主要以α-Fe0的形式存在.批实验结果表明,5 g·L-1的n ZVI,n ZVI/Cu和n ZVI/Ni对菲溶液均有去除效果,其去除效率依次为n ZVI/Nin ZVI/Cun ZVI.溶液初始p H为7.5时,5 g·L-1的n ZVI/Ni去除88%0.5 mg·L-1的菲只需3 h,而n ZVI/Cu和n ZVI分别需要29 h和40 h.3种纳米铁对菲的去除率均随着n ZVI投加量的增加而升高,随着菲溶液初始浓度的增加而降低.反应温度的升高可提高n ZVI/Ni对菲的去除效率,高温时(≥30℃)菲的降解遵循一级反应动力学模型.p H对反应影响不大.GC-MS结果表明,n ZVI/Ni降解菲溶液主要为催化加氢反应,而n ZVI/Cu和n ZVI对菲溶液的去除主要为吸附作用.     

两种Keggin型有机-无机混配物的结构及催化消除甲醇的研究

为了寻找高效消除挥发性有机污染物的新材料,克服单纯杂多酸催化剂催化性能低、稳定性差的缺点,采用水热法合成了两种新的具有Keggin型杂多酸骨架的有机-无机混配配合物单晶,分别为(4-C6H7N)2(4-C6H8N)3PW12O40·H2O(配合物1)和(4-C5H7N2)3(PW12O40) ·5H2O(配合物2),用X-射线单晶衍射、红外光谱、紫外光谱、差热-热重进行了表征.配合物1和2由1个Keggin型PW12O40阴离子与有机配体4-甲基吡啶或4-氨基吡啶组成,并通过广泛的氢键作用在空间上无限延展形成超分子网络结构.配合物1为单斜晶系,晶胞参数为:a=16.0569(10)(A),b=19.8781(17)(A),c=18.4728(15)(A),α=90.00°,β=98.384(7)°,γ=90.00°.配合物2为单斜晶系,晶胞参数为:a=11.8880(9)(A),b=20.0148(15)(A),c=25.495(2)(A),α=90.00°,β=96.279(5)°,γ=90.00°.在流动催化反应体系中,探讨了该两种配合物催化消除甲醇的能力.体系流速为10mL/min,甲醇初始质量浓度为3.0g/m3,配合物1在150℃时对甲醇的消除率达到85.25％,配合物2在140℃对甲醇的消除率达到53.00％.     

Reuse of nickel recovered from spent Ni–Cd batteries for the preparation of C/Ni and C/Ni/Pd layered electrodes for energy sources

Nickel recovered in the recycling process of Ni–Cd batteries was used as a main component of bath for electrodeposition of nickel onto carbon fabric in order to obtain C/Ni composite. A part of the obtained composite was additionally coated with a thin layer of palladium (C/Ni/Pd composite). All the materials were investigated to assess the possibility of their use in the processes of electrochemical storage (sorption/desorption) of hydrogen and electrochemical oxidation of methanol. The obtained results showed the composites to be active electrode materials in these processes. The electrodes exhibited high activity and cyclability, especially in the process of methanol oxidation due to electrocatalytic activity of both nickel deposited onto carbon fabric and the outer layer of porous palladium coating nickel substrate.     

DDTs对水生哺乳动物的组织残留基准初步研究

作为一种曾经广泛使用的氯化烃杀虫剂,DDT及其主要代谢产物DDE和DDD(合称为DDTs)是一类典型的具有持久性和生物累积性的有毒污染物。亲脂性和持久性使得DDTs可以通过食物链进行生物放大,从而对处于高营养级的水生哺乳动物造成严重的毒害作用。在综述DDTs对哺乳动物的毒性研究基础上,采用物种敏感度分布(species sensitivity distribution,SSD)和毒性百分数排序法(toxicity percentile rank method,TPRM)推导DDTs保护水生哺乳动物的组织残留基准(Tissue Residue Guideline,TRG)。使用SSD和TPRM得到的TRG分别为23.9和22.7 ng·g-1食物(湿重)。相应的,DDTs保护水生哺乳动物的水质基准分别为188.2和178.7 pg·L-1。依据研究得到的DDTs的组织残留基准及其在鱼类体内的含量评估对水生哺乳动物的风险。研究结果可用于评估DDTs对水生哺乳动物的生态风险,并为DDTs的风险管理提供理论依据。