Synthesis, Structure and Physical Properties of Mn and Cd Complexes with 1,1,2,2-Tetracarboxyl-ethylene Acid

Complex [Mn(tce) 0.5(H2O) 4](1) was obtained from Mn(OAc) 2 and tce,where tce is 1,1,2,2-tetracarboxyl-ethane. The structure of 1 is a single molecule,in which Mn(II) is a distorted octahedron coordinated to six oxygen atoms. Complex [Cd(tce) 0.5(H2O) 3](H2O) (2) fea-tures a pillared layer architecture. The Cd(II) atom is in an octahedral environment coordinated by six oxygen donors from water molecules and tce ligands. Cd(II) atoms are interlinked by the tce ligand to generate a 2-D wavelike layer. The layers are strutted by the intermolecular O-H···O hydrogen bonds to form a 3-D open framework. Luminescence property of complex 2 was investigated. Magnetic property of complex 1 was also studied. 1 belongs to triclinic,space group P1 with a = 6.2901(12) ,b = 8.0212(15) ,c = 8.0769(15) ,α = 108.522(3) ,β = 95.068(3) ,γ = 97.086(3) °,V = 379.92(12) 3,Mr = 456.08,Dc = 1.993 g/cm3,F(000) = 232,μ = 1.748 mm-1,Z = 1,the final R = 0.0297 and wR = 0.0731 for 1575 observed reflections with I > 2σ(I) . 2 is of monoclinic system,space group P21/c with a = 6.4367(14) ,b = 9.495(2) ,c = 13.907(3) ,β = 117.405(8) °,V = 754.6(3) 3,Mr = 285.51,Dc = 2.513 g/cm3,F(000) = 556,μ = 2.905 mm-1,Z = 4,the final R = 0.0375 and wR = 0.0737 for 1521 observed reflections with I > 2σ(I).     

水蒸气对有机污染物微波光催化氧化反应的影响

 以C2H4和C2HCl3为模型有机污染物,考察了不同反应条件下水蒸\r\n气对微波催化反应性能的影响．结果表明,水蒸气的存在是影响微波光\r\n催化反应性能的重要因素．由于微波对物质的极化作用不同,在加水的\r\n微波光催化反应过程中微波能量主要被水吸收,微波场对水的脱附有利\r\n于提高加水条件下C2H4微波光催化氧化活性,但不利于需要水的C2HCl\r\n3氧化反应的进行．     

二氧化钛薄膜上三氯乙烯光催化氧化反应机理

 研究了二氧化钛薄膜上三氯乙烯(TCE)气相光催化氧化的反应机理. 结果表明,TCE气相光催化氧化反应生成的氯气可引发TCE的连锁反应. 当添加氯气的浓度相同时TCE表面光催化反应的初速率约为光化学反应初速率的2倍,说明连锁反应主要发生在催化剂表面. 氯可吸附在催化剂表面,作为电子的接受体抑制空穴与电子复合,提高TiO2光催化剂的活性. 除了TCE与吸附在催化剂表面的·OH的相互作用及反应产物/中间产物二氯乙酰氯的光催化分解可生成氯气以外,光气在与氯气共存时的光分解也有利于氯的生成.     

搅拌对三氯乙烯及糠醛水溶液液-液分层的影响

糠醛是用玉米芯、麦杆等农林植物纤维废料生产的重要的有机溶剂和原料。用于生产糠醇，石油化工中润滑油精制及C4、C5馏分的分离纯化。传统的糠醛精致方法是将水解后的糠醛稀溶液多次蒸馏，能耗高，作者采用液-液萃取法分离糠醛，工艺简单，能耗低。本文选择三氯乙烯为萃取剂，考察了萃取分离糠醛水溶液体系的影响因素，为进一步中试及工业放大提供参考。     

乙醇/水体系负载型纳米Cu/Fe二元合金的合成、改性及其还原三氯乙烯的性能

在乙醇/水体系中采用KBH4液相还原法, 以石墨微粉为载体, Cu为复合金属, 通过两步法合成了具有球状团簇结构的负载型纳米Cu/Fe二元合金. 与单纯负载型纳米Fe0相比, 该复合材料对三氯乙烯(TCE)具有更高的还原脱氯性能, 纳米Fe0的质量浓度为10 g/L时, 5 h内能将10 mg/L的TCE完全去除. 将十六烷基三甲基溴化铵(CTAB)用于负载型纳米二元合金的表面改性, 改性后的材料对TCE的还原脱氯性能提高. 改性材料连续降解TCE 36 d, 10.2 mg/L TCE在7 h内即完全去除, 材料改性后不易氧化失活, 还原性能保持长期稳定.     

利用真空紫外脉冲场电离-光电子方法研究三氯乙烯阳离子振动光谱

在 76 4 0 0～ 796 5 0cm-1的能量范围内测量了三氯乙烯的真空紫外脉冲场电离 光电子 (VUV PFI PE)谱 .根据量子化学理论计算的频率以及Franck Condon因子 ,对VUV PFI PE谱的振动谱带进行了标定 ,确认了11个三氯乙烯阳离子的振动频率 ,分别为 :ν1+ =14 8cm-1,ν2 + =180cm-1,ν3 + =2 86cm-1,ν4+ =4 0 2cm-1,ν5+=4 72cm-1,ν6+ =6 6 0cm-1,ν7+ =875cm-1,ν8+ =990cm-1,ν9+ =10 38cm-1,ν10 + =12 6 7cm-1,ν11+ =14 0 8cm-1.这些测量和新近用真空紫外 红外光诱导电离确定的ν12 + =30 73cm-1一起 ,提供了三氯乙烯阳离子电子基态的所有 12个振动频率的实验值 .通过对VUV PFI PE谱 (0 ,0 )跃迁带的光谱拟合 ,确定了三氯乙烯的电离能为(76 4 4 1.7± 2 .0 )cm-1((9.4 776± 0 .0 0 0 2 )eV) .     

ADSORPTION OF CHLOROFORM AND TRICHLOROETHYLENE IN WATER WITH A NEW KIND OF HYPERCROSSLINKED RESINS

In this paper two newly developed hypercrosslinked resins were used to treat micropolluted drinking water and their static and kinetic adsorption were investigated at 293 K. The results show that these two adsorbents are superior to Amberlite XAD-4 for removing chloroform and trichloroethylene in aqueous solutions. The breakthrough capacity and the total capacities from mini-column adsorption studies for chloroform and trichloroethylene on XAD-4, ZH-01 and ZH-00 are calculated respectively under experimental conditions     

连续二氧化碳激光敏化氧化CF2HCL,CF2=CF2,CF2=CFCl,CHCl3,CHCl=CCl2和CH2=CH2

本文报道了连续二氧化碳激光敏化氧化CF_2HCl,CF_2==CF_2,CF_2==CFCL,CHCl_3,CHCl==CCl_2和CH_2==CH_2的反应,讨论了某些反应的机制。结果表明,激光敏化方法可以使不能直接吸收激光的反应物分子在气相中发生反应,并有可能产生卡宾。     

Trichloroethylene Dechlorination by Copper-contained Zero-valent Iron Slurry

Zero valent iron technology has been widely used for treating contaminated wastewater these years. However, it always results in inefficiency in the processes of drying and storage due to oxidation and passivation. This could be avoided by in situ synthesized zero valent iron slurry in an emergency if it possesses the same performance as zero valent iron. In this study, iron slurry was synthesized and directly used for dechlorinating trichloroe- thylene to measure its degradation efficiencies and properties. Results show that 2%（mass ratio） copper-contained zero-valent iron slurry exhibits the optimal performance compared with the other iron slurries. Batch experiments in- dicate that factors such as the concentration of trichloroethylene, pH, dissolved oxygen and equilibrium to a certain extent affect the reduction oftrichloroethylene by 2%（mass ratio） copper-contained zero-valent iron slurry. Persistent, high-efficiency degradation performance could last 7 cycles. These demonstrate that the application of coppercontained zero-valent iron slurry in treating trichloroethylene-contained wastewater is realistic.     

金掺杂对碳负载钯催化还原性能的促进作用

在许多催化应用中双金属的PdAu催化剂性能优于单金属催化剂.科研人员对具有可控纳米结构和高活性的PdAu催化剂进行了广泛的研究,但该催化剂的制备需要多步且通常步骤复杂.本文仅通过浸渍和焙烧制得了Au掺杂的负载型Pd催化剂,所得PdAu/C催化剂用于室温水相三氯乙烯加氢脱氯反应.当Pd和Au负载量分别为1.0 wt%和1.1 wt%时,在经过干燥、空气处理和H2还原的过程后，所制得的PdAu/C催化剂活性最高,初始转化频率(TOF)为34.0×10–2 molTCEmolPd–1 s–1,是单金属1.0 wt%Pd/C催化剂TOF (2.2×10–2 molTCEmolPd–1 s–1)的15倍以上. X射线吸收光谱结果表明,金的加入避免了400oC焙烧时Pd的氧化.本文还提出了可能的催化剂纳米结构演变路径,以解释所观察到的催化现象.