氰根桥联CrⅢ-CrⅡ一维配合物{[Cu(cyclam)] [Cr(bpb)(CN)2]2·2H2O}n的合成、结构与磁性

基于构筑单元K[Cr(bpb)(CN)₂] 和[Cu(cyclam)] (ClO₄)合成了一个氰根桥联的Cr^Ⅲ-Cr^Ⅱ一维化合物{[Cu(cyclam)] [Cr(bpb)(CN)₂]₂·2H₂O}_n[cyclam=1,4,8,11-四氮杂环十四烷;bpb^2-=1,2-二(2-吡啶甲酰胺基)苯] (1),并通过X-衍射单晶分析表征其结构特征.结果表明:化合物1是由氰根桥联的2种不同金属组成的聚合物,其结构属于三斜晶系, P1空间群,a=0.9667 3(19) nm,b=1.345 1(3) nm,c=1.382 0(3) nm,α=77.12(3)°,β=76.93(3)°,γ=82.02(3)°,V=1.699 1(6) nm³,Z=2,D_c=1.567 g·cm^-3,μ=1.086 mm^-1,F(000)=828,R₁=0.0413,wR₂=0.1200.磁性研究表明:配合物1中的Cr^Ⅲ离子和Cr^Ⅱ离子之间存在弱的铁磁耦合作用.     

两个具stp三维拓扑构型的稀土配位聚合物{[Ln2（pda）3（H2O）2]2H2O}n（Ln=Nd/La）

本文利用水热合成方法,将稀土氧化物与邻苯二乙酸（H₂pda）反应得到了2个新颖的稀土配位聚合物{[Ln₂（pda）₃（H₂O）₂]·2H₂O}_n（Ln=Nd（1）,La（2））。测定了它们的晶体结构,并进行了X-射线单晶衍射、红外光谱、荧光光谱和热重分析等性质的表征。晶体结构测定表明这2个化合物为异质同晶化合物。属单斜晶系,C2/c空间群。晶体学参数分别为配合物1：a=2.62906（18）nm,b=1.61172（11）nm,c=0.78327（5）nm,β=93.173（5）°,V=3.3139（4）nm³,Z=4,F（000）=1840,μ=3.173mm^-1,D_c=1.878g·cm^-3,R₁=0.0226,wR₂=0.0609;配合物2：a=2.6271（14）nm,b=1.6149（8）nm,c=0.7966（4）nm,β=92.850（9）,V=3.375（3）nm³,Z=4,F（000）=1816,μ=2.570mm^-1,D_c=1.823g·cm^-3,R₁=0.0466,wR₂=0.1416。化合物中邻苯二乙酸配体连接相邻的稀土金属离子,形成复杂的具有stp拓朴构型的三维网络结构。     

二核双席夫碱铜(Ⅱ)配合物的合成、晶体结构及抗菌活性研究

合成了一对结构类似的双核铜配合物,[CuL¹]₂（1）和[CuL²]₂（2）,其中L¹是双席夫碱配体N,N’-二（5-氟水杨基）-1,3-丙二胺（H₂L¹）的二价阴离子,L²是N,N’-二（5-氟水杨基）-1,2-乙二胺（H₂L²）的二价阴离子,通过元素分析、红外光谱以及单晶X-射线衍射表征了它们的结构。配合物1以单斜晶系P2₁/c空间群结晶,其晶体学参数a=1.3488（1）nm,b=0.6814（1）nm,c=1.7087（1）nm,β=108.903（3）°,V=1.4857（2）nm³,Z=4,R₁=0.0480,wR₂=0.1141,Goof=1.115。配合物2以单斜晶系C2/c空间群结晶,其晶体学参数a=2.7568（2）nm,b=0.7036（1）nm,c=1.4547（1）nm,β=94.758（2）°,V=2.8118（5）nm³,Z=4,R₁=0.0472,wR₂=0.1139,Goof=1.094。X-射线分析表明2个化合物都是中心对称的双核配合物,其中Cu原子都是四方椎配位构型。通过MTT法研究了这2个配合物的抗细菌（枯草芽孢杆菌,金黄色葡萄球菌,大肠杆菌和荧光假单胞菌）和抗真菌（白假丝酵母菌和黑曲霉菌）活性。     

配合物(BenzMeIm)2[PtCl4]的合成与表征

通过离子液体氯化1-苄基-3-甲基咪唑（BenzMeIm-Cl）与PtCl₂的反应,合成了配合物（BenzMeIm）₂[PtCl₄],并用元素分析、红外光谱、紫外-可见光谱、¹H NMR、¹³C NMR和单晶X射线衍射对其进行了表征。单晶X射线分析表明,配合物结构属于P2₁/c空间群,晶胞参数和结构解析参数为：a=0.981 80（5）nm,b=0.861 47（3）nm,c=0.144 332（7）nm,β=92.480（2）°,V=121.96（1）nm³,R₁=0.014 4,wR₂=0.038 8。     

两个三环己基锡芳香羧酸酯的合成、结构、热稳定性及体外抗癌活性研究

甲醇中三环己基氢氧化锡分别与呋喃-2-甲酸、2,4,6-三甲基苯甲酸反应,合成了2个三环己基锡芳香羧酸酯Cy₃SnO₂CC₄H₃O（1）和Cy₃SnO₂CC₆H₂Me₃（2）（Cy为环己基）。通过IR、¹H和¹³C NMR、元素分析及X-射线单晶衍射表征结构。（1）和（2）均属单斜晶系,配合物（1）空间群P2₁,晶体学参数：a=0.82304（2）nm,b=1.11119（3）nm,c=1.28390（3）nm,β=101.090（2）°,Z=2,V=1.15227（5）nm³,D_c=1.381g·cm^-3,μ（Mo Kα）=1.127mm^-1,F（000）=496,R₁=0.0529,wR₂=0.1387。配合物（2）空间群P2₁/c,晶体学参数：a=0.99962（2）nm,b=1.41597（2）nm,c=1.97359（3）nm,β=94.0420（10）°,Z=4,V=2.78653（8）nm³,D_c=1.266g·cm^-3,μ（Mo Kα）=0.937mm^-1,F（000）=1112,R₁=0.0540,wR₂=0.1619。配合物（1）和（2）的中心锡原子均为畸变四面体构型。通过分子间氢键作用,配合物（1）形成二维网状结构。试验表明,配合物（1）和（2）具有良好的热稳定性,对人癌细胞Colo205、HepG2、MCF-7、Hela、NCI-H460增殖均有较强的抑制作用。     

配合物(BenzMeIm)2[PtCl4]的合成与表征

通过离子液体氯化1-苄基-3-甲基咪唑（BenzMeIm-Cl）与PtCl₂的反应,合成了配合物（BenzMeIm）₂[PtCl₄],并用元素分析、红外光谱、紫外-可见光谱、¹H NMR、¹³C NMR和单晶X射线衍射对其进行了表征。单晶X射线分析表明,配合物结构属于P2₁/c空间群,晶胞参数和结构解析参数为：a=0.981 80（5）nm,b=0.861 47（3）nm,c=0.144 332（7）nm,β=92.480（2）°,V=121.96（1）nm³,R₁=0.014 4,wR₂=0.038 8。     

一种酰腙Schiff碱及其镉配合物的合成、晶体结构及体外抗癌活性的研究

2-硝基苯甲醛与异烟肼在无水乙醇中反应合成了1种异烟酰腙化合物C₁₃H₁₀N₄O₃并培养了单晶,采用X-射线单晶衍射法测定了其晶体结构,结果表明,它的一水合物C₁₃H₁₀N₄O₃·H₂O（1）的晶体属正交晶系,空间群Pna2₁,晶胞参数：a=1.5699（4）nm,b=0.71612（17）nm,c=1.1399（3）nm,V=1.2815（5）nm³,Z=4,Mr=288.27,D_c=1.494g·cm^-3,F（000）=600。采用常规溶液挥发法制备了该酰腙的镉配合物[Cd（H₂O）₄（C₁₃H₁₀N₄O₃）₂]（NO₃）₂（2）,化合物2的晶体属单斜晶系,空间群P2₁/n,晶胞参数：a=0.78248（13）nm,b=1.7398（3）nm,c=1.2080（2）nm,β=98.570（3）°,V=1.626.2（5）nm³,Z=2,Mr=848.99,D_c=1.734g·cm^-3,F（000）=860。同时,化合物经元素分析、红外光谱、紫外光谱和热重分析进行了表征。初步测试了二者的体外抗癌活性,结果表明2对人结肠癌细胞SW620有较强的增殖抑制作用。     

两个基于二噻吩乙烯结构单元双核钌乙烯配合物的合成, 表征和性质

合成了2个含二噻吩乙烯结构单元双核钌乙烯配合物[RuCl（CO）（PMe₃）₃]₂（μ-2,2’-（CH=CH）^2-DTE）（1a）和[RuCl（CO）（PMe₃）₃]₂（μ-2,5-（CH=CH）₂-DTE）（1b）,利用元素分析、红外、核磁共振谱和电化学对它们的结构进行了表征,X-射线单晶衍射分析表明,配合物1a晶体属单斜晶系,C2/c空间群,晶胞参数为：a=3.44575（6）nm,b=1.45945（2）nm,c=2.32191（5）nm,β=110.9770（10）°,V=10.9028（3）nm³,Z=8,D_c=1.467g·cm^-3,λ=0.071073nm,μ（MoKα）=0.956mm^-1,F（000）=4912。测定了它们光照前后的紫外-可见吸收光谱变化图,并对其光致变色性质进行了讨论。     

Cr2O3和CrO3/Cr2O3催化剂的2-氯-1,1,1-三氟乙烷气相氟化反应的活性物种和失活

采用沉淀法和浸渍法制备了2种铬基（Cr₂O₃和CrO₃/Cr₂O₃）催化剂,用于气相氟化2-氯-1,1,1-三氟乙烷合成1,1,1,2-四氟乙烷。研究发现含有低价铬（Cr³⁺）物种的Cr₂O₃催化剂上2-氯-1,1,1-三氟乙烷的稳态转化率为18.5%,而含有高价铬（Cr⁶⁺）物种和低价铬（Cr³⁺）物种的CrO₃/Cr₂O₃催化剂初始转化率达到30.6%,然而存在明显的失活。含有Cr⁶⁺物种的CrO₃/Cr₂O₃催化剂的2-氯-1,1,1-三氟乙烷氟化反应初始TOF值为1.71×10^-4 mol_HCFC-133a·mol_Cr（Ⅵ）^-1·s^-1,高于含有Cr³⁺物种的Cr₂O₃催化剂（4.16×10^-5 mol_HCFC-133a·mol_Cr（Ⅲ）^-1·s^-1）。Cr₂O₃催化剂在氟化反应前后催化剂的物相结构保持不变;而含有高价铬物种的CrO₃/Cr₂O₃催化剂经HF反应后生成了CrO_xF_y活性物种。然而,CrO_xF_y物种在反应中挥发或转化成稳定但无活性的CrF₃,从而导致催化剂失活。     

基于3, 3’, 5, 5’-(1, 3-苯基)-联苯四羧酸构筑的两个配位聚合物的合成、晶体结构和荧光性质

以3,3’,5,5’-（1,3-苯基）-联苯四羧酸（H₄btb）与1,10-菲咯啉（phen）为配体,分别与硝酸镉和硝酸锌在水热条件下反应合成2个一维[Cd（H₂btb）（phen）]_n（1）和二维{[Zn₂（btb）（phen）]·1.5H₂O}_n（2）配位聚合物,并对其进行了元素分析、红外光谱、热重分析和X-射线单晶衍射测定。配合物1属于单斜晶系,空间群为C2/c,晶胞参数：a=2.82845（13）nm,b=1.08554（5）nm,c=1.81768（8）nm,β=96.4850（10）°,V=5.5453（4）nm³,Z=8,D_c=1.670Mg·m^-3,F（000）=2800,R₁=0.0339,wR₂=0.0718[I >2σ（I）],配体H₄btb的2个羧基分别采取μ₁-η¹：η¹、μ₂-η²：η¹配位模式连接镉原子形成一维带状结构。化合物2也属于单斜晶系,空间群为P2₁/c,晶胞参数：a=1.7471（3）nm,b=1.2511（2）nm,c=2.1870（3）nm,β=120.911（11）°,V=4.1014（11）nm³,Z=4,D_c=1.491Mg·m^-3,F（000）=1876,R₁=0.0673,wR₂=0.1749[I>2σ（I）],全部去质子的H₄btb配体的4个羧基分别采取μ₁-η¹：η⁰、μ₁-η¹：η¹、μ₂-η¹：η¹配位模式连接锌原子形成一维链,链间通过μ₂-η¹：η¹桥连羧基扩展为（3,5）-连接的二维（4²·6⁷·8）（4²·6）网状结构。同时研究了2个配合物的荧光性质。     

The coulometric determination of chemical oxygen demand

The chemical oxygen demand (COD) of solutions containing various organic compounds is calculated from the net faradaic charge (Q_net) estimated for the total electrolytic oxidation of Cr^III generated during oxidative degradation of the organic compounds in acidic media containing excess Cr^VI. Values of Q_net for conversion of Cr^III to Cr^VI are estimated from the linearized chronoamperometric data plotted as In {i_{tat, t}} vs. t. This procedure is preferred over determinations of Q_net from the total integrals of i_tot over the entire electrolysis period because of large errors that can result from uncertainty in the background current (i_bkg) for t → ∞. The proposed coulometric procedure offers the benefit that reagent solutions can be reused, thereby minimizing the need for disposal of wastes containing toxic Cr^VI. This procedure was applied in a single digest solution for consecutive determinations of COD. Average COD values for potassium acid phthalate and glucose were 103.8% (s - 6.0, N - 10) and 100.2% (s - 4.2, N - 11), respectively, based on the theoretical degradation to CO₂. In comparison for these same samples, an EPA approved method, based on colorimetric determination of Cr^III, gave COD values of 101.4% (S - 1.4, N - 5) and 100.1% (s - 1.4, N - 5) of the theoretical. Statistical tests indicate no significant difference in the COD values determined for these compounds using the coulometric and EPA methods.     

A pilot plant study on reclamation of sewage effluent by radiation treatment

A pilot plant was developed for the reclamation and reuse of secondary effluent from a sewage treatment plant. The plant system consists of sand filtration, gamma-irradiation, ozonation and ion-exchange. Gamma-irradiation showed effective organic contaminant decomposition and this resulted in the reduction of 5-day biochemical oxygen demand (BOD₅), color, chemical oxygen demand (COD_Cr) and total organic carbon (TOC). Ion-exchange significantly removed inorganic ions, and thus reduced total nitrogen (TN) and total phosphorus (TP). The average reduction in color, COD_Cr, BOD₅, TOC, TN and TP, which was obtained after 12 operations, was 64, 52, 67, 61, 95 and 92%, respectively. Irrespective of applied radiation dose, the treated water fully satisfied the quality requirements of household water that can be used for all home uses except for drinking and human contact uses. This revised version was published online in August 2006 with corrections to the Cover Date.     

阴阳离子双隔膜三室电解槽电渗析处理垃圾渗滤液

采用阴阳离子双隔膜三室电解槽,将电渗析技术与Ｆｅｎｔｏｎ试剂法结合,去除垃圾渗滤液中氨氮和ＣＯＤ_Ｃｒ。垃圾渗滤液中的氨氮通过电渗析技术富集到阴极液中,随后用化学沉淀法加以去除。同时,在铁阳极上生成的Ｆｅ^２＋离子,与滴加入阳极液中的Ｈ_２Ｏ_２反应生成Ｆｅｎｔｏｎ试剂,降解有机物,降低ＣＯＤ_Ｃｒ。实验结果表明,模拟废水中的氨氮透过率达８０％,垃圾渗滤液中氨氮浓度和ＣＯＤ_Ｃｒ由原来的１９８２和２２４８ ｍｇ／Ｌ分别降至２００和１２７ ｍｇ／Ｌ。     

Ultrasonic Decomposition of Ammonia‐Nitrogen and Organic Compounds in Coke Plant Wastewater

The investigations of the ultrasonic decomposition of NH₃‐N and organic compounds (i.e., COD_Cr) in coke plant wastewater are presented in this work. The process parameters were controlled with respect to the presence (or absence) of air atmosphere, initial pH value, initial concentration, and ultrasonic power density in the process of ultrasonic decomposition. It is noted that the ultrasonic removal efficiencies for both the NH₃‐N and the COD_Cr were increased in the presence of the air atmosphere and significantly affected by the initial pH value. The removal efficiencies increased with increasing the ultrasonic power density while they decreased with increasing the initial concentration. The effects of n‐butyl alcohol as an effective OH radical scavenger on the removal efficiencies indicates that the ultrasonic decomposition of the NH₃‐N was carried out mainly via the mechanism of thermal decomposition in cavitation bubbles or in the interfacial region, whereas the ultrasonic decomposition of the COD_Cr mainly resulted from the reactions with OH radicals in the bulk solution. The GC/MS analysis indicates that most of the organic compounds in the wastewater were effectively destroyed by ultrasound.     

Preparation of the Mn-Fe-Ce/γ-Al2O3 ternary catalyst and its catalytic performance in ozone treatment of dairy farming wastewater

The quality of dairy farming wastewater in different regions is particular and different. In Southern China, the Chemical Oxygen Demand (COD_Cr) and colourity of effluent from conventional dairy farming wastewater treatment processes are similar. Catalytic ozonation is a very promising technical method. In this paper, the Mn-Fe-Ce/γ-Al₂O₃ catalyst was prepared via the optimized preparation method of impregnation roasting using γ-Al₂O₃ as the carrier, and this catalyst was used in the ozonation of actual dairy farming wastewater from treatment facilities. The performance of the Mn-Fe-Ce/γ-Al₂O₃ catalyst on dairy farming wastewater was investigated using a simulated dynamic test. The effects of the reaction time, pH and catalyst dosage on COD_Cr and the colourity removal ratio were investigated. The results show that the optimum treatment conditions were a reaction time of 20 min, pH 9, and catalyst dosage of 15 g/L. The COD_Cr removal ratio reached 48.9% and the colourity was 95% under the optimum conditions. BOD₅/COD_Cr increased from 0.21 to 0.54 after catalytic ozonation, indicating that the biodegradability of wastewater was significantly improved. This research provides a new method and theoretical guidance for dairy farming wastewater treatment.     

球磨法制备Y3+/TiO2光催化剂及处理海水养殖废水

采用机械球磨法制备Y~(3+)修饰TiO_2光催化剂,利用紫外-可见漫反射光谱(UV-Vis DRS)、X射线光电子能谱(XPS)、X射线粉末衍射(XRD)、扫描电镜(SEM)等对其进行表征,在紫外光下,以亚甲基蓝(MB)为去除物来考察催化剂活性并优化球磨工艺。将最佳条件下制得的Y~(3+)/TiO_2光催化剂负载于不同半径的塑料浮球上,分别在紫外光和模拟太阳光照射下处理海水养虾废水,通过CODCr(chemical oxygen demand)及三维荧光观察有机物含量变化。结果表明,当Y~(3+)的物质的量分数为2%,球磨时间4 h,球料质量比4∶1,转速为500 r·min~(-1)时,MB光催化降解反应速率常数可达0.111 3 min~(-1),是纯TiO 2的4.2倍。由UV-Vis DRS、XPS、N_2吸附-脱附、XRD、SEM等表征结果显示,2%Y~(3+)/TiO_2样品的禁带宽度降低至3.05 eV,光吸收发生红移,并产生可见光响应,表面吸附氧含量明显增加,比表面积增大到104 m~2·g~(-1)。采用纯TiO_2及2%Y~(3+)/TiO_2为光催化剂处理养虾废水,在可见光和紫外光下CODCr的去除率分别为14.7%和18.8%、26.9%和37.5%。考察3种直径分别为1、2、3 cm负载Y~(3+)/TiO_2浮球的光催化效果,显示直径为2 cm浮球效果最佳,CODCr去除率可达38.5%。     

掺氮TiO2可见光降解有机污染物的比较研究

用溶胶-凝胶法制备了不同掺杂量的N/TiO₂复合纳米粉末, 采用X射线衍射(XRD)、扫描透镜(TEM)、紫外-可见反射吸收光谱(UV-vis)对催化剂进行了初步表征. 通过X射线光电子能谱(XPS)、元素分析仪(EA)测定其含氮量. XPS分析结果显示TiO₂晶格中的氧被氮原子取代, N/TiO₂表面存在Ti^3＋离子; 紫外-可见反射吸收光谱测得不同掺杂量的N/TiO₂的禁带宽度(E_g), 推测在TiO₂价带上方生成了由N诱导产生的中间带, 当氮、钛摩尔比为0.0880时N/TiO₂的E_g最小, 为2.50 eV. 在可见光下, 以酸性桃红(SRB)和无色小分子对氯苯酚(4-CP)作为可见光活性实验的探针反应, 确定了最佳掺杂比为n_N/n_Ti＝0.0880. 结果表明, 最佳掺杂量下N/TiO₂能显著降解SRB和4-CP, 通过测定ESR, IR, TOC, COD, 重点比较了TiO₂在掺杂N前后在降解SRB和4-CP时的差异, 包括氧化物种、矿化率、最终产物等, 证明在可见光下, N/TiO₂的降解机理为电子从独立的N 2p轨道激发到Ti 3d轨道, 产生羟基自由基等氧化物种, 达到降解有机物的目的.     

Operation of industrial-scale electron beam wastewater treatment plant

Textile dyeing processes consume large amount of water, steam and discharge filthy and colored wastewater. A pilot scale e-beam plant with an electron accelerator of 1 MeV, 40 kW had constructed at Daegu Dyeing Industrial Complex (DDIC) in 1997 for treating 1,000 m³ per day. Continuous operation of this plant showed the preliminary e-beam treatment reduced bio-treatment time and resulted in more significant decreasing TOC, COD_Cr, and BOD₅. Convinced of the economics and efficiency of the process, a commercial plant with 1 MeV, 400 kW electron accelerator has constructed in 2005. This plant improves the removal efficiency of wastewater with decreasing the retention time in bio-treatment at around 1 kGy. This plant is located on the area of existing wastewater treatment facility in DDIC and the treatment capacity is 10,000 m³ of wastewater per day. The total construction cost for this plant was USD 4 M and the operation cost has been obtained was not more than USD 1 M per year and about USD 0.3 per each m³ of wastewater.     

Electrocatalytic Sensor for the Determination of Chemical Oxygen Demand Using a Lead Dioxide Modified Electrode

An amperometric method that makes use of a nano‐PbO₂ modified electrode as an electrocatalytic sensor for the determination of chemical oxygen demand (COD) is described. The sensor signal was observed as a result of the detection of the oxidation current due to electrocatalytic oxidation of organic compounds in the sample solution. This sensor responded linearly to the COD_Cr of standard samples in the range of 5–3 000 ppm and the detection limit was 2.5 ppm. When using the sensor to determine real samples, it displays short analysis time, simplicity and no sample pretreatment. The sensor was stable for over 20 days in real wastewater samples and has successfully been applied to the determination of COD in real wastewater samples.     

Performance of a photocatalytic hybrid system coupled with a stainless steel membrane for removal of humic acid

The objective of this study was to evaluate the performance of a photocatalysis/H₂O₂/metal membrane hybrid system in the degradation of humic acid. A metal membrane of nominal pore size 0.5 μm was used in the experiment for separation of TiO₂ particles. Hydrogen peroxide was tested as an oxidant. The efficiency of removal of COD_Cr and color increased rapidly for initial hydrogen peroxide concentrations up to 50 mg L⁻¹. The efficiency of removal of COD_Cr and color by 50 mg L⁻¹ initial hydrogen peroxide concentration was approximately 95 and 98%, respectively. However, addition of hydrogen peroxide over 50 mg L⁻¹ inhibited the efficiency of the system. Addition of hydrogen peroxide to a UV/TiO₂ system enhanced efficiency of removal of COD_Cr and color compared with no addition of hydrogen peroxide. This may be ascribed to capture electrons ejected from TiO₂ and to the production of OH radicals. Application of the metal membrane in the UV/TiO₂/H₂O₂ system enhanced the efficiency of removal of COD_Cr and color because of adsorption by the metal membrane surface and the production of OH radicals. By application of a metal membrane with a nominal pore size of 0.5 μm, TiO₂ particles were effectively separated from the treated water by metal membrane rejection. The photocatalytic metal membrane had much less resistance than the humic acid, TiO₂, and humic acid/TiO₂ because of the degradation of humic acid by the photocatalytic reaction.