多金属氧酸盐/介孔分子筛杂化材料的制备与表征

采用嵌段共聚物模板P123和缺位Keggin结构的多金属氧酸盐K₈SiW₁₁O₃₉•12H₂O, 由溶胶-凝胶法合成了具有类六方结构的SiW₁₁/SBA-15杂化介孔分子筛材料, 并通过X射线衍射(XRD)、傅立叶变换红外光谱(FT-IR)、紫外漫反射光谱(UV/DRS)、电感耦合等离子原子发射光谱(ICP-AES)、低温N₂吸附、透射电子显微镜(TEM)等手段对其进行了表征. 结果表明, 杂化材料中不仅规整均一的类六方介孔结构得以保持, 而且多金属氧酸盐的Keggin单元保留完整(含量达25%左右), 并共价键联于介孔材料的孔道内部. 稳定性实验表明, 杂化材料中多金属氧酸盐在水中的流失率远低于一般浸渍法制备的样品.     

Strongly Basic Anion Exchange Resin Based on a Cross-Linked Polyacrylate for Simultaneous C.I. Acid Green 16, Zn(II), Cu(II), Ni(II) and Phenol Removal

The adsorption ability of Lewatit S5528 (S5528) resin for C.I. Acid Green 16 (AG16), heavy metals (Zn(II), Cu(II) and Ni(II)) and phenol removal from single-component aqueous solutions is presented in this study to assess its suitability for wastewater treatment. Kinetic and equilibrium studies were carried out in order to determine adsorption capacities, taking into account phase contact time, adsorbates’ initial concentration, and auxiliary presence (NaCl, Na₂SO₄, anionic (SDS) and non-ionic (Triton X100) surfactants). The pseudo-second-order kinetic model described experimental data better than pseudo-first-order or intraparticle diffusion models. The adsorption of AG16 (538 mg/g), phenol (14.5 mg/g) and Cu(II) (5.8 mg/g) followed the Langmuir isotherm equation, while the uptake of Zn(II) (0.179 mg^1−1/nL^1/n/g) and Ni(II) (0.048 mg^1−1/nL^1/n/g) was better described by the Freundlich model. The auxiliary’s presence significantly reduced AG16 removal efficiency, whereas in the case of heavy metals the changes were negligible. The column studies proved the good adsorption ability of Lewatit S5528 towards AG16 and Zn(II). The desorption was the most effective for AG16 (>90% of dye was eluted using 1 mol/L HCl + 50% v/v MeOH and 1 mol/L NaCl + 50% v/v MeOH solutions).     

氧负离子自由基与乙烯反应机理的计算研究

在G3MP2B3理论水平下研究了氧负离子自由基(O^－)与乙烯(C₂H₄)的反应机理. 计算结果表明, O^－与C₂H₄经碰撞快速复合形成离子诱导偶极络合物中间体, 然后经历异构化、解离生成各种产物, 分别对应分子离子异构解离与复合电子剥离反应通道. 通过比较各个反应途径上势垒的相对高度, 发现主要产物通道为复合电子剥离通道, 相应的中性产物主要为c-C₂H₄O; 而分子离子解离通道的通道分支比较小, 其中生成水反应通道相应的阴离子产物主要是CH₂＝C^－. 当前的计算证实了以往实验观察的结论.     

密度泛函理论研究DMSO溶剂中邻-二(吡咯-2-甲酰胺基)亚苯与卤素阴离子间的超分子作用

采用混合密度泛函B3LYP方法, 在LANL2DZ水平上优化DMSO溶剂中邻-二(吡咯-2-甲酰胺基)亚苯(PFP)及其卤素阴离子复合物的几何构型, 从几何结构参数、电荷布居、前线轨道、结合能以及热力学参数等角度探讨复合物形成过程中主体分子的构象变化以及主客体间的超分子作用. 研究结果表明, 邻-二(吡咯-2-甲酰胺基)亚苯识别卤素阴离子是一个自发过程. 复合阴离子过程中, 两者的前线轨道发生作用, 电子容易从卤素阴离子的HOMO向主体分子的LUMO转移. 在所形成的四种复合物PFP:X^－(X^－＝F^－, Cl^－, Br^－, I^－)中, 以PFP:F^－最稳定, 与文献报道邻-二(吡咯-2-甲酰胺基)亚苯识别卤素阴离子能力的实验结果相一致. 设计合成含多个吡咯酰胺基团、并能形成合适“杯口”大小的主体化合物, 将增强对卤素阴离子的识别能力.     

磷酸三丁酯萃取脱硫废液中硫氰酸根的初步研究

焦炉煤气含污染物H_2S 5g/m~3-8gm~3、HCN1g/m~3-2.5g/m~(3[1]),目前主要用催化氧化-氨水吸收法(NH_3-OMC)工艺处理.由此产生的脱硫脱氰废液中主要含有NH_4SCN、(NH_4)_2S_2O_3等无机盐,其中,SCN~-及S_2O_3~(2-)浓度均影响脱硫催化剂的效率,规定其总浓度不得超过250g/L.     

Synthesis and Crystal Structure of a Novel Bimetallic Porphyrin Complex Salt {[MnTPP(CH3OH)2]3Fe(CN)6}·13H2O

A novel bimetallic porphyrin complex salt, {[MnTPP(CH3OH)2]3Fe(CN)6}·13H2O (TPP = tetraphenylporphyrin), has been synthesized and structurally characterized by X-ray diffraction analysis. The crystal is of trigonal, space group R-3 with a = b = 31.0618(10), c = 11.8366(8) (A), Z = 3, V = 9890.3(8) (A)3, C144H134FeMn3N18O19, Mr = 2641.36, Dc = 1.330 g/cm3, μ(MoΚα) = 0.463 mm-1, F(000) = 4131, R = 0.0525 and wR = 0.1382 for 3045 observed reflections (I ＞ 2((I)). The title complex is composed of one [Fe(CN)6]3- anion, three [MnTPP(CH3OH)2] cations and thirteen water molecules, which are connected by multiform hydrogen bonds leading to a 3D supramolecular network structure.     

络合阴离子的杯芳烃受体的研究进展

综述了络合阴离子的杯芳烃受体, 详细介绍了连有金属和Lewis酸的杯芳烃阴离子受体, 连有酰胺、脲、多胺的杯芳烃和杯吡咯等含氢键受体的阴离子受体, 并对其应用前景进行了展望.     

Synthesis and Crystal Structure of an Ion-Pair Compound:[HL]2[Ni(CN)4]·4H2O(L=4-(2-Hydroxyphenyl)-1,5,9-triazacyclododecan-2-one)

An ion-pair compound,[HL]2[Ni(CN)4]·4H2O 1 has been obtained as an unexpected product when we attempt to prepare a heterometallic cyano-bridged complex by the reaction of GdCl3·nH2O,K2Ni(CN)4 and L (L=4-(2-hydroxyphenyl)-1,5,9-triazacyclododecan-2-one) in aqueous solution,and characterized by single-crystal X-ray diffraction.It crystallizes in monoclinic,space group P21/n with a=12.380(1),b=9.9637(8),c=17.087(1)A,β=105.947(2)°,V=2026.6(3) A3,Rint=0.0509,Z=2,Dc=1.297g/cm3,C34H56O8N10Ni,Mr=791.60,F(000)=844,μ(MoKα)=0.538 mm-1,S=1.030,the final R=0.0644 and wR=0.1299 for 2023 observed reflections with I≥2σ(I).The title compound 1 contains one anion of [Ni(CN)4]2-,two cations of [HL]+and four packing water molecules,which are held together by the N-H…O and O-H…O hydrogen bonds to form a three-dimensional framework.     

Keggin结构杂多酸盐[(C2H5)4N]3[PMo12O40]单晶的水热合成及其结构表征

将苯基磷酸和CoCl2.6H2O,Na2MoO4.2H2O,MoO3混合,采用水热合成的方法制备出了标题化合物[(C2H5)4N]3[PMo12O40],并对其结构进行了X射线单晶衍射的测定.此晶体属于立方晶系,空间群为Cmca,晶体数据为a=1.9777(2)nm,b=1.6882(2)nm,c=1.7161(3)nm,α=90.00°,β=90.00°,γ=90.00°,V=5.7299(13)nm3,Z=4,R1=0.0533,wR2=0.1219.标题化合物含有四乙基胺阳离子和十二钼磷酸的阴离子,其中十二钼磷酸的阴离子具有典型的Keggin结构.     

甲基吡啶侧链金属化和烷基化反应的研究

甲基吡啶侧链上的氢易于质子化被碱金属所取代,但传统的侧链金属化的方法,其实验操作都比较繁复。前文报道,吡啶与金属钠在乙醚回流中可形成吡啶自由基负离子钠络合物(C_5H_5N~-Na~ ),它是一种有效的金属