咪唑类离子液体混合物吸收CO2性能研究

结合常规离子液体和功能型离子液体在吸收CO₂方面的优势,将两类咪唑类离子液体进行混合,对其吸收CO₂的效果和再生性能进行了实验研究。结果表明,两类咪唑类离子液体混合后流动性明显改善,与CO₂接触气液传质顺畅;常规离子液体[bmim][BF₄]和[bmim][Tf₂N]与胺功能型离子液体[NH₂e-mim][BF₄]混合物较单一的离子液体吸收CO₂的量大,[bmim][CH₃CO₂]与[NH₂e-mim][BF₄]混合后较单一的[bmim][CH₃CO₂]吸收量有明显的减低;随着常规咪唑类离子液体阳离子碳链增长,混合离子液体吸收CO₂的效果变强;与胺乙基功能型离子液体混合吸收CO₂时,阴离子为[Tf₂N]的常规咪唑类离子液体要比阴离子为[BF₄]的吸收效果好;离子液体混合物吸收CO₂后经再生循环利用10次,混合物质量基本不变,循环使用后吸收CO₂性能为初始吸收性能的75%~85%。     

离子液体型表面活性剂研究

以1-甲基咪唑为原料, 制备了6个常规离子液体: 1-正丁基-3-甲基咪唑四氟硼酸盐及六氟磷酸盐(简称[bmim][BF₄]及[bmim][PF₆])、1-正己基-3-甲基咪唑四氟硼酸盐及六氟磷酸盐(简称[hmim][BF₄]及[hmim][PF₆])、1-正十六烷基-3-甲基咪唑四氟硼酸盐及六氟磷酸盐(简称[C₁₆mim][BF₄]及[C₁₆mim][PF₆])和4个功能化离子液体: 1-(2-羟乙基)-3-甲基咪唑四氟硼酸盐及六氟磷酸盐(简称[2-hemim][BF₄]及[2-hemim][PF₆])、1-乙氧羰基甲基-3-甲基咪唑四氟硼酸盐及六氟磷酸盐(简称[eocmmim][BF₄]及[eocmmim][PF₆]). 研究了这两类离子液体的一些物理性能, 旨在挖掘离子液体在香料香精化妆品工业中的应用价值. 分别检测了它们与一般溶剂的互溶性, 并测定了它们的表面张力和发泡性能, 实验结果表明, 仅[C₁₆mim][BF₄]和[C₁₆mim][PF₆]具有发泡性能, 发泡力分别为68和120 mm.     

室温离子液体对氨基苯磺酸的萃取性能

系统研究了[C₄mim][PF₆], [C₆mim][PF₆], [C₆mim][BF₄]和[C₈mim][BF₄]室温离子液体对间氨基苯磺酸、对氨基苯磺酸稀水溶液的萃取平衡. 实验结果表明: 萃取温度和相体积比的变化对分配比影响不大; 水相pH值对萃取平衡有较大的影响, 氨基苯磺酸在离子液体/水体系中的分配比在pH＝4.2时达到最大值; 水相中CaCl₂或Na₂SO₄的存在能较大幅度地提高氨基苯磺酸的分配比; 离子液体的阴离子的性质对分配比有显著的影响, 阴离子为[BF₄]^－的离子液体对氨基苯磺酸的萃取能力大于阴离子为[PF₆]^－的离子液体; 咪唑环上烷基链的长度也对萃取效果有一定的影响. 在所研究的离子液体中, [C₆mim][BF₄]和[C₈mim][BF₄]对氨基苯磺酸有较好的萃取性能, 且萃取相中的氨基苯磺酸可回收利用, 离子液体也可循环使用.     

新型离子液体1-烷基-3-甲基咪唑苯甲酰基三氟硼酸盐的合成与性质

合成了新型离子液体1-烷基-3-甲基咪唑苯甲酰基三氟硼酸盐[C_nmim][BTB](n=4,6,8),并通过NMR、差热、热重等方法研究了其基础物化性质。 结果发现,3种离子液体的分解温度在200 ℃左右;随着阳离子碳链的增长,离子液体的粘度、熔点逐渐升高,并从亲水性变为疏水性。 尤其是疏水性的[C₆mim][BTB]和[C₈mim][BTB]在与水长时间的混合中表现出较好的稳定性,基本解决了四氟硼酸盐离子液体亲水性强、$BF^{-}_{4}$易水解的缺点,有望用于乏燃料后处理并提高临界安全。     

离子液体[bmim][PF6]与[moemim][PF6]结构微不均匀性以及微粘度的光谱探测

室温离子液体由于其极低的蒸汽压、比较好的热稳定性和化学稳定性、良好的分子结构与性能的可设计性等优点,作为一种新型的环境友好溶剂在很多领域有着广泛的应用.对于离子液体的微观结构和微观性能的研究是设计新型离子液体以及扩展离子液体应用的关键.本文通过荧光探针分子香豆素153(C153)的转动动力学和对微观环境敏感的荧光探针分子1, 3-二(1-芘基)丙烷(BPP)的稳态荧光光谱,探测和表征了烷基取代的离子液体1-丁基-3-甲基咪唑六氟磷酸盐([bmim][PF₆])和与其具有相似结构的醚键官能化的离子液体1-甲氧基乙基-3-甲基咪唑六氟磷酸盐([moemim][PF₆])的微观结构和微粘度. C153探针分子在离子液体[bmim][PF₆]中的转动过程具有快、慢两个组分表明离子液体[bmim][PF₆]内部存在松散和紧密的两种结构微区;而C153探针分子在离子液体[moemim][PF₆]中的转动动力学只存在一种过程,说明醚键的引入使得[moemim][PF₆]内部趋于一种类型的微环境.通过C153探针分子的转动时间研究发现,醚键官能化的离子液体[moemim][PF₆]的微粘度小于烷基链取代的离子液体[bmim][PF₆],同时通过BPP探针分子的二聚体激基复合物(excimer)与单体(monomer)荧光发射强度的比值(I_E/I_M)研究也证明这一结果.醚键的引入使得离子液体[moemim][PF₆]相对于离子液体[bmim][PF₆],侧链的极性更大、柔顺性更好,同时醚键有可能作为氢键的受体与阳离子形成氢键从而削弱离子液体中阴、阳离子间的相互作用,使得离子液体[moemim][PF₆]的微观环境比离子液体[bmim][PF₆]更为均一,同时具有更小的微粘度.     

阴离子插层镁铝水滑石结构及相互作用的理论研究

采用密度泛函理论(DFT)计算了MgAl-LDHs层板与无机阴离子(F^-、Cl^-、NO₃^-、CO₃^2-、SO₄^2-)和有机阴离子(水杨酸根离子([HO(C₆H₄)COO]^-)、苯甲酸根离子([(C₆H₅)COO]^-)、对二甲氨基苯甲酸根离子([p-(CH₃)₂N(C₆H₄)COO]^-)、十二烷基磺酸根离子[C₁₂H₂₅SO₃]^-、己烷基磺酸根离子[C₆H₁₃SO₃]^-、丙烷基磺酸根离子[C₃H₇SO₃]^-)间的相互作用,获得稳定超分子几何结构及相互作用能。层板主体与客体间存在较强的超分子作用,包括主客体间静电作用和氢键等。主、客体间相互作用能数值大小顺序为CO₃^2- > SO₄^2- > F^-> Cl^-> NO₃^-;[p-(CH₃)₂N(C₆H₄)COO]^-> [(C₆H₅)COO]^-> [HO(C₆H₄)COO]^-和[C₁₂H₂₅SO₃]^-> [C₆H₁₃SO₃]^- > [C₃H₇SO₃]^-。另外,还采用自然键轨道(NBO)计算和分析了LDHs 层板与阴离子间作用机理,从二阶微扰理论计算得到的稳定化能变化趋势与相互作用能数据基本吻合。     

系列Sm3+配合物的合成、结构及光物理性能

采用水热方法合成了4种Sm³⁺配合物, 即{[SmZn(2,5-pdc)₂(tp)_0.5(H₂O)]·2H₂O}_n(1), [Sm₂Zn₂(C₆H₅COO)₁₀(Imh)₂(H₂O)₂](2), {[Sm₂(NO₂C₆H₄COO)₆(H₂O)₄]·H₂O}_n(3)和{[SmN(CH₂COO)₃(H₂O)₂]·H₂O}_n(4)[2,5-pdc=2,5-吡啶二羧酸根, tp=对苯二甲酸根, C₆H₅COO=苯甲酸根, Imh=咪唑, NO₂C₆H₄COO=对硝基苯甲酸根, N(CH₂COO)₃=氨三乙酸根]. 通过单晶X射线衍射确定了其晶体结构. 在室温下测定了其红外光谱、 紫外-可见-近红外光谱以及在近红外区和可见区的发射光谱. 结果表明, 4种配合物在近红外区或可见区均出现Sm³⁺离子的特征发射. 这是形成配合物后, Zn-配体部分和配体对Sm³⁺离子发光的敏化作用所致. 此外, 讨论了不同有机配体或d过渡金属离子对Sm³⁺离子发光的影响, 并分析了配合物中Sm³⁺离子的近红外发射带位移、 劈裂和加宽的原因.     

双子型Br?nsted酸性离子液体催化高级脂肪酸与醇反应合成生物柴油（英文）

合成了一系列双子型酸性离子液体,该类型离子液体以乙二铵为连接链,由碳链长度可调的双子型阳离子与不同的阴离子组成.因此,具有相分离催化剂的性质,并应用于高级脂肪酸与醇的酯化反应,以合成生物柴油.详细考察了各参数的影响.结果表明,[C12Sb][p-CH3C6H4SO3]表现出高催化活性及可重复使用性能.     

含稀土离子液体[Cnmim][Ln（NO3）4]的合成、表征及荧光性能研究

以N-甲基咪唑,溴代烷烃和硝酸钠为原料,合成了5种离子液体[Cnmim]NO3(n=2,4,6,8,10;mim=N-甲基咪唑),并对离子液体进行了表征.用[Cnmim]NO3与硝酸铕、硝酸铽反应,得到了含稀土离子液体[Cnmim][Ln(NO3)4](Ln=Eu,Tb).利用电喷雾质谱对[Cnmim][Ln(NO3)4]的结构进行了表征,结果表明稀土离子与来自4个硝酸根的8个氧原子配位,形成[Ln(NO3)4]阴离子,阳离子为1-烷基-3-甲基咪唑.荧光研究表明,[Cnmim][Ln(NO3)4](Ln=Eu,Tb)的溶液存在较强荧光;温度和浓度影响荧光强度.     

羧酸根阴离子型功能化离子液体对纤维素的溶解性能

通过两步法合成了1,3-二甲基咪唑乙酸盐([C₁mim][CH₃COO])和1,3-二甲基咪唑羟基乙酸盐([C₁mim][HOCH₂COO])两种羧酸根阴离子型功能化离子液体。 研究了纤维素在这两种离子液体中的溶解性能。 结果表明,阴离子的结构对纤维素的溶解性能有明显影响,在120 ℃下,两种离子液体对纤维素的溶解度分别为19.7%和21.2%。 通过傅里叶变换红外光谱(FT-IR)、X射线衍射(XRD)以及热重分析(TG)等技术手段对再生纤维素的结构和热稳定性进行表征,表明两种离子液体均为纤维素的直接溶剂,纤维素在溶解及再生过程中晶体结构由I型转变为无定型结构,且热稳定性有所下降。 此外,研究发现溶解温度的提高和溶解时间的延长均会导致再生纤维素聚合度的降低。 所获得的研究结果为纤维素溶剂体系的开发具有指导意义。     

Formation of [C60C5H5] adduct cations and theoretical study of the isomers

We study here the reactions between C₆₀ and planar C₅H₅⁺ cations that lead to the formation of [C₆₀C₅H₅]⁺ adduct cations in the chemical ionization source of the mass spectrometer. The structures, stabilities and charge locations of some possible isomers of [C₆₀C₅H₅]⁺: σ-adduct, π-complex, [1,4]- and [l,2]-addition cations, are studied by AM1 semiempirical molecular orbital calculations. We find that the most stable is the σ-addition cation. Another interesting and stable structure is the π-complex cation which is bonded by the electrostatic interaction at the inter-ring distance of 1.589 Å with the C_5v symmetry. The C₅H₅⁺ cyclopentadienium cation seems to be an “inverted umbrella” sitting on a five-membered ring of the C₆₀ cage.     

Arylkomplexe des typs trans-[Ir(Ar)(CO)(PPh3)2]

The preparation and properties as well as some reactions of a series of arylcarbonylbis(triphenylphosphine)iridium(I) complexes [Ir(Ar)(CO)(PPh₃)₂] (Ar = C₆H₅, C₆F₅, 2-C₆H₄CH₃, 3-C₆H₄CH₃, 4-C₆H₄CH₃, 2-C₆H₄OCH₃, 2,6-C₆H₃-(OCH₃)₂, 4-C₆H₄N(CH₃)₂, 3-C₆H₄Cl, 4-C₆H₄Cl, 4-C₆H₄Cl, 3-C₆H₄CF₃, 4-C₆H₄CF₃) are described, and the most important IR data as well as the ³¹P NMR parameters of these, without exception trans-planar, compounds are given.

Some of the complexes react with molecular oxygen to form well defined dioxygen adducts [Ir(Ar)(O₂)(CO)(PPh₃)₂] (Ar = C₆H₅, 3-C₆H₄CH₃, 4-C₆H₄CH₃). Complexes with ortho-substituted aryl ligands are not oxygenated. This effect is referred to as a steric shielding of the metal center by the corresponding ortho-substituents. With SO₂ the similar irreversible addition compound [Ir(4-C₆H₄CH₃)-(SO₂)(CO)(PPh₃)₂] is obtained. Sulfur dioxide insertion into the Ir---C bond cannot be observed.

The first step of the reaction between [Ir(4-C₆H₄CH₃)(CO)(PPh₃)₂] and hydrogen chloride involves an oxidative addition of HCl to give [Ir(H)(Cl)(4-C₆-H₄CH₃)(CO)(PPh₃)₂]. Ir---C bond cleavage by reductive elimination of toluene from the primary adduct does not occur except at elevated temperature.     

Synthesis, characterization and reactivity of palladium(II) compounds containing terdentate [Csp, N, S] or [Csp, N, S] ligands

The study of the reactivity of R---CH=N---(C₆H₄-2-SMe) with R=C₆H₅ or 2,4,6-Me₃-C₆H₂ with palladium(II) salts is reported. These studies have allowed us to prepare and characterize the coordination complexes: cis-[Pd{R---CH=N---(C₆H₄-2-SMe)}Cl₂] {R=C₆H₅ or 2,4,6-Me₃-C₆H₂} and the cyclopalladated compounds [Pd{C₆H₄---CH=N---(C₆H₄-2-SMe)}Cl] and [Pd{(2-CH₂-4,6-Me₂-C₆H₂)---CH=N---(C₆H₄-2-SMe)}Cl]. The X-ray crystal structures of the latter complexes reveal that the thioimines act as a [Csp², phenyl,N,S]⁻ and as a [Csp³, N,S]⁻ terdentate group, respectively. The study of the reactions of the cyclopalladated compounds with PPh₃ is also reported.     

Reaction of [(C6H6)RuCl2]2 with 7,8-benzoquinoline and 8-hydroxyquinoline

The reaction of [(C₆H₆)RuCl₂]₂ with 7,8-benzoquinoline and 8-hydroxyquinoline in methanol were performed. The obtained complexes have been studied by IR, UV–VIS, ¹H and ¹³C NMR spectroscopy and X-ray crystallography. In the reaction with 8-hydroxyquinoline the arene ruthenium(II) complex oxidized to Ru(III). The electronic spectra of the obtained compounds have been calculated using the TDDFT method. Magnetic properties of [Ru(C₉H₆NO)₃] · CH₃OH complex suggest the antiferromagnetic coupling of the ruthenium centers in the crystal lattice. EPR spectrum of [Ru(C₉H₆NO)₃] · CH₃OH compound indicates single isotropic line only characteristic for Ru³⁺ with spin equal to 1/2.     

Darstellung und Molekülstruktur des (μ-Alkylidenamido)titanocenkomplexes [(C5H5)2TiCl]2[μ-{N=C(CH2C6H5)C(CH2C6H5)=N}]

Reduction of (C₅H₅)₂TiCl₂ with Zn in presence of benzyl cyanide gives the (μ-alkyl-ideneamido)titanocene complex [(C₅H₅)₂TiCl]₂[μ-{N=C(CH₂C₆H₅)---C(CH₂C₆H₅)=N}] with C---C bond formation between two benzyl cyanide molecules.

X-ray structure investigation indicates a symmetrical structure. The C=N distances are smaller than usual, the Ti---N distances are very short, and the Ti---N---C angle differs only a little from 180°, which infers a heteroallene structure of the complex.     

Synthesis,structural study,thermal, optical properties and characterization of the new compound [C_6H_7N_2O_2]_3TeCl_5·2Cl

The new organic-inorganic compound, [C_6H_7N_2O_2]_3TeCl_5·2Cl was synthesized and its structure was determined at room temperature in the triclinic system (P~-1) with the following parameters: a = 10.5330(11) ?, b = 10.6663(11) ?, c = 15.9751(16)?, α = 82.090(2)°, β = 71.193(2)°, γ = 68.284(2)°and Z = 2. The final cycle of refinement led to R = 0.057 and Rw = 0.149. The crystal structure was stabilized by an extensive network of N--H···Cl and non-classical C--H···Cl hydrogen bonds between the cation and the anionic group. Several thermal analysis techniques such as thermogravimetric analysis, differential scanning calorimetric analysis and evolved gas analysis were used. We used isoconversional kinetics methods to determine the kinetics parameters. We observe that the decomposition of [C_6H_7N_2O_2]_3TeCl_5·2Cl entails the formation hydrochloric acid of nitroaniline as volatiles. The infrared spectra were recorded in the4000–400 cm~(-1)frequency region. The Raman spectra were recorded in the external region of the anionic sublattice vibration 50–1500 cm~(-1). The optical band gap was calculated from the UV-Vis absorbance spectra using classical Tauc relation which was found to be 3.12 and 3.67 eV.     

Theoretical study of tricyclo[3,3,1,1]decane, tricyclo[3,3,1,1]decsilane molecules and their halogen derivatives, C10H12X4 and Si10H12X4 (X=F, Cl, Br, I)

The B3LYP/3-21G* ab initio molecular orbital method from the program package was applied to study tricyclo[3,3,1,1^3,7]decane and tricyclo[3,3,1,1^3,7]decsilane molecules and their halogen derivatives (1,3,5,7-tetrahalotricyclo[3,3,1,1^3,7]decane and 1,3,5,7-tetrahalotricyclo[3,3,1,1^3,7]decsilane, C₁₀H₁₂X₄ and Si₁₀H₁₂X₄ respectively). The optimized structures of these compounds were obtained. Ionization potentials, HOMO and LUMO energies, energy gaps, heats of formation, atomization energies and vibration frequencies were calculated. The calculations indicate that these molecules are stable and have T_d symmetry. Tricyclo[3,3,1,1^3,7]decsilane and its halogen derivatives (Si₁₀H₁₂X₄) are found to have higher conductivity than tricyclo[3,3,1,1^3,7]decane and its halogen derivatives (C₁₀H₁₂X₄). 1,3,5,7-Tetrafluorotricyclo[3,3,1,1^3,7]decane (C₁₀H₁₂F₄) and 1,3,5,7-tetrafluorotricyclo[3,3,1,1^3,7]decsilane (Si₁₀H₁₂F₄) were found to be the easiest compounds to form and the most difficult to dissociate of all 1,3,5,7-tetrahalotricyclo[3,3,1,1^3,7]decane and 1,3,5,7-tetrahalotricyclo[3,3,1,1^3,7]decsilane compounds, respectively.     

Optically active transition metal compounds : LXXXI. Crystal structure of (+)546-[C5H5Mo(CO)2LL]PF (LL = 2-benzoylpyridine-(R)-1-phenylethylimine)

Racemic [C₅H₅Mo(CO)₂LL]PF₆, (2) with LL = 2-benzoylpyridine-1-phenylethylimine, undergoes spontaneous resolution upon crystallization from acetone/CH₂Cl₂/ethanol. The absolute configuration of the (+)₅₄₆-isomer was shown to be (R) at the Mo atom and (R) at the asymmetric carbon atom. Comparison of 2 with [C₅H₅Mo(CO)₂LL]PF₆ (1) (LL = 2-carbaldehydepyridine-1-phenylethylimine) reveals distinct changes caused by the differences resulting from the presence of the phenyl group in 2 and the change from the (RR)- to the (RS)-configuration.     

Reactions of pentafluorophenylxenon(II) hexafluoroarsenate [C6F5Ze] [AsF6] with halide anions in acetonitrile

Reactions of [C₆F₅Xe]⁺ [AsF₆]⁻ in acetonitrile with halide anions X⁻ show different results depending on X. If X = I, Br or Cl, then C₆F₅X is obtained. If X = F, then C₆F₅H and C₆F₅---C₆F₅ are produced, and if X = HF₂, then C₆F₆, C₆F₅H and C₆F₅---C₆F₅ are formed.