硼特效树脂吸附硼的动力学研究

采用动边界模型对硼特效树脂XSC-800吸附模拟废水中硼酸根离子的动力学进行了描述.采用有限浴方法考察了体系温度、搅拌速度、树脂粒径及溶液中硼酸根离子浓度对交换过程的影响,并得到了交换动力学总方程.确定了硼酸根离子的交换过程属颗粒扩散控制,交换过程的表现活化能为20.38kJ/mol,表观反应级数为1.661.     

Ferrocene-decorated (phthalocyaninato)(porphyrinato) double- and triple-decker rare earth complexes: synthesis, structure, and electrochemical properties

A series of four mixed (phthalocyaninato)(porphyrinato) rare earth double-decker complexes (Pc)M[Por(Fc)(2)] [Pc = phthalocyaninate; Por(Fc)(2) = 5,15-di(ferrocenyl)-porphyrinate; M = Eu (1), Y (2), Ho (3), Lu (4)] and their europium(III) triple-decker counterpart (Pc)Eu(Pc)Eu[Por(Fc)(2)] (5), each with two ferrocenyl units at the meso-positions of their porphyrin ligands, have been designed and prepared. The double- and triple-decker complexes 1-5 were characterized by elemental analysis and various spectroscopic methods. The molecular structures of two double-deckers 1 and 4 were also determined by single-crystal X-ray diffraction analysis. Electrochemical studies of these novel sandwich complexes revealed two consecutive ferrocene-based one-electron oxidation waves, suggesting the effective electronic coupling between the two ferrocenyl units. Nevertheless, the separation between the two consecutive ferrocene-based oxidation waves increases from 1 to 4, along with the decrease of rare earth ionic radius, indicating the effect of rare earth size on tuning the coupling between the two ferrocenyl units. Furthermore, the splitting between the two ferrocene-based one-electron oxidations for triple-decker 5 is even smaller than that for 1, showing that the electronic interaction between the two ferrocene centers can also be tuned through changing the linking sandwich framework from double-decker to triple-decker. For further understanding of the electronic coupling between ferrocenyl groups, DFT calculation is carried out to clarify the electronic delocalization and the molecular orbital distribution in these double-decker complexes.     

Arrangement of tris(phthalocyaninato) gadolinium triple-decker complexes with multi-octyloxy groups on water surface

A series of five carefully designed tris(phthalocyaninato) gadolinium triple-decker complexes [Pc(R)8]Gd[Pc(R')8]Gd[Pc(R')8] (R=R'=R'=H; R=R'=H, R'=OC8H17; R=R'=H, R'=OC8H17; R=H, R'=R'=OC8H17; R=R'=R'=OC8H17) (1-5) were prepared and the film forming properties on water surface were systematically investigated. The limited mean molecular area obtained by pi-A isotherms revealed an "edge-on" conformation for all these compounds. UV-vis absorption spectra showed red-shifted Q bands, indicating the formation of J aggregates and effective intermolecular interaction in solid film. Phthalocyanine rings were found to take tilted orientation with respect to the normal of substrate according to the polarized absorption spectroscopic measurements. Low angle X-ray diffraction results provide direct evidence and therefore clearly clarify the point, for the first time, that unsymmetrical triple-decker molecules pack on the water surface with the unsubstituted phthalocyanine ring set close to the water surface and the substituted phthalocyanine ligand with octyloxy groups lies on the top.     

盐湖资源的开发和综合利用技术

中国是世界上盐湖资源最丰富的国家之一,钾、钠、锉、镁资源储量巨大.随着我国国民经济特别是农业的持续发展,要以钾为龙头,注重资源的综合利用,加快盐湖资源的开发。本文评述了我国盐湖资源的特点、开发现状和现阶段盐湖资源开发和综合利用中有代表性的化工技术:冷结晶法生产氛化钾、从盐湖资源制取硫酸钾、卤水中锉的分离提取、水氯镁石脱水和热解技术以及盆湖资源的深加工和高值化。     

Synthesis and Structure of the Tetrameric [Cp*V(μ‐F)2]4 (Cp* = C5Me5); Preparation of the Imido Molybdenum Fluoride [(2,6‐i‐Pr2C6H3N)2MoF2] · THF and the Structural Investigation of [(2,6‐i‐Pr2C6H3N)6Mo4(μ3‐F)2Me2(μ‐O)4]

Treating [Cp*V(μ‐Cl)₂]₃ (Cp* = C₅Me₅) and [(2,6‐i‐Pr₂C₆H₃N)₂MoMe₂], respectively, with Me₃SnF afforded the title compounds [Cp*V(μ‐F)₂]₄ ( 1 ) and [(2,6‐i‐Pr₂C₆H₃N)₂MoF₂] · THF ( 2 ). 1 has a tetrameric structure, in which four V atoms can be regarded as being arranged at the vertices of a distorted tetrahedron, with four long edges bridged by one F atom and each of the other two short edges bridged by two F atoms with a mean V–F bond length of 2.00 Å. A hydrolyzed product of 2 , [(2,6‐i‐Pr₂C₆H₃N)₆Mo₄(μ₃‐F)₂Me₂(μ‐O)₄] ( 3 ) was characterized by elemental analyses and X‐ray single crystal study. The X‐ray diffraction analysis reveals that 3 has a unique tetranuclear structure, containing two five and two six coordinated Mo atoms connecting each other by four μ‐O and two μ₃‐F atoms. The geometries around the two Mo atoms can be described having distorted trigonal bipyramidal and distorted octahedral coordination spheres, respectively. The Mo–(μ‐O) bond lengths are 1.813 Å (average) for five coordinated Mo atoms and 2.030 Å (average) for those of six coordinated, respectively, indicating an additional π bonding between five coordinated Mo atoms and the μ‐O atoms. The Mo–(μ₃‐F) distances range from 2.291 to 2.352 Å.