交联壳聚糖树脂对Ni(II)的吸附行为研究

研究了甲醛、环氧氯丙烷交联壳聚糖树脂(AECTS)对Ni(II)的吸附行为和吸附Ni(II)对树脂结构及性能的影响.用FTIR,WAXD,TGA和DSC对吸附产物进行了结构表征,并深入分析了AECTS与Ni(II)之间的作用机理.结果表明:AECTS主要以配位形式吸附Ni(II);AECTS吸附Ni(II)后,结晶度下降、总体上热稳定性变差;Ni(II)对AECTS的主链分解具有明显的催化功能,而空气气氛中对AECTS在500℃附近的分解表现出火焰缓蚀作用.AECTS对Ni(II)的吸附行为符合Langmuir模型,属于单分子层吸附,所有吸附位对Ni(II)的作用近似相同;与壳聚糖(CTS)比较,造成AECTS对Ni(II)吸附量增大的主要原因是AECTS结晶度下降和孔隙率增加,二者导致在交联处理前Ni(II)难于接近的吸附位点“活性”相对增大,使其更容易与Ni(II)相结合;不同介质对AECTS吸附Ni(II)的影响大小顺序为HCl>CdCl2>MgCl2>NaCl,前两者使吸附量减小,MgCl2使吸附量稍有增加,NaCl对吸附量基本没有影响.     

交联壳聚糖树脂吸附Cu2+的机理研究

研究了甲醛、环氧氯丙烷交联壳聚糖(AECTS)对Cu2+的吸附热力学行为,用FTIR对吸附产物进行了结构表征,并研究了溶液中介质种类的不同对Cu2+吸附量的影响.结果表明AECTS主要以配位形式吸附Cu2+;AECTS对Cu2+的吸附符合Langmuir等温方程,属于单分子层吸附;吸附为自发的、吸热的熵增加过程;同时不同介质对树脂吸附Cu2+的影响大小顺序为HCl＞CdCl2＞MgCl2＞NaCl,并对其作用机理进行了探讨.     

交联壳聚糖树脂吸附Co2+的机理研究

研究了甲醛、环氧氯丙烷交联壳聚糖 (AECTS) 对Co2 的吸附热力学行为,用FTIR、WXRD对吸附产物进行了结构表征,并研究了溶液中介质种类的不同对Co2 吸附量的影响.结果表明:AECTS主要以配位吸附和物理吸附形式吸附Co2 ;树脂与Co2 配位后,结晶度下降;AECTS对Co2 的吸附行为同时符合Freundlich模型和Langmuir模型;吸附为自发的、放热的熵减小过程;不同介质对树脂吸附Co2 的影响大小顺序为HCl>CdCl2>MgCl2>NaCl,前两者使吸附量减小,后两者使吸附量增加,作用机理相差较大.     

交联壳聚糖树脂与Zn2+的配位作用

研究了甲醛、环氧氯丙烷交联壳聚糖树脂(Chitosan crosslinked by aldehyde and epichlorohydrin,AECTS)吸附Zn2 后对树脂结构及性能所产生的影响.用FTIR、XRD、TG、DSC和SEM对吸附产物进行了结构表征,并分析了AECTS与Zn2 之间的作用机理.结果表明,Zn2 与AECTS中的氨基发生配位而被吸附;AECTS吸附Zn2 后,结晶度下降、总体上热稳定性变差;Zn2 对AECTS的主链分解具有明显的催化功能;Zn2 的配位使得AECTS的表面形态发生了改变.     

Hg2+-交联壳聚糖配合物的合成与表征

研究了甲醛、环氧氯丙烷交联壳聚糖树脂(AECTS)对Hg2 的吸附行为和吸附Hg2 对树脂结构及性能的影响。用FT-IR、XRD、TG、DSC和SEM对吸附产物进行了结构表征,并深入分析了AECTS与Hg2 之间的作用机理。结果表明,Hg2 与AECTS中的氨基发生配位、与AECTS中的羟基形成离子键而被吸附;AECTS吸附Hg2 后,结晶度下降,总体上热稳定性变差;Hg2 对AECTS的主链分解具有明显的催化功能;Hg2 的成键使得AECTS的表面形态发生了改变。     

交联壳聚糖树脂与Zn2+的配位作用

研究了甲醛、环氧氯丙烷交联壳聚糖树脂(Chitosan crosslinked by aldehyde and epichlorohydrin,AECTS)吸附Zn2 后对树脂结构及性能所产生的影响.用FTIR、XRD、TG、DsC和SEM对吸附产物进行了结构表征,并深入分析了AECTS与Zn2 之间的作用机理.结果表明,Zn2 与AECTS中的氨基发生配位而被吸附;AECTS吸附Zn2 后,结晶度下降、总体上热稳定性变差:Zn2 对AECTS的主链分解具有明显的催化功能;Zn2 的配位使得AECTS的表面形态发生了改变.     

新型吸附剂的合成、表征及其对Ni(II)的吸附研究

利用滴加法合成了球形含Ni^2＋交联壳聚糖, 并通过胺化引入大量活性氨基, 再经除镍制成对重金属镍离子具有较好吸附能力的新型吸附剂[P-C-CTS(Ni)]. 通过Ni^2＋吸附容量的测定, IR及XPS分析, 验证了合成技术路线的正确性. 通过研究pH值对吸附量的影响, 初步讨论了无柠檬酸根(Cit)配位体存在时, 吸附剂对Ni(II)的吸附为螯合作用. 通过Cit存在条件下(c_Ni＝c_Cit＝0.852 mmol•L^－1), 吸附剂对Ni(II)离子和Cit的吸附量随pH值的变化, 结合相应pH值下金属镍的形态分布, 探讨了其对Ni(II)的吸附机理, 研究认为不仅仅是简单的螯合作用, 其吸附机理和吸附量与溶液中金属离子的存在形式有关, 引入静电吸附原理解释了吸附剂对Ni(II)的吸附现象.     

交联壳聚糖对Zn2+的吸附性能

研究了甲醛、环氧氯丙烷交联壳聚糖树脂(AECTS)对Zn 2 的吸附行为,探讨温度、溶液的pH、反应时间、再生次数等因素对吸附性能的影响,并用红外光谱(FTIR)和光电子能谱(XPS)对吸附产物表面的元素结构及其结合能的变化进行表征. 结果表明,AECTS对Zn 2 的吸附导致AECTS结构和性能发生显著变化. FTIR和XPS分析表明,Zn 2 以配位键的形式吸附于AECTS,使AECTS中氨基的伸缩振动、变形振动发生了明显变化,N原子发生化学位移,而AECTS分子链上的羟基没有直接参与配位反应;AECTS对Zn 2 有较强的吸附能力和较快的吸附速率,在30 ℃、Zn 2 初始质量浓度为1 g/L的溶液中,吸附量可达163 mg/g树脂,是壳聚糖饱和吸附量的1.7倍左右;吸附量受pH的影响较大,在pH＝5时吸附量最高;AECTS对Zn 2 的吸附行为符合Freundlich等温吸附方程,温度升高吸附量增大,该过程为一吸热过程;AECTS经再生重复使用5次,吸附量基本不变.     

交联壳聚糖-Co配聚物结构与性能初步研究

制备了微球状交联壳聚糖并合成了交联壳聚糖(AECTS)-Co配聚物。用FTIR、WXRD、TGA和DSC等对配聚物进行了结构表征。结果表明：Co^2 与AECTS中的氨基、羟基发生配位而被吸附;树脂与Co^2 配位后,结晶度下降、热稳定性降低。     

Cr(VI)在Mg-Al型类水滑石上的吸附-脱附性研究I. 吸附性

研究了Cr(VI)在带结构正电荷的Mg-Al型类水滑石(HTlc)上的吸附性能, 考察了pH、无机电解质添加剂NaCl, NaNO₃, Na₂SO₄和Na₃PO₄及有机添加剂EDTA和柠檬酸等因素的影响, 并结合红外光谱和XRD实验结果探讨了吸附机理. 研究表明, Mg-Al型HTlc对Cr(VI)有很强的吸附能力, 其吸附动力学和吸附等温线分别符合准二级速率方程和Langmuir方程, 饱和吸附量达105 mg/g, 有望成为一种优良的含Cr(VI)污水处理剂和Cr(VI)污染土壤修复剂. 初始pH增大, 吸附量降低. 无机电解质和有机添加剂均能明显抑制Cr(VI)在HTlc上的吸附, 其抑制吸附作用的强弱顺序分别为Na₃PO₄≥Na₂SO₄≥NaCl>>NaNO₃和柠檬酸＞EDTA. Cr(VI)在HTlc上的吸附可分为层间的离子交换吸附和外表面的吸附, 其中外表面的吸附层在微观上又可分为因化学键合作用而形成的内络合层和因静电作用而形成的外络合层.     

Adsorption of copper(II) ions from aqueous solutions on alumina industrial wastes

Equilibrium adsorption of copper(II) ions on red mud (alumina industrial wastes) modified by various methods was studied. The effect exerted by the nature the modifier (NaHSO₄, NaCl + HCl, and H₂SO₄) on the sorption activity of red mud was determined.     

Activity coefficient of hydrochloric acid in HCl/MgCl2 mixtures and HCl/NaCl/MgCl2 mixtures from 5 to 45°C

Magnesium, the dominant bivalent cation in natural seawater, exerts a substantial influence on the patterns of ion interactions in this saline medium. Mean activity coefficients of hydrochloric acid in mixtures of this acid with magnesium chloride at four ionic strengths, namelyI=0.1, 0.3809, 0.6729, and 0.8720 mole-kg^–1, were obtained from emf measurements of cells without liquid junction at nine temperatures from 5 to 45°C. The three highest ionic strengths correspond to seawater of salinities 20, 35, and 45, respectively. In addition, mixtures of HCl, NaCl, and MgCl₂ were studied atI=0.6729, the molal ratio of NaCl to MgCl₂ being maintained at 7.202 as in natural seawater. The Harned coefficients _{1 2} were found to decrease slowly with increase in temperature. The trace activity coefficient of HCl in solutions of MgCl₂ as well as in NaCl MgCl₂ mixtures was found to be nearly identical with that measured earlier in synthetic seawater of the same ionic strength but containing NaCl, MgCl₂, KCl, and CaCl₂.     

The effect of the dehydration conditions of chitosan-based polymeric adsorbents on the adsorption of nickel cations

The structure and adsorption properties (with respect to water vapor and nickel cations) of chitosan samples dehydrated by either lyophilization after precipitation with NaOH or Na₂CO₃ or drying in air are investigated. IR spectroscopy and X-ray diffraction data testify that the lyophilization causes both changes in the conformation of chitosan macromolecules and a substantial rise in the crystallinity of the polymer to compare with the air dried one. Chitosan structure ordering resultant from the lyophilization noticeably increases its sorption ability with respect to both water vapor and nickel cations. For example, the sorption capacity of the lyophilized chitosan with respect to nickel cations is as high as 4.5 mmol/g and, thus, is threefold higher than that of air-dried chitosan. The comparative analysis of water adsorption isotherms in the region of low degrees of filling indicates that chitosan structure ordering resultant from the lyophilization changes the number and the energy of primary adsorption sites.     

THE THEORETICAL STUDY OF ADSORPTION OF METAL IONS ON CHITOSAN

The interactions between metal ions such as Zn2+, Pb2+, Mn2+, Hg2+, Cd2+, Ni2+ and chitosan have been investigated using the model cluster model method and density functional method. Full optimization and frequency analysis of all cluster models have been performed employing B3LYP hybrid method at 3-21G basis set level except metal ions which were invoked to use effective core potential (ECP) method. The energy changes, and the main structural parameters have been obtained during the theoretical study of the adsorption of metal ions on the chitosan. The calculations showed that the coordination modes of metal ions with chitosan models were different, the geometries of Mn2+, Zn2+, Cd2+, Hg2+, Pb2+ ions coordinated with two nitrogen atoms and two oxygen atoms were distorted tetrahedral, while the square planar structure of Ni2+ coordinated two nitrogen atoms and two oxygen atoms was observed. The heat of reaction between six metal ions and chitosan models showed the order: Mn2+ ＞Ni2+ ＞Zn2+ ＞Pb2+ ＞Hg2+ ＞Cd2+, this suggested that the coordination strength of Mn2+ ＞Ni2+ ＞Zn2+ ＞Pb2+ ＞Hg2+ ＞Cd2+.     

The adsorption and decomposition of ethylene on Ni(100)

The adsorption behavior of ethylene on Ni(100) at a variety of temperatures has been studied using temperature programmed desorption, and X-ray and UV photoemission. The adsorption of ethylene at 98 K results in molecular adsorption with a saturation C/Ni ratio of 0.76. Heating this surface to any temperature between 213 and 683 K reduces the C/Ni ratio to 0.5. Exposure to ethylene at 300 K leads to decomposition producing surface carbide, adsorbed hydrogen atoms and an adsorbed C_xH_2x species. A comparison with other work on Ni(111) indicates that ethylene adsorption processes are structure sensitive.     

Transition Metal Complexes with Pyrazole Based Ligands

The complex formation of cobalt(II)-, nickel(II) and copper(II) sulphate hydrates with 3,5-dimethyl-1-thiocarboxamidepyrazole (HL) was studied. The influence of the anions on the course of the reaction was also examined, using nickel(II) salts with various anions. Beside the NiSO₄·7H₂O the reaction has been carried out with Ni(OAc)₂, Ni(CF₃COO)₂ and Ni(SCN)₂. Compounds with the following composition were obtained: Co(L)₃, Ni(L)₂ and [Cu(SCN)L]₂. The structure of the ligand and the Co(L)₃ complex was determined by single crystal X-ray analysis, while that of the Ni(L)₂ was solved by analysis of powder diffraction X-ray data. The most probable structure of the copper(II) complex is proposed on the basis of the elemental analyses data, FT-IR spectrometry and magnetic measurement. The thermal decomposition of the complexes was investigated by thermogravimetry, DSC and coupled TG-MS measurements. In the case of the nickel(II) compound, a relatively stable intermediate was detected in the 550-650 K temperature range. The composition of the intermediate, Ni(SCN)(NCS), was determined by FT-IR-spectrometry. This revised version was published online in July 2006 with corrections to the Cover Date.