B-Z振荡反应论文：四氮杂大环四烯镍(Ⅱ)配合物催化的新型B-Z振荡反应.doc

B-Z振荡反应论文：四氮杂大环四烯镍（）配合物催化的新型B-Z振荡反应【中文摘要】化学振荡反应是典型的非线性、非平衡化学现象,是化学反应中的某些中间体随着时间或者空间而周期性变化的体系。经典的化学振荡反应体系(Ce4+、Mn2+、2+或2+催化的振荡)和四氮杂大环配合物为催化剂的振荡反应体系都引起了广大科学工作者的广泛兴趣。目前,对化学振荡反应的研究主要体现在新型振荡器的设计、机理的研究、化学振荡的实际应用等方面。本文介绍了化学振荡的绪论、催化剂的合成具体步骤、两种新型振荡器的研究。具体体现在以下四个方面：一.化学振荡的绪论介绍了化学振荡的动力学和热力学上的研究进展,还介绍了化学振荡的六个分类以及化学振荡发生的三个必须条件,最后具体说明了化学振荡在各个领域的应用和化学振荡的意义。二.催化剂的合成步骤及其结构表征按照文献方法合成四氮杂大环四烯镍()的配合物(ClO4)2),并对其进行了结构表征。由元素分析、红外光谱和紫外-可见吸收光谱图可知,合成出来的物质为所需要的目标物质(ClO4)2,它具有高度对称的结构,分子中含有两个N=C-C=N共轭双键。三.四氮杂大环镍()配合物催化的苹果酸为有机底物的新型B-Z振荡反应本文报道了新的振荡体系NaBrO3-Malic acid-H2SO4-(ClO4)2,其中的TIM是2,3,9,10-四甲基-1,4,8,11-四氮杂环十四-1,3,8,10-四烯。配合物(ClO4)2作为这个振荡反应的催化剂,其中的大环配合物中含有两个N=C-C=N结构。通过研究发现振荡周期(tp)是与DL-苹果酸和硫酸的浓度有关,但是和溴酸根的浓度无关。因此,振荡周期(tp)可以表达为：tp(s)000-1.23 0-0.29。实验的结果表明Br-的浓度是振荡反应过程的总开关,与此同时说明了自由基和HBrO2参与了振荡反应。最后提出了振荡反应的FKN机理。四.四氮杂大环镍()配合物催化的新型B-Z振荡反应报道了一种以四氮杂大环四烯镍()配合物(C104)2为催化剂,柠檬酸为有机底物的硫酸环境的新型的B-Z振荡反应体系。讨论了不同浓度的溴酸钠、硫酸、柠檬酸对振荡周期(tp)、振幅(A)、振荡次数(n)的影响,发现振荡周期tp与溴酸钠、硫酸、柠檬酸的浓度有关,关系表达式：tp(s)0-2.003 0-2.881 0-3.16。研究了各种【英文摘要】Chemical oscillation is the phenomenon of nonlinearity and nonequilibrium, and it is a chemical system in which some intermediate states vary with time or space in periodic manner. Both the typical B-Z oscillating system(oscillating using Ce4+、Mn2+、Fe(phen)32+or Ru(bipy)32+as catalyst) and tetraazamacrocycle-complexes-catalyzed oscillating chemical reactions have become of great interest in the field of kinetics. Recently, the research for the oscillation chemistry mainly focuses on the design of new oscillator, the study of mechanism model and their application on the analytical field. In this paper, we introduced the summary of chemical oscillating reaction, the specific of the synthesis of the catalyst and the designation of two new oscillators. The specifics were showed in the following four aspects:1. The summary of chemical oscillating reactionIt introduced progress on chemical oscillation in the filed of kinetics and thermodynamics. It also introduced the six species of the chemical oscillation and three conditions for occurrence of the chemical oscillation. At last, it was showed the application on the analytical determination of the analytes.2. Systhesis of macrocyclic complex Ni(TIM)(ClO4)2.The catalyst(Ni(TIM)(C104)2) was synthesized according to literature, then was identified by elementary analysis, infrared spectrum and UV-Vis spectrum. The structure of the Ni(TIM) (ClO4)2 was high symmetry, and it contained two conjugated N=C-C=N structural units.3. A new B-Z oscillating reaction catalyzed by a tetramethyl tetraaza-cyclotetradeca-tetraene (TIM) nickel () complex with malic acidas organic substrateA new B-Z oscillator of the NaBrO3-Malic acid-H2SO4-Ni(TIM)(ClO4)2 system is reported, among which the TIM is 2,3,9,10-tetramethyl-1,4,8,11-tetraaza-cyclotetradeca-1,3,8,10-Tetraene. The complex Ni(TIM)(ClO4)2, with a macrocyclic ligand containing two conjugated N=C-C=N structural units, can serve as a catalyst in the titled system. It is found that the oscillation period (tp) is dependent on the initial concentrations of DL-malic acid and H2SO4, but it is independent on the concentrations of BrO3-. So the oscillation period tp can be expressed as: tp(s)NaBrO300H2S040-1.23Malic acid0-0.29. The experiments results have shown that the concentrations of Br- may act as an on-off switch while free radicals and HBrO2 may be involved in the oscillating process. A tentative mechanism based on the FKN is proposed.4. New B-Z oscillating reaction catalyzed by a tetramethyl tetraazacyclotetradeca-tetraene Nickel () complex Ni(TIM)(ClO4)2In this paper, a new B-Z oscillating reaction in which a tetramethyl tetraazacyclotetradeca-tetraene (TIM) Nickel () complex Ni(TIM) (ClO4)2 serves as catalyst and Citric acid as organic substrate in aqueous H2SO4 is reported. The experimental results have shown that the different concentrations of NaBrO3, H2SO4 and Citric acid have effects on the oscillation period(tp), the amplitude of oscillation (A), and the oscillating cycles (n). It is found that the oscillation period(tp) is dependent on the initial concentrations of NaBrO3, H2SO4 and Citric acid. The oscillation period tp can be expressed as:tp(s)NaBrO30-2.003 H2SO40-2.881 Citric acid0-3.16. The effect of some reducing agent, free radicals, Ag+, Hg2+ on the oscillation is also studied. A tentative mechanism based on the FKN is proposed latter.【关键词】B-Z振荡反应 苹果酸 柠檬酸 杂大环配合物【英文关键词】B-Z oscillating reaction Malic acid Citric acid macrocyclic complex【目录】四氮杂大环四烯镍（）配合物催化的新型B-Z振荡反应摘要3-5Abstract5-6第一章 绪论9-381.1 引言9-121.2 化学振荡反应的研究概况12-171.2.1 化学振荡反应的历史背景12-141.2.2 化学振荡反应的研究现状14-161.2.3 化学振荡反应的展望16-171.3 化学振荡反应的分析17-181.3.1 化学振荡反应的热力学分析17-181.3.2 化学振荡反应的动力学分析181.4 化学振荡体系的分类18-231.4.1 B-Z振荡反应体系18-201.4.2 B-L振荡反应体系20-211.4.3 B-R振荡反应体系211.4.4 Cu()组分的振荡反应体系211.4.5 过氧化物酶-氧化物酶生物体系21-221.4.6 液膜振荡体系22-231.5 化学振荡反应发生的条件23-241.5.1 体系中必须具有双稳态23-241.5.2 体系必须远离平衡态241.5.3 体系中必须有反馈存在241.6 化学振荡体系的应用24-261.6.1 在分析化学领域的应用251.6.2 在生物领域的应用25-261.6.3 在医药领域的应用261.6.4 在环境领域的应用261.7 本论文的研究意义26-29参考文献29-38第二章 催化剂的合成及结构表征38-462.1 引言382.2 四氮杂大环四烯镍()的高氯酸盐的合成及其结构表征38-442.2.1 实验试剂与仪器38-402.2.2 四氮杂大环四烯镍()的高氯酸盐的合成步骤40-422.2.3 四氮杂大环四烯镍()配合物的结构表征42-442.2.3.1 Ni(TIM)(ZnCl_4)_2的结构表征422.2.3.2 Ni(TIM)(ClO_4)_2的结构表征42-44参考文献44-46第三章 四氮杂大环镍()配合物Ni(TIM)(ClO_4)_2催化的苹果酸为有机底物的新型B-Z振荡反应46-663.1 引言46-473.2 实验试剂与实验仪器47-493.2.1 实验试剂47-483.2.2 实验仪器48-493.3 实验过程与讨论49-603.3.1 化学振荡现象的分析49-513.3.2 化学振荡影响因素的讨论51-603.3.2.1 苹果酸浓度对化学振荡现象的影响51-533.3.2.2 溴酸钠浓度对化学振荡现象的影响53-553.3.2.3 硫酸浓度对化学振荡现象的影响55-573.3.2.4 温度对化学振荡现象的影响57-603.3.2.