金属切削机床行业现状及发展趋势分析

1、 金属-有机骨架论文：纳米孔洞金属有机骨架的选择性吸附与催化性质研究【中文摘要】目前,纳米孔洞金属-有机骨架(MOFs)材料在异相催化,选择性吸附、气体分离与存储、光学、电学、磁学等方面展现了广阔的应用前景。近年来有关纳米孔洞金属-有机骨架材料应用开发的文章大量被报道,但将其应用在工业染料处理方面的研究还比较少。本论文将纳米孔洞金属-有机骨架材料的吸附和催化性质用于有机染料污染物的催化降解,经吸附和催化降解产物无污染。传统的去除工业染料的方法通常治标不治本,它们只能将这些有机物质从污水中转移到另外一种物种中,容易引起二次污染。而使用纳米孔洞金属-有机骨架材料对有机染料的去除具有彻底性。因此,使

2、用纳米孔洞金属-有机骨架处理工业有机染料污染明显的优越性。本论文的主要研究内容如下：1、研究了MIL-53(M)(M=Al, Cr, Fe)在不同溶剂里对甲基橙(MO)的吸附性质。实验过程中考察了不同溶剂对MIL-53(M)对MO吸附量的影响,同时考察了和MIL-53(Fe)结构相似的MIL-53(M)(M=Al, Cr)对MO吸附的影响,对比了不同溶剂对MIL-53(M)(M=Al, Cr)吸附MO吸附量的影响。研究发现,该吸附过程遵循二级动力学模型,基于所建立的二级动力学模型,计算出了吸附动力学反应常数k、相关系数R和平衡吸附量qe。通过对比不同溶剂中MIL-53吸附甲基橙的影响发现：MI

3、L-53不仅在吸附、分离方面有着巨大的应用价值,在选择性催化方面也有着巨大的潜在价值。2、以纳米孔洞金属-有机骨架材料n(M=CuII, CoII, NiII, BTC=均苯三酸)为催化剂,以过氧化氢为氧化剂,在超声条件下,降解工业染料亚甲基蓝(MB),并对其超声降解机理进行研究；以具有介孔尺寸的纳米孔洞金属-有机骨架材料n(M=CuII, CoII, NiII)为催化剂,过氧化氢为氧化剂,研究其超声降解亚甲基蓝的动力学行为,考察了具有不同孔洞尺寸的金属-有机骨架催化剂、氧化剂过氧化氢浓度、超声功率、染料浓度对超声降解亚甲基蓝的影响,研究结果表明,该超声降解反应遵循一级动力学模型,随着氧化剂过

4、氧化氢浓度的增加以及超声功率的提高,该准一级反应速率常数k也会随之增大。根据实验结果,讨论了超声降解MB的反应动力学机理,建立了超声降解的动力学模型。基于所建立的动力学模型和准一级反应速率常数k,计算出了超声降解MB的表观一级速率常数K。3、考察了MIL-53(M)(M=Al, Cr, Fe)光催化降解染料亚甲基蓝(MB)的光催化性质。MOFs MIL-53是坚实的三维多孔结构,这种多孔结构是由无数的无机链组成,孔的节点是以金属M=Al, Cr, Fe, Ga, In, V为中心,对苯二甲酸做配体的八面体结构。就像Ti02半导体,它的导带是由空的3d轨道组成,而MOFs包含的过渡金属作为结构节

5、点形成半导体,因此,空的金属d轨道与有机配体的LUMOs杂化进而形成导带。因此,MOFs是也是一种活泼的光催化剂。目前,MIL-53是在分离气体,如CO2, CH4, H2S和多数有机物质等方面是一个很有价值的材料。然而,目前并没有MIL-53在光催化性能方面的报道。最近,我们发现MIL-53 (Fe)在紫外-可见和可见光源下,降解MB染料有着很好的光催化性质。溶液中电子吸收剂的引入对MIL-53(Fe)光催化降解MB有很大的影响。据我们所知,不同电子吸收剂和MIL-53(Fe)的协同大大提高了有机污染物的降解速率,目前还没有这方面的文献报道。同时,对与MIL-53 (Fe)结构相似的MIL-

6、53 (Al)和MIL-53(Cr)的光催化活性也做了研究,考察了结构相似,中心金属离子不同的MIL-53对光催化性质的影响。【英文摘要】Nanoporous Metal-organic frameworks (MOFs) have showed their potential applications in heterogeneous catalysis, selectivity adsorption, gas separation and storage, nolinear optical material, electrical material, and magnetic materi

7、al. Although many nanoporous metal-organic frameworks have been reported, studies on removing industrial pollution remain largely unexplored. In this thesis, selective adsorption and degrading catalyzed by nanoporous metal-organic frameworks was investigated, the products turned out to be environmen

8、t-friendly. The kinetics method involved was also investigated in this paper.This thesis mainly composed of three parts as follows:1. We studied that MIL-53(M) (M=Al, Cr, Fe) adsorbed the methyl orange (MO) in the different solutions due to the breathing of the MIL-53(M). As the iso-structure of MIL

9、-53(M) (M=Al, Cr,) and MIL-53(Fe), we also studied that MIL-53(M) (M=Al, Cr,) adsorbed the methyl orange (MO), and the effect of different solutions. Based on the experimental results, the adsorption mechanism for the adsorption of methyl orange was discussed, and a kinetic model was proposed. The a

10、pparent pseudo-second-order rate constants (k) with correlation constants (R) and the amount adsorbed at equilibrium (qe) of the adsorption reaction taking place on the surface of channels in the framework for each reaction have been calculated.2. Ultrasonic degradation industries dyes methyl blue (

11、MB) catalyzed by nanoporous metal-organic frameworks M3(BTC)2(H2O)xn (M=CuII, CoII, NiII, BTC= benzene-1,3,5-tricarboxylate) was studied using UV-vis spectral method. The effects of different sizes of M3(BTC)2(H2O)x, initial concentration of oxidant H2O2, the initial concentration of MB, and the pow

12、er of ultrasound have been comprehensively investigated. It was found that the apparent first-order rate constant increased remarkably with the increasing of initial concentration of oxidant H2O2, the power of ultrasound. Based on the experimental results, ultrasonic degradation mechanism for the de

13、gradation MB was discussed, and a kinetic model was proposed. The apparent first-order rate constants of the catalytic reaction taking place on the surface of channels in the framework (K) for each reaction have been calculated.3. We report the photocatalytic activities of MIL-53(M) (M=Al, Cr, Fe) i

14、n photodegradation of methylene blue (MB) dye. MOFs MIL-53 is three-dimensional porous solids built up by infinite inorganic chains of corner-sharedMO4(OH, F)2(M= Al, Cr, Fe, Ga, In, V) octahedral, cross-linked by bis-bidentate terephthalate (1,4-benzenedicarboxylate) linkers. Like TiO2 semiconducto

15、r whose conduction band was constructed by empty Ti 3d orbital, MOFs containing transition metals as structural nodes are also expected to be semiconductors since the empty d metal orbital mixed with the LUMOs of the organic linkers would formed the conduction band. Therefore, MOFs are expected to a

16、ctive photocatalysts, as reviewed above. Presently, MIL-53(M) is a value-added material for separating gases, including CO2, CH4, H2S and a variety of organic species. To the best of our knowledge, no attention, however, has ever been paid to study the photocatalytic properties of MIL-53(M) to date.

17、 Recently, we found that MIL-53 (Fe) exhibited photocatalytic activity for MB dye degradation under both UV-visible and visible light irradiation. The introduction of different electron acceptors in the MB aqueous solution greatly promoted the photocatalytic property of MIL-53 (Fe). To our knowledge

18、, this synergistic enhancement in the degradation of organic pollutants by the combination of different electron acceptor and MIL-53(Fe) photocatalyst has not yet been reported. Meanwhile, the photocatalytic activities of MIL-53(A1) and MIL-53(Cr), the isostructure to MIL-53 (Fe), were also investig

19、ated to provide an insight on the correlation between metal centers of a MOFs photocatalyst and its photocatalytic activity.【关键词】金属-有机骨架 选择性吸附 降解 动力学【英文关键词】Metal-organic frameworks selective adsorption degradation kinetic【目录】纳米孔洞金属有机骨架的选择性吸附与催化性质研究摘要3-5Abstract5-6第一章 绪论10-281.1 引言101.2 纳米孔洞金属-有机骨架(M

20、OFs)材料简介10-111.3 纳米孔洞金属-有机骨架(MOFs)的构成11-121.3.1 节点和连接基团111.3.2 成键类型111.3.3 次级结构单元11-121.4 纳米孔洞金属-有机骨架(MOFs)的国内外研究现状12-171.5 纳米孔洞金属-有机骨架(MOFs)的应用17-221.5.1 在催化方面的应用17-201.5.2 在气体分离与存储方面的应用20-211.5.3 在光学、电学和磁学方面的应用21-221.6 本论文选题的目的与意义22-24参考文献24-28第二章 不同溶剂对柔性金属-有机骨架MIL-53吸附甲基橙的影响28-442.1 引言28-292.2 实验

21、部分29-302.2.1 实验试剂292.2.2 表征方法和手段292.2.3 MIL-53的合成29-302.2.4 MIL-53的XRD测试302.2.5 MIL-53吸附甲基橙302.3 结果与讨论30-392.3.1 MIL-53XRD和BET表征30-312.3.2 MIL-53(Fe)吸附甲基橙水溶液,吸附时间的影响31-322.3.3 溶剂对MIL-53(Fe)吸附甲基橙的影响32-332.3.4 不同中心离子MIL-53(M)(M=Fe、Al、Cr)对甲基橙水溶液吸附的影响33-342.3.5 不同中心离子MIL-53(M)(M=Fe、Al、Cr)对甲基橙二甲苯溶液吸附的影响34-352.3.6 MIL-53吸附甲基橙动力