联吡啶铂复合物合成MOF催化剂的研究
发布时间：2018-09-04 20:05
【摘要】：金属有机骨架(MOFs)大多是由含氧、氮等多齿有机配体与无机金属离子通过配位作用自组装形成的一种有序网络状多孔结构材料。它具有大的比表面积,高的孔隙率,且结构多样等特点。还可以依据需要使用不同的配体进行孔尺寸的调节。这些特点使得MOFs材料在气体分离与储存、催化、药物缓释和荧光材料等领域被研究者广泛应用。在催化领域中,MOFs也经常作为载体,实现催化剂从均相到非均相的转变,使得催化剂在保留有催化活性的基础上能循环多次利用。使用含氮配体合成的MOFs会因为氮的存在能使载体具有独特的电子性质、提高金属-载体相互作用力。本论文主要选用MOFs材料中UIO-67材料进行实验研究。使用2,2'-联吡啶-5,5'-二羧酸(bpydc)与4,4'-联苯二甲酸(bpdc)作为配体,合成UIO-67材料。通过对合成UIO-67材料的配体进行修饰,设计合成出能应用于工业催化的新型高效MOFs催化剂,并对催化剂的结构性质与催化性能之间的内在关系进行研究。论文的主要研究内容如下:1.在UIO-67原有的合成基础上,首先对两种配体的摩尔用量比与锆源的摩尔用量比进行调节。在锆源与配体摩尔用量比达到1:1,两种配体之间摩尔用量比达到1:1时为合成我们所需材料的最佳条件。然后将配体2,2'-联吡啶-5,5'-二羧酸(bpydc)与[Pt(Ph)2(Et2S)]2在无水乙醚中氮气保护下进行反应,到含铂金属复合物的配体Pt(Ph)2@bpydc。随后将锆源与两种配体在DMF溶剂中,120 oC氮气保护下进行原位一步还原合成含有铂纳米粒子的UIO-67催化剂。通过调节Pt(Ph)2@bpydc与bpdc两种配体的摩尔用量比至1:9时,得到形貌最佳的催化剂。将催化剂应用至催化5-羟甲基糠醛生成2,5-二羟甲基呋喃反应,反应物转化率达到99.5%,最终产率达到90%以上,说明催化剂的应用具有一定的前景。2.为了解决工业上使用Friedel-Crafts法制备烷基芳烃方法的缺点(催化剂回收困难,得到的产物不是单一产物含有多种副产物的缺点)。我们参考了美国弗吉尼亚大学T.Brent.Gunnoe教授使用铂的联吡啶配合物作为催化剂制备烷基芳烃文献,将[Pt(Ph)2(Et2S)]2负载至UIO-67上制备Pt(Ph)2@UIO-67催化剂。首先在前一部分对配体2,2'-联吡啶-5,5'-二羧酸(bpydc)进行修饰得到含铂金属复合物的配体Pt(Ph)2@bpydc的基础上,使用DMSO溶剂替换DMF溶剂进行合成催化剂。在DMSO溶液中采用一步法合成Pt(Ph)2@UIO-67。通过调节酸的种类(苯甲酸与乙酸)与浓度(锆源摩尔量的40倍-70倍),确立了乙酸为辅助酸,40倍用量的浓度为合成所需催化剂的条件,并对催化剂进行表征。在本部分,我们也尝试使用后嫁接合成法合成催化剂,先使用bpdc与bpydc在DMF溶剂中120 oC下合成UIO-67,然后将其与[Pt(Ph)2(Et2S)]2在无水乙醚中氮气保护下进行反应,得到Pt(Ph)_2@UIO-67,并对其进行结构形貌表征。
[Abstract]:The metal-organic skeleton (MOFs) is a kind of ordered network porous structure material, which is composed of oxygen, nitrogen and inorganic metal ions through the coordination interaction self-assembly. It has the characteristics of large specific surface area, high porosity and diverse structure. Different ligands can also be used to adjust the pore size. These characteristics make MOFs materials widely used in gas separation and storage, catalysis, drug delivery and fluorescent materials. In the field of catalysis, MOFs are often used as support to realize the transition from homogeneous to heterogeneous, which makes the catalyst can be reused on the basis of keeping catalytic activity. MOFs synthesized with nitrogen-containing ligands can enhance the metal-carrier interaction force because of the unique electronic properties of the carrier due to the presence of nitrogen. In this paper, UIO-67 materials in MOFs materials are selected for experimental study. The UIO-67 material was synthesized by using the ligand of 2O2O2-bipyridine-5Ca-dicarboxylic acid (bpydc) and (bpdc) (4C4C4-biphenyl dicarboxylic acid) as ligands. By modifying the ligands of synthetic UIO-67 materials, a new type of high efficient MOFs catalyst which can be used in industrial catalysis was designed and synthesized, and the relationship between the structure properties and catalytic properties of the catalysts was studied. The main contents of this thesis are as follows: 1. On the basis of the original synthesis of UIO-67, the molar ratio of the two ligands and the molar ratio of zirconium source were first adjusted. When the molar ratio of zirconium source to ligand reaches 1: 1, and the molar ratio between the two ligands reaches 1:1, the optimum conditions for the synthesis of the materials we need are obtained. Then the ligands 2O2O2-bipyridine-5Ca-dicarboxylic acid (bpydc) reacted with [Pt (Ph) _ 2 (Et2S)] _ 2 under the protection of nitrogen in anhydrous ether to the ligand Pt (Ph) _ 2bpyridine containing platinum complex. Then the zirconium source and two ligands were prepared by in situ one-step reduction under the protection of 120 oC nitrogen in DMF solvent to synthesize UIO-67 catalyst containing platinum nanoparticles. The best catalyst was obtained by adjusting the molar ratio of Pt (Ph) 2@bpydc and bpdc to 1:9. The catalyst was used to catalyze the reaction of 5-hydroxymethylfural to produce 2o 5-dihydroxymethyl furan. The conversion of the reactant was 99.55.The final yield was over 90%, which indicated that the catalyst had a certain prospect. In order to solve the disadvantage of the method of preparing alkyl aromatics by Friedel-Crafts method in industry (the catalyst is difficult to recover, the product is not a single product containing a variety of by-products). We refer to the literature on the preparation of alkyl aromatics using platinum bipyridine complex as catalyst by Professor T.Brent.Gunnoe of the University of Virginia, USA. [Pt (Ph) _ 2 (Et2S)] _ 2 was supported on UIO-67 to prepare Pt (Ph) 2@UIO-67 catalyst. Firstly, the ligand Pt (Ph) 2@bpydc containing platinum complex was prepared by modifying the ligand 2O2O2-bipyridine-5Ca-dicarboxylic acid (bpydc), and then the solvent of DMSO was used to replace the solvent of DMF for the synthesis of the catalyst. Pt (Ph) _ 2 @ UIO-67 was synthesized by one-step method in DMSO solution. By adjusting the kinds of acids (benzoic acid and acetic acid) and their concentration (40 to 70 times of the molar amount of zirconium source), the conditions of 40 times amount of acetic acid as the catalyst for the synthesis were established, and the catalyst was characterized. In this part, we also try to use the post-grafting synthesis catalyst to synthesize UIO-67, with bpdc and bpydc in DMF solvent for 120 oC and then react with [Pt (Ph) _ 2 (Et2S)] _ 2 under the protection of nitrogen in anhydrous ether. Pt (Ph) 2 @ UIO-67 was obtained and its structure was characterized.
【学位授予单位】：上海师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O643.36
本文编号：2223194
[Abstract]:The metal-organic skeleton (MOFs) is a kind of ordered network porous structure material, which is composed of oxygen, nitrogen and inorganic metal ions through the coordination interaction self-assembly. It has the characteristics of large specific surface area, high porosity and diverse structure. Different ligands can also be used to adjust the pore size. These characteristics make MOFs materials widely used in gas separation and storage, catalysis, drug delivery and fluorescent materials. In the field of catalysis, MOFs are often used as support to realize the transition from homogeneous to heterogeneous, which makes the catalyst can be reused on the basis of keeping catalytic activity. MOFs synthesized with nitrogen-containing ligands can enhance the metal-carrier interaction force because of the unique electronic properties of the carrier due to the presence of nitrogen. In this paper, UIO-67 materials in MOFs materials are selected for experimental study. The UIO-67 material was synthesized by using the ligand of 2O2O2-bipyridine-5Ca-dicarboxylic acid (bpydc) and (bpdc) (4C4C4-biphenyl dicarboxylic acid) as ligands. By modifying the ligands of synthetic UIO-67 materials, a new type of high efficient MOFs catalyst which can be used in industrial catalysis was designed and synthesized, and the relationship between the structure properties and catalytic properties of the catalysts was studied. The main contents of this thesis are as follows: 1. On the basis of the original synthesis of UIO-67, the molar ratio of the two ligands and the molar ratio of zirconium source were first adjusted. When the molar ratio of zirconium source to ligand reaches 1: 1, and the molar ratio between the two ligands reaches 1:1, the optimum conditions for the synthesis of the materials we need are obtained. Then the ligands 2O2O2-bipyridine-5Ca-dicarboxylic acid (bpydc) reacted with [Pt (Ph) _ 2 (Et2S)] _ 2 under the protection of nitrogen in anhydrous ether to the ligand Pt (Ph) _ 2bpyridine containing platinum complex. Then the zirconium source and two ligands were prepared by in situ one-step reduction under the protection of 120 oC nitrogen in DMF solvent to synthesize UIO-67 catalyst containing platinum nanoparticles. The best catalyst was obtained by adjusting the molar ratio of Pt (Ph) 2@bpydc and bpdc to 1:9. The catalyst was used to catalyze the reaction of 5-hydroxymethylfural to produce 2o 5-dihydroxymethyl furan. The conversion of the reactant was 99.55.The final yield was over 90%, which indicated that the catalyst had a certain prospect. In order to solve the disadvantage of the method of preparing alkyl aromatics by Friedel-Crafts method in industry (the catalyst is difficult to recover, the product is not a single product containing a variety of by-products). We refer to the literature on the preparation of alkyl aromatics using platinum bipyridine complex as catalyst by Professor T.Brent.Gunnoe of the University of Virginia, USA. [Pt (Ph) _ 2 (Et2S)] _ 2 was supported on UIO-67 to prepare Pt (Ph) 2@UIO-67 catalyst. Firstly, the ligand Pt (Ph) 2@bpydc containing platinum complex was prepared by modifying the ligand 2O2O2-bipyridine-5Ca-dicarboxylic acid (bpydc), and then the solvent of DMSO was used to replace the solvent of DMF for the synthesis of the catalyst. Pt (Ph) _ 2 @ UIO-67 was synthesized by one-step method in DMSO solution. By adjusting the kinds of acids (benzoic acid and acetic acid) and their concentration (40 to 70 times of the molar amount of zirconium source), the conditions of 40 times amount of acetic acid as the catalyst for the synthesis were established, and the catalyst was characterized. In this part, we also try to use the post-grafting synthesis catalyst to synthesize UIO-67, with bpdc and bpydc in DMF solvent for 120 oC and then react with [Pt (Ph) _ 2 (Et2S)] _ 2 under the protection of nitrogen in anhydrous ether. Pt (Ph) 2 @ UIO-67 was obtained and its structure was characterized.
【学位授予单位】：上海师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O643.36
【参考文献】
相关期刊论文 前1条
1 魏文英,方键,孔海宁,韩金玉,常贺英;金属有机骨架材料的合成及应用[J];化学进展;2005年06期
，本文编号：2223194
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