聯(lián)吡啶鉑復(fù)合物合成MOF催化劑的研究
發(fā)布時間：2018-09-04 20:05
【摘要】：金屬有機骨架(MOFs)大多是由含氧、氮等多齒有機配體與無機金屬離子通過配位作用自組裝形成的一種有序網(wǎng)絡(luò)狀多孔結(jié)構(gòu)材料。它具有大的比表面積,高的孔隙率,且結(jié)構(gòu)多樣等特點。還可以依據(jù)需要使用不同的配體進行孔尺寸的調(diào)節(jié)。這些特點使得MOFs材料在氣體分離與儲存、催化、藥物緩釋和熒光材料等領(lǐng)域被研究者廣泛應(yīng)用。在催化領(lǐng)域中,MOFs也經(jīng)常作為載體,實現(xiàn)催化劑從均相到非均相的轉(zhuǎn)變,使得催化劑在保留有催化活性的基礎(chǔ)上能循環(huán)多次利用。使用含氮配體合成的MOFs會因為氮的存在能使載體具有獨特的電子性質(zhì)、提高金屬-載體相互作用力。本論文主要選用MOFs材料中UIO-67材料進行實驗研究。使用2,2'-聯(lián)吡啶-5,5'-二羧酸(bpydc)與4,4'-聯(lián)苯二甲酸(bpdc)作為配體,合成UIO-67材料。通過對合成UIO-67材料的配體進行修飾,設(shè)計合成出能應(yīng)用于工業(yè)催化的新型高效MOFs催化劑,并對催化劑的結(jié)構(gòu)性質(zhì)與催化性能之間的內(nèi)在關(guān)系進行研究。論文的主要研究內(nèi)容如下:1.在UIO-67原有的合成基礎(chǔ)上,首先對兩種配體的摩爾用量比與鋯源的摩爾用量比進行調(diào)節(jié)。在鋯源與配體摩爾用量比達到1:1,兩種配體之間摩爾用量比達到1:1時為合成我們所需材料的最佳條件。然后將配體2,2'-聯(lián)吡啶-5,5'-二羧酸(bpydc)與[Pt(Ph)2(Et2S)]2在無水乙醚中氮氣保護下進行反應(yīng),到含鉑金屬復(fù)合物的配體Pt(Ph)2@bpydc。隨后將鋯源與兩種配體在DMF溶劑中,120 oC氮氣保護下進行原位一步還原合成含有鉑納米粒子的UIO-67催化劑。通過調(diào)節(jié)Pt(Ph)2@bpydc與bpdc兩種配體的摩爾用量比至1:9時,得到形貌最佳的催化劑。將催化劑應(yīng)用至催化5-羥甲基糠醛生成2,5-二羥甲基呋喃反應(yīng),反應(yīng)物轉(zhuǎn)化率達到99.5%,最終產(chǎn)率達到90%以上,說明催化劑的應(yīng)用具有一定的前景。2.為了解決工業(yè)上使用Friedel-Crafts法制備烷基芳烴方法的缺點(催化劑回收困難,得到的產(chǎn)物不是單一產(chǎn)物含有多種副產(chǎn)物的缺點)。我們參考了美國弗吉尼亞大學T.Brent.Gunnoe教授使用鉑的聯(lián)吡啶配合物作為催化劑制備烷基芳烴文獻,將[Pt(Ph)2(Et2S)]2負載至UIO-67上制備Pt(Ph)2@UIO-67催化劑。首先在前一部分對配體2,2'-聯(lián)吡啶-5,5'-二羧酸(bpydc)進行修飾得到含鉑金屬復(fù)合物的配體Pt(Ph)2@bpydc的基礎(chǔ)上,使用DMSO溶劑替換DMF溶劑進行合成催化劑。在DMSO溶液中采用一步法合成Pt(Ph)2@UIO-67。通過調(diào)節(jié)酸的種類(苯甲酸與乙酸)與濃度(鋯源摩爾量的40倍-70倍),確立了乙酸為輔助酸,40倍用量的濃度為合成所需催化劑的條件,并對催化劑進行表征。在本部分,我們也嘗試使用后嫁接合成法合成催化劑,先使用bpdc與bpydc在DMF溶劑中120 oC下合成UIO-67,然后將其與[Pt(Ph)2(Et2S)]2在無水乙醚中氮氣保護下進行反應(yīng),得到Pt(Ph)_2@UIO-67,并對其進行結(jié)構(gòu)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.
【學位授予單位】：上海師范大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O643.36
本文編號：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.
【學位授予單位】：上海師范大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O643.36
【參考文獻】
相關(guān)期刊論文 前1條
1 魏文英,方鍵,孔海寧,韓金玉,常賀英;金屬有機骨架材料的合成及應(yīng)用[J];化學進展;2005年06期
，本文編號：2223194
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