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CN111151301B - Bifunctional heterogeneous Pd @ MIL-101@ SGO composite material and preparation method and application thereof - Google Patents

Bifunctional heterogeneous Pd @ MIL-101@ SGO composite material and preparation method and application thereof Download PDF

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CN111151301B
CN111151301B CN202010029856.7A CN202010029856A CN111151301B CN 111151301 B CN111151301 B CN 111151301B CN 202010029856 A CN202010029856 A CN 202010029856A CN 111151301 B CN111151301 B CN 111151301B
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张渝阳
汤宏
李鑫
周美丽
吴琼
刘大亮
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Liaoning University
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Abstract

本发明涉及一种双官能团非均相Pd@MIL‑101@SGO复合材料及其制备方法和应用。采用的技术方案是：将磺化氧化石墨烯(SGO)、对苯二甲酸、九水合硝酸铬、盐酸和水加入到容器内搅拌、超声至悬浊液均匀分散，密封后放入烘箱内，于473K下保持8小时，冷却到室温，洗涤，过滤，干燥，得MIL‑101@SGO复合材料；再将氯钯酸钠的甲醇溶液缓慢滴加到MIL‑101@SGO材料中，用还原剂进行还原，得Pd@MIL‑101@SGO复合材料。本发明所制备的Pd@MIL‑101@SGO复合材料是一种催化苯乙烯一锅串连法合成β‑烷氧基醇反应的双官能团非均相催化剂。

Figure 202010029856

The invention relates to a bifunctional heterogeneous Pd@MIL-101@SGO composite material, a preparation method and application thereof. The technical scheme adopted is: adding sulfonated graphene oxide (SGO), terephthalic acid, chromium nitrate nonahydrate, hydrochloric acid and water into a container, stirring, ultrasonicating until the suspension is evenly dispersed, sealing and then placing it in an oven, Keep at 473K for 8 hours, cool to room temperature, wash, filter, and dry to obtain MIL-101@SGO composite material; then slowly drop the methanol solution of sodium chloropalladate into MIL-101@SGO material, use a reducing agent After reduction, Pd@MIL‑101@SGO composites were obtained. The Pd@MIL-101@SGO composite material prepared by the invention is a bifunctional heterogeneous catalyst for catalyzing the reaction of synthesizing β-alkoxy alcohol by a one-pot series method of styrene.

Figure 202010029856

Description

Bifunctional heterogeneous Pd @ MIL-101@ SGO composite material and preparation method and application thereof
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a palladium-loaded metal organic framework and sulfonated graphene oxide composite material and application thereof in a reaction of synthesizing beta-alkoxy alcohol by a catalytic styrene one-pot series connection method.
Background
The palladium nano particles are a high-efficiency heterogeneous catalyst and have high catalytic activity. In recent years, palladium nanoparticles have often been supported on a carrier for catalyzing various organic reactions. The metal organic framework material is a good carrier, has an ultrahigh specific surface area, is stable in structure and good in thermal stability, and has a plurality of advantages compared with other porous material carriers. However, it is difficult to directly introduce strong Bronsted acid groups onto metal organic framework materials, the yield is low and mass production is not favored.
The one-pot series reaction is a high-efficiency, energy-saving and environment-friendly chemical synthesis method, and attracts the interest of the majority of chemical researchers more and more. The series reaction usually refers to the continuous reaction of two or more steps, and the final product is directly synthesized without separating intermediate products, so that the discharge of pollutants can be effectively reduced. Beta-alkoxy alcohol is an organic solvent, a fine chemical raw material, a general synthon and a medical intermediate. The existing main approach for synthesizing beta-alkoxy alcohol is to synthesize olefin through multi-step reaction, including epoxidation of olefin and alcoholysis of epoxide, and the method used at present is complex, needs to separate intermediate products and has great environmental pollution.
Disclosure of Invention
The invention aims to provide a bifunctional heterogeneous catalyst Pd @ MIL-101@ SGO composite material and a preparation method thereof. The prepared Pd @ MIL-101@ SGO composite material has catalytic performance when used as a metal nano particle and a Bronsted acid bifunctional catalyst for synthesizing beta-alkoxy alcohol by a styrene one-pot series connection method.
According to the invention, a metal organic framework MIL-101(Cr) grows on Sulfonated Graphene Oxide (SGO) through a hydrothermal method, and then palladium nanoparticles are loaded through an equivalent impregnation method to form a novel composite material Pd @ MIL-101@ SGO.
In order to achieve the purpose, the invention adopts the following technical scheme: a preparation method of a bifunctional heterogeneous Pd @ MIL-101@ SGO composite material comprises the following steps:
1) adding sulfonated graphene oxide, terephthalic acid, chromium nitrate nonahydrate, concentrated hydrochloric acid and water into a container, stirring and ultrasonically treating until the suspension is uniformly dispersed, introducing the suspension into a reaction kettle, sealing the reaction kettle, putting the reaction kettle into an oven, keeping the reaction kettle at 493K for 8 hours, cooling to room temperature, standing for 1 day, washing with water, ethanol and dichloromethane, filtering and drying to obtain an MIL-101@ SGO solid;
2) dissolving palladium chloride with a solvent, adding sodium salt, and reacting to obtain a sodium chloropalladate solution;
3) slowly dripping the sodium chloropalladate solution into the MIL-101@ SGO solid to obtain an intermediate Pd2+@MIL-101@SGO；
4) The intermediate Pd2+The @ MIL-101@ SGO is subjected to reduction reaction by using a reducing agent to obtain the bifunctional heterogeneous Pd @ MIL-101@ SGO composite material.
Further, in the above preparation method, step 1), the preparation method of sulfonated graphene oxide includes the following steps: adding graphite powder, a mixed solution of concentrated sulfuric acid and phosphoric acid and potassium permanganate into a container cooled in an ice bath, uniformly mixing, stirring for 12 hours at 423K, cooling to room temperature, introducing the suspension into the container filled with a mixture of ice water and hydrogen peroxide, stirring for 12 hours at room temperature, washing with water, concentrated hydrochloric acid and ethanol, filtering, and drying in vacuum at 353K for 12 hours to obtain the solid sulfonated graphene oxide SGO.
Further, in the preparation method, in step 1), the mass ratio of the sulfonated graphene oxide to the terephthalic acid to the chromium nitrate nonahydrate to the concentrated hydrochloric acid is 1:2.6-3.2:6.8-7.4: 1.4-2.0.
Further, in the above preparation method, in step 2), the solvent is methanol, and the sodium salt is sodium chloride.
Further, in the above preparation method, the molar ratio of sodium chloride to palladium chloride is 19: 17.
Further, in the preparation method, in the step 4), the reducing agent is sodium borohydride, the reduction reaction temperature is 298K, and the reduction time is 30 min.
Application of bifunctional heterogeneous Pd @ MIL-101@ SGO composite material in synthesizing beta-alkoxy alcohol by a catalytic styrene one-pot tandem method. The method comprises the following steps: taking styrene, an oxidant, a solvent and a catalyst into a reaction tube, and stirring and reacting for 5 hours under the condition of 343K; the catalyst is the bifunctional heterogeneous Pd @ MIL-101@ SGO composite material.
Further, the oxidant is tert-butyl hydroperoxide, and the solvent is a mixed solution of methanol and water.
Further, in the solvent, the ratio of methanol to water is 1:3 by volume.
The invention has the beneficial effects that:
sulfonated Graphene Oxide (SGO) is a material with a strong Bronsted acid, and the sheet-like structure material is not beneficial to the loading of palladium nanoparticles. According to the invention, a metal organic framework MIL-101 and sulfonated graphene oxide are combined to form a composite material MIL-101@ SGO, and then palladium nanoparticles are loaded on the composite material, so that a novel composite material Pd @ MIL-101@ SGO with bifunctional groups is formed. The Pd @ MIL-101@ SGO composite material prepared by the invention is a bifunctional heterogeneous catalyst simultaneously provided with metal nanoparticles and Bronsted acid. The catalyst has excellent catalytic activity for the reaction of synthesizing beta-alkoxy alcohol by a styrene one-pot series method, the reaction time is only 5 hours, the yield can reach 100 percent, and the catalyst is easy to separate from reactants and has good recycling capability. Therefore, the catalyst has very high application value.
Drawings
FIG. 1 is an XRD pattern of a Pd @ MIL-101@ SGO composite material and MIL-101@ SGO of the present invention.
FIG. 2 is a transmission electron microscope image of the Pd @ MIL-101@ SGO composite of the present invention.
FIG. 3 shows the catalytic activity of the Pd @ MIL-101@ SGO composite material of the present invention in five catalytic cycles.
Detailed Description
In order that the invention may be better understood, the invention is further illustrated by the following examples, which are to be construed as being better understood and not limiting upon the scope of the invention.
Example 1 Pd @ MIL-101@ SGO composite
The preparation method comprises
1. Preparation of Sulfonated Graphene Oxide (SGO): adding 30g of graphite powder, 400mL of mixed solution of concentrated sulfuric acid and phosphoric acid (volume ratio is 9:1) and 9g of potassium permanganate into a container cooled in an ice bath, uniformly mixing, stirring for 12 hours at 423K, cooling to room temperature, introducing the suspension into a container filled with 400mL of ice water and 3mL of hydrogen peroxide, stirring for 12 hours at room temperature, sequentially washing with water, concentrated hydrochloric acid and ethanol, filtering, and vacuum-drying for 12 hours at 353K to obtain the SGO solid.
2. Preparation of MIL-101@ SGO composite: h is to be2BDC(1.328g,8mmol)、Cr(NO3)3·9H2Dissolving O (3.2g,8mmol) and concentrated hydrochloric acid (0.789g) in 40mL of ultrapure water, adding 0.4528g of SGO, stirring, performing ultrasonic treatment until the suspension is uniformly dispersed, pouring the suspension into an 80mL reaction kettle, sealing the reaction kettle, heating in a 493K oven for 8 hours, sequentially washing with water, ethanol and dichloromethane for 3 times, filtering and drying to obtain the MIL-101@ SGO composite material.
3. Activation of MIL-101@ SGO composite: the dried MIL-101@ SGO was spread in a thin layer in an open container and dried under vacuum at 423K for 12 h.
4. Preparing a sodium chloropalladate solution: dissolving palladium chloride (20mg, 0.68mmol) in 4mL of methanol, adding sodium chloride (44mg, 0.76mmol), and stirring at room temperature for 12 hr to obtain sodium chloropalladate solution (Na)2PdCl4)。
5. Preparation of Pd @ MIL-101@ SGO composite material: 50mg of activated MIL-101@ SGO was placed in a vial, and 60. mu.L of Na was added dropwise thereto2PdCl4(0.17mol/L) Methanol solution to Na2PdCl4The methanol solution is completely absorbed to obtain an intermediate Pd2+@MIL-101@SGO。
Then, the intermediate Pd is stirred2+0.6mol/L NaBH is added dropwise while @ MIL-101@ SGO is added43mL of methanol solution is subjected to reduction reaction at 298K for 30 min. After filtering, vacuum drying for 12h at 393K to obtain the target product Pd @ MIL-101@ SGO composite material.
FIG. 1 is a powder X-ray diffraction (PXRD) pattern of a Pd @ MIL-101@ SGO composite material, showing the structural integrity of the Pd @ MIL-101@ SGO composite material during the preparation process.
FIG. 2 is a Transmission Electron Microscope (TEM) image of the Pd @ MIL-101@ SGO composite material, wherein the microscopic morphology of Pd @ MIL-101 can be observed, and palladium nanoparticles are well loaded in the pores of the MIL-101@ SGO.
Example 2 Pd @ MIL-101@ SGO composite catalytic function in one pot tandem Synthesis of beta-alkoxy alcohol with styrene
The Pd @ MIL-101@ SGO composite material prepared in example 1 is used as a catalyst to catalyze the reaction of synthesizing beta-alkoxy alcohol by a styrene one-pot tandem method.
The method comprises the following steps: 1mmol of styrene, 2mmol of t-butyl hydroperoxide, 1mL of methanol, 3mL of water, and 50mg of a catalyst were put in a 10mL reaction tube, and stirred and heated under 343K. The experimental results were monitored by gas chromatograph GC, and as the reaction proceeded, the yield of the reaction gradually increased, and the yield reached 100% at 5 hours. The reaction formula is as follows:
Figure BDA0002363897360000041
after the reaction is completed, the catalyst is separated by filtration, washed several times with water, methanol, filtered off again and dried in vacuo. The recovered catalyst was subjected to the next cycle experiment. As shown in fig. 3, the activity of the catalyst did not decrease even after the cycle experiment was performed to the 5 th round. The Pd @ MIL-101@ SGO composite material can be recycled as a reaction catalyst for synthesizing beta-alkoxy alcohol by a styrene one-pot series method.

Claims (9)

1.一种双官能团非均相Pd@MIL-101@SGO复合材料的制备方法，其特征在于，包括如下步骤：1. a preparation method of bifunctional heterogeneous Pd@MIL-101@SGO composite material, is characterized in that, comprises the steps: 1）将磺化氧化石墨烯、对苯二甲酸、九水硝酸铬、浓盐酸和水加入到容器内搅拌、超声至悬浊液均匀分散后，将悬浊液导入反应釜中，将反应釜密封后放入烘箱内，在493 K下保持8小时，冷却到室温，静置1天后，用水、乙醇和二氯甲烷洗涤，过滤，干燥，得MIL-101@SGO固体；1) Add sulfonated graphene oxide, terephthalic acid, chromium nitrate nonahydrate, concentrated hydrochloric acid and water into the container, stir and ultrasonicate until the suspension is evenly dispersed, then introduce the suspension into the reaction kettle, and put the reaction kettle After sealing, it was placed in an oven, kept at 493 K for 8 hours, cooled to room temperature, and after standing for 1 day, washed with water, ethanol and dichloromethane, filtered and dried to obtain MIL-101@SGO solid; 2）取氯化钯用溶剂进行溶解，加入钠盐，反应得氯钯酸钠溶液；2) dissolving palladium chloride in a solvent, adding sodium salt, and reacting to obtain sodium chloropalladate solution; 3）将氯钯酸钠溶液缓慢滴加到MIL-101@SGO固体中，得中间体Pd2+@MIL-101@SGO；3) Slowly add sodium chloropalladate solution dropwise to the MIL-101@SGO solid to obtain the intermediate Pd 2+ @MIL-101@SGO; 4）将中间体Pd2+@MIL-101@SGO用硼氢化钠进行还原反应，得双官能团非均相Pd@MIL-101@SGO复合材料。4) The intermediate Pd 2+ @MIL-101@SGO was reduced with sodium borohydride to obtain bifunctional heterogeneous Pd@MIL-101@SGO composites. 2.根据权利要求1所述的制备方法，其特征在于，步骤1）中，所述磺化氧化石墨烯的制备方法包括如下步骤：将石墨粉、浓硫酸与磷酸混合液、高锰酸钾加入到冰浴降温的容器内，混合均匀后，在423 K下搅拌12小时，冷却到室温后，将悬浊液导入装有冰水、过氧化氢混合物的容器中，在室温下搅拌12小时，用水、浓盐酸、乙醇洗涤，过滤，于353 K真空干燥12h，得固体磺化氧化石墨烯SGO。2. The preparation method according to claim 1, wherein in step 1), the preparation method of the sulfonated graphene oxide comprises the following steps: mixing graphite powder, concentrated sulfuric acid and phosphoric acid, potassium permanganate Add it to a container cooled by an ice bath, mix well, stir at 423 K for 12 hours, cool to room temperature, introduce the suspension into a container containing a mixture of ice water and hydrogen peroxide, and stir at room temperature for 12 hours , washed with water, concentrated hydrochloric acid, and ethanol, filtered, and vacuum-dried at 353 K for 12 h to obtain solid sulfonated graphene oxide SGO. 3.根据权利要求1所述的制备方法，其特征在于，步骤1）中，按质量比，磺化氧化石墨烯:对苯二甲酸:九水硝酸铬:浓盐酸=1 : 2.6-3.2 : 6.8-7.4 : 1.4-2.0。3. preparation method according to claim 1, is characterized in that, in step 1), by mass ratio, sulfonated graphene oxide: terephthalic acid: chromium nitrate nonahydrate: concentrated hydrochloric acid=1: 2.6-3.2: 6.8-7.4: 1.4-2.0. 4.根据权利要求1所述的制备方法，其特征在于，步骤2）中，所述溶剂为甲醇，所述钠盐为氯化钠。The preparation method according to claim 1, wherein in step 2), the solvent is methanol, and the sodium salt is sodium chloride. 5.根据权利要求4所述的制备方法，其特征在于，按摩尔比，氯化钠:氯化钯=19:17。5. preparation method according to claim 4 is characterized in that, in molar ratio, sodium chloride: palladium chloride=19:17. 6.根据权利要求1所述的制备方法，其特征在于，步骤4）中，所述还原反应温度为298K，还原时间为30 min。6 . The preparation method according to claim 1 , wherein in step 4), the reduction reaction temperature is 298K, and the reduction time is 30 min. 7 . 7.根据权利要求1所述的方法制备的双官能团非均相Pd@MIL-101@SGO复合材料在催化苯乙烯一锅串连法合成β-烷氧基醇中的应用。7. Application of the bifunctional heterogeneous Pd@MIL-101@SGO composite material prepared by the method according to claim 1 in catalyzing the synthesis of β-alkoxy alcohol by styrene one-pot tandem method. 8.根据权利要求7所述的应用，其特征在于，方法如下：取苯乙烯、氧化剂、溶剂和催化剂于反应管中，在343 K的条件下搅拌反应5 h；所述催化剂是权利要求1所述的双官能团非均相Pd@MIL-101@SGO复合材料；所述氧化剂是叔丁基过氧化氢，所述溶剂是甲醇和水的混合溶液。8. application according to claim 7, is characterized in that, method is as follows: get styrene, oxidant, solvent and catalyzer in reaction tube, under the condition of 343 K stirring reaction 5 h; Described catalyzer is claim 1 The bifunctional heterogeneous Pd@MIL-101@SGO composite material; the oxidant is tert-butyl hydroperoxide, and the solvent is a mixed solution of methanol and water. 9.根据权利要求8所述的应用，其特征在于，所述溶剂中，按体积比，甲醇:水=1:3。9. application according to claim 8, is characterized in that, in described solvent, by volume ratio, methanol: water=1:3.
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