CN111151301A - 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 PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 13
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 10
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 7
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 5
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 claims abstract description 5
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- 238000003756 stirring Methods 0.000 claims description 11
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- 239000002904 solvent Substances 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
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- 239000007787 solid Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
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- 238000001816 cooling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
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- 159000000000 sodium salts Chemical class 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical group CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
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- 230000002194 synthesizing effect Effects 0.000 description 4
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- 150000001336 alkenes Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000013177 MIL-101 Substances 0.000 description 1
- 239000013178 MIL-101(Cr) Substances 0.000 description 1
- 229910003244 Na2PdCl4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
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- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- B01J35/393—
-
- B01J35/396—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
Abstract
The invention relates to a bifunctional heterogeneous Pd @ MIL-101@ SGO composite material and a preparation method and application thereof.A technical scheme adopted by the invention is that Sulfonated Graphene Oxide (SGO), terephthalic acid, chromium nitrate nonahydrate, hydrochloric acid and water are added into a container to be stirred and ultrasonically treated until suspension is uniformly dispersed, the container is sealed and then placed into an oven to be kept for 8 hours at 473K, the container is cooled to room temperature, washed, filtered and dried to obtain the MIL-101@ SGO composite material, a methanol solution of sodium chloropalladate is slowly dripped into the MIL-101@ SGO material and is reduced by a reducing agent to obtain the Pd @ MIL-101@ SGO composite material.
Description
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 the reaction of synthesizing β -alkoxy alcohol by a catalytic styrene one-pot series 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 cascade reaction is usually characterized by continuous reaction of two or more steps, does not need to separate intermediate products, directly synthesizes final products and can effectively reduce the emission of pollutants, β -alkoxy alcohol is an organic solvent, a fine chemical raw material, a general synthon and a medical intermediate, the existing main way for synthesizing β -alkoxy alcohol is that olefin is synthesized by multi-step reaction, including the epoxidation of olefin and the alcoholysis of epoxide, the method used at the present stage is complex, the intermediate products need to be separated, and the environmental pollution is great.
Disclosure of Invention
The invention aims to provide a bifunctional heterogeneous catalyst Pd @ MIL-101@ SGO composite material and a preparation method thereof, wherein the prepared Pd @ MIL-101@ SGO composite material has catalytic performance when used as a metal nanoparticle and a Bronsted acid bifunctional catalyst for synthesizing β -alkoxy alcohol by a one-pot series method for styrene.
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.
The application of the bifunctional heterogeneous Pd @ MIL-101@ SGO composite material in the synthesis of β -alkoxy alcohol by a styrene one-pot tandem catalysis method comprises the following steps of putting styrene, an oxidant, a solvent and a catalyst into a reaction tube, and stirring and reacting for 5 hours under the condition of 343K, wherein 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:
the invention combines a metal organic framework MIL-101 and sulfonated graphene oxide to form a composite material MIL-101@ SGO, and then the composite material is loaded with palladium nano particles to form a novel composite material Pd @ MIL-101@ SGO with double functional groups, the Pd @ MIL-101@ SGO composite material prepared by the invention is a double functional group heterogeneous catalyst simultaneously provided with the metal nano particles and the Bronsted acid, the catalyst has excellent catalytic activity for synthesizing β -alkoxy alcohol by a one-pot tandem method for styrene, the reaction time is only 5 hours, the yield can reach 100%, and the catalyst is easy to separate from reactants and has good recycling capability, so 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: palladium chloride (20mg, 0.68mmol) was dissolved in 4mL of methanol, and sodium chloride (44mg, 0.76mmol) was added thereto at room temperatureStirring and reacting for 12 hours to obtain a reaction 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 for the one-pot tandem Synthesis of β -alkoxy alcohol with styrene
The Pd @ MIL-101@ SGO composite material prepared in example 1 is used as a catalyst to catalyze the synthesis of β -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:
after the reaction is finished, the catalyst is separated by filtration, washed by water and methanol for a plurality of times, filtered and dried in vacuum, and the recovered catalyst is subjected to the next circulation experiment, as shown in figure 3, the activity of the catalyst is still not reduced when the circulation experiment is carried out to the 5 th round, which shows that the Pd @ MIL-101@ SGO composite material can be recycled as the β -alkoxy alcohol synthesized by the styrene one-pot series method.
Claims (10)
1. A preparation method of a bifunctional heterogeneous Pd @ MIL-101@ SGO composite material is characterized by comprising 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.
2. The preparation method according to claim 1, wherein in step 1), the preparation method of the sulfonated graphene oxide comprises 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.
3. The preparation method according to claim 1, wherein 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.
4. The method according to claim 1, wherein in step 2), the solvent is methanol and the sodium salt is sodium chloride.
5. The method according to claim 4, wherein the molar ratio of sodium chloride to palladium chloride is 19: 17.
6. The preparation method according to claim 1, wherein in the step 4), the reducing agent is sodium borohydride, the reduction reaction temperature is 298K, and the reduction time is 30 min.
7. The use of the bifunctional heterogeneous Pd @ MIL-101@ SGO composite prepared according to the method of claim 1 in the catalytic one-pot tandem synthesis of β -alkoxyalcohols.
8. Use according to claim 7, characterized in that the method is as follows: 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 of claim 1.
9. The use according to claim 8, wherein the oxidant is t-butyl hydroperoxide and the solvent is a mixed solution of methanol and water.
10. The use according to claim 9, wherein the ratio of methanol to water is 1:3 by volume in the solvent.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112210081A (en) * | 2020-09-29 | 2021-01-12 | 西安建筑科技大学 | Sulfonated graphene oxide loaded metal organic framework modified forward osmosis nano composite membrane and preparation method thereof |
| CN112210081B (en) * | 2020-09-29 | 2022-06-21 | 西安建筑科技大学 | Sulfonated graphene oxide loaded metal organic framework modified forward osmosis nano composite membrane and preparation method thereof |
| CN114452945A (en) * | 2022-02-15 | 2022-05-10 | 中国船舶重工集团公司第七一九研究所 | Preparation method of MOF composite material adsorbent for removing toluene gas |
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