CN114618593B - Prussian blue analogue/Cux-Coy-MOF composite material and preparation method and application thereof - Google Patents
Prussian blue analogue/Cux-Coy-MOF composite material and preparation method and application thereof Download PDFInfo
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- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000012924 metal-organic framework composite Substances 0.000 title claims abstract description 32
- 229960003351 prussian blue Drugs 0.000 title claims abstract description 24
- 239000013225 prussian blue Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 title abstract description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000011159 matrix material Substances 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims abstract description 5
- 239000012266 salt solution Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000012257 stirred material Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 19
- 239000002244 precipitate Substances 0.000 abstract description 7
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 abstract description 4
- 238000001132 ultrasonic dispersion Methods 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 239000012918 MOF catalyst Substances 0.000 description 9
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000011084 recovery Methods 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- -1 acetyl Diamide Chemical compound 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 230000007847 structural defect Effects 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
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- 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]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/26—Cyanides
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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
- B01J31/22—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
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- 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
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/72—Epoxidation
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
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Abstract
The invention discloses a Prussian blue analogue/Cu x ‑Co y MOF composite material, preparation method and application thereof, wherein Prussian blue analogue is used as matrix, and Cu is used as matrix x ‑Co y -MOF is an active component, which is supported on the surface of the prussian blue analogue; the preparation process comprises the following steps: will K 3 [Co(CN) 6 ]Dripping the solution into a metal salt solution, stirring, standing, centrifuging, collecting precipitate, washing, and vacuum drying to obtain solid powder; cu (NO) 3 ) 2 ·3H 2 O、Co(NO 3 ) 2 ·6H 2 O and H 3 Dissolving BTC in a mixed solution of DMF and ethanol for ultrasonic dispersion; and adding the solid powder into the mixed solution, stirring, and transferring to a hydrothermal reaction kettle for reaction to obtain the composite material. The composite material prepared by the invention can effectively improve the conversion rate of styrene to styrene oxide, and the catalyst can be recycled for a plurality of times.
Description
Technical Field
The invention relates to a composite material, a preparation method and application thereof, in particular to Prussian blue analogues/Cu x -Co y -MOF composite material, and preparation method and application thereof.
Background
Prussian blue analogues (Prussian blue analoggues, PBA) have a structure similar to molecular sieves, and therefore considerable research has been done on the use of PBA in small molecule storage. Prussian blue analogues are double metal cyanide complexes with large surface areas and Lewis acid sites. These properties make Prussian blue complexes good catalysts for many reactions. Meanwhile, PBA was originally an epoxy ring-opening polymerization catalyst developed by general rubber company in the united states, and PBA was also used as a solid phase catalyst as a simple double metal cyanide complex.
In the study of Prussian blue analogues as catalysts, it was found that the catalytic activity for preparing the synthesized product was not ideal. Furthermore, the catalytic activity of the PBA catalyst is strongly dependent on the composition of the ligand. Thus, research into combining PBA materials with other materials to increase their activity is increasingly gaining attention. The factors affecting the activity were found to be: preparation process, metal ion type and content, organic ligand type, etc. In addition, PBA catalysts are also combined with, for example, molecular sieves, oxides, inorganic salts to increase their activity.
When Prussian blue analogues are generated by the existing method, the catalyst has a plurality of structural defects, so that the existing catalyst has a skeleton structure which is easy to collapse and cannot be recycled for multiple times, and therefore, the recovery rate is low, and the activity of the catalyst is low. In addition, the existing preparation method has the defects of most of complexity, long preparation period and the like.
Disclosure of Invention
The invention aims to: the invention aims to provide Prussian blue analogues/Cu which can effectively improve the conversion rate of styrene and the yield of epoxy phenylethane, have stable structure and can be recycled for multiple times x -Co y -MOF composite; another object of the present invention is to provide the Prussian blue analog/Cu x -Co y -a method of preparing a MOF composite; another object of the present invention is to provide the Prussian blue analog/Cu x -Co y -the use of MOF composites in the catalytic oxidation of styrene.
The technical scheme is as follows: prussian blue analogues/Cu according to the invention x -Co y MOF composite material taking Prussian blue analogues as matrix and Cu x -Co y -MOF is an active component, the active component is loaded on the surface of Prussian blue analogues, and the Cu is x -Co y The MOF is composed of Cu (NO 3 ) 2 ·3H 2 O、Co(NO 3 ) 2 ·6H 2 O and trimesic acid H 3 BTC.
Further, x=0.25 to 0.75, and y=1 to x.
Further, the Prussian blue analog is one of FeCoPBA, niCoPBA, znCoPBA or CoCoPBA.
The Prussian blue analogues/Cu x -Co y -a method of preparing a MOF composite comprising the steps of: will K 3 [Co(CN) 6 ]Dropwise adding the solution into a metal salt solution, and stirring at room temperature; sequentially standing the stirred materials,Washing and drying to obtain solid powder; cu (NO) 3 ) 2 ·3H 2 O、Co(NO 3 ) 2 ·6H 2 O and H 3 Dissolving BTC in a mixed solution of DMF and ethanol, adding the solid powder after ultrasonic treatment, and stirring; transferring the mixture into a hydrothermal reaction kettle for reaction, centrifuging, washing and vacuum drying the reaction product to obtain the composite material.
Further, the Cu (NO 3 ) 2 ·3H 2 O and Co (NO) 3 ) 2 ·6H 2 The molar ratio of O is 1:3-3:1 respectively.
Further, the volume ratio of DMF to ethanol is 1:1-3.
Further, the reaction temperature in the hydrothermal reaction kettle is 90-110 ℃, the reaction time is 40-60 hours, and the vacuum drying temperature is 80-110 ℃.
Further, the metal salt is ZnCl 2 、Cu(NO 3 ) 2 、Co(NO 3 ) 2 Or FeSO 4 。
The Prussian blue analogues/Cu x -Co y The MOF composite can be applied to catalytic oxidation of styrene.
Aiming at the problems of more structural defects, easy collapse of a catalyst framework, incapability of multiple recycling and low recovery rate in the preparation of Prussian blue analogues in the prior art, the invention provides the Prussian blue analogues/Cu x -Co y The MOF composite material and the preparation method thereof can effectively improve the conversion rate of styrene, improve the yield of styrene oxide and inhibit the yield of byproduct benzaldehyde, and the catalyst can be recycled for a plurality of times.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages: (1) The surface structure defect of the Prussian blue analogues can be effectively improved, the skeleton strength of the Prussian blue analogues is enhanced, and the formation of a micropore structure is promoted. When styrene is oxidized to form styrene oxide, the styrene is fully contacted with the oxidant through the micropore structure, so that the reaction can be effectively promoted. Meanwhile, metal ions are attached to the surface of Prussian blueSo as to fully expose the active sites required by the reaction and promote the reaction; (2) Prussian blue analogues/Cu of the invention x -Co y The MOF composite material has stable structure, good catalytic effect after being recovered for many times, and good hydrothermal stability; (3) The preparation method has the advantages of simple preparation steps and equipment, low cost and easy large-scale industrialized preparation.
Drawings
FIG. 1 is a FT-IR diagram of a ZnCoPBA catalyst;
FIG. 2 is ZnCoPBA/Cu 0.75 -Co 0.25 -FT-IR diagram of MOF composite.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments.
Example 1
Prussian blue analogue/Cu x -Co y -MOF composite material whose structural composition can be expressed as: znCoPBA/Cu 0.75 -Co 0.25 MOF, the composite material takes Prussian blue analogue ZnCoPBA as a matrix and Cu 0.75 -Co 0.25 -MOF is an active ingredient, which is supported on the surface of the prussian blue analogue.
The ZnCoPBA/Cu 0.75 -Co 0.25 The preparation method of the MOF composite material specifically comprises the following steps:
(1) 100mL K 3 [Co(CN) 6 ]The solution was slowly added dropwise to 100mL ZnCl 2 Obtaining a new mixed solution from the solution; stirring the new mixed solution at constant rotation speed for 2 h, and standing for 24 h at room temperature;
(2) Centrifuging the material obtained in the step (1) by a centrifuge to collect precipitate, and washing the precipitate with deionized water and ethanol for 3 times respectively; drying the obtained solid for 8 hours at 60 ℃ under vacuum condition to obtain white powder;
(3) Cu (NO) 3 ) 2 ·3H 2 O（0.3mol）、Co(NO 3 ) 2 ·6H 2 O (0.1 mol) and trimesic acid (H) 3 BTC) in a mixed solution of acetyl Diamide (DMF) and ethanol for 20 minutesAfter the clock, the white powder in (2) was added, followed by stirring for 1 hour;
(4) Transferring the mixture stirred in the step (3) into a hydrothermal reaction kettle, and keeping the reaction temperature at 110 ℃ for reaction for 60 hours;
(5) The reaction product in (4) was washed three times with deionized water and ethanol, and the solid purified after filtration was collected and dried in a vacuum oven at 110℃for 8 hours.
ZnCoPBA/Cu prepared in example 1 0.75 -Co 0.25 -MOF composite application in styrene oxidation reaction:
into a 50ml round bottom flask was successively added 10mmol of styrene, 10ml of acetonitrile, 30mmol of t-butylhydroperoxide (TBHP), 60mg of ZnCoPBA/Cu 0.75 -Co 0.25 -MOF catalyst, the round bottom flask was placed in an oil bath, heated to 80 ℃, and reacted for 8 hours.
And centrifuging the reacted mixture, separating the product from the catalyst, calculating the conversion rate of styrene by gas chromatography of the collected product, and finding that the conversion rate of styrene is 98.26% and the yield of ethylene oxide reaches 54.08. ZnCoPBA/Cu after reaction 0.75 -Co 0.25 The MOF catalyst is recovered after washing and drying, and is continuously used as the catalyst in the styrene oxidation reaction, after repeated recovery and repeated application for 4 times, a small amount of reaction solution is taken, and the conversion rate of the styrene is measured to be 94.73%. Description of the modified ZnCoPBA/Cu according to the invention 0.75 -Co 0.25 The MOF catalyst still has good catalytic effect after being recovered for a plurality of times.
FIG. 1 is a FT-IR diagram of a ZnCoPBA catalyst, FIG. 2 is a ZnCoPBA/Cu 0.75 -Co 0.25 -FT-IR diagram of MOF composite. As can be seen from FIG. 2, znCoPBA/Cu 0.75 -Co 0.25 The MOF composite was successfully prepared.
Example 2
Prussian blue analogue/Cu x -Co y -MOF composite material whose structural composition can be expressed as: znCoPBA/Cu 0.5 -Co 0.5 MOF, the composite material takes Prussian blue analogue ZnCoPBA as a matrix and Cu 0.5 -Co 0.5 -MOF is an active ingredient, which is supported on the surface of the prussian blue analogue.
The ZnCoPBA/Cu 0.5 -Co 0.5 The preparation method of the MOF composite material specifically comprises the following steps:
(1) 100mL K 3 [Co(CN) 6 ]The solution was slowly added dropwise to 100mL ZnCl 2 Obtaining a new mixed solution from the solution; stirring the new mixed solution at constant rotation speed for 2 h, and standing for 24 h at room temperature;
(2) Centrifuging the material obtained in the step (1) by a centrifuge to collect precipitate, and washing the precipitate with deionized water and ethanol for 3 times respectively; drying the obtained solid for 8 hours at 60 ℃ under vacuum condition to obtain white powder;
(3) Cu (NO) 3 ) 2 ·3H 2 O（0.1mol）、Co(NO 3 ) 2 ·6H 2 O (0.1 mol) and trimesic acid (H) 3 BTC) was dissolved in a mixed solution of acetyl Diamide (DMF) and ethanol, followed by addition of the white powder of (2) followed by stirring for 1 hour;
(4) Transferring the mixture stirred in the step (3) into a hydrothermal reaction kettle, and keeping the reaction temperature at 110 ℃ for reaction for 60 hours;
(5) The reaction product in (4) was washed three times with deionized water and ethanol, and the solid purified after filtration was collected and dried in a vacuum oven at 110℃for 8 hours.
ZnCoPBA/Cu prepared in example 2 0.5 -Co 0.5 -MOF composite application in styrene oxidation reaction:
into a 50ml round bottom flask was successively added 10mmol of styrene, 10ml of acetonitrile, 30mmol of t-butylhydroperoxide (TBHP), 60mg of ZnCoPBA/Cu 0.5 -Co 0.5 -MOF catalyst, the round bottom flask was placed in an oil bath, heated to 80 ℃, and reacted for 8 hours.
Centrifuging the reacted mixture, separating the product and the catalyst, calculating the conversion rate of styrene by gas chromatography, and finding that the conversion rate of styrene is 98.73% and the conversion rate of styrene oxide is 98.73%The alkane yield was 71.25%. ZnCoPBA/Cu after reaction 0.5 -Co 0.5 The MOF catalyst is recovered after washing and drying, and is continuously used as the catalyst in the styrene oxidation reaction, after repeated recovery and repeated application for 4 times, a small amount of reaction solution is taken, and the conversion rate of the styrene is measured to be 92.17 percent. Description of the modified ZnCoPBA/Cu according to the invention 0.5 -Co 0.5 The MOF catalyst still has good catalytic effect after being recovered for a plurality of times.
Example 3
Prussian blue analogue/Cu x -Co y -MOF composite material whose structural composition can be expressed as: znCoPBA/Cu 0.25 -Co 0.75 MOF, the composite material takes Prussian blue analogue ZnCoPBA as a matrix and Cu 0.25 -Co 0.75 -MOF is an active ingredient, which is supported on the surface of the prussian blue analogue.
The ZnCoPBA/Cu 0.25 -Co 0.75 The preparation method of the MOF composite material specifically comprises the following steps:
(1) 100mL K 3 [Co(CN) 6 ]The solution was slowly added dropwise to 100mL ZnCl 2 Obtaining a new mixed solution from the solution; stirring the new mixed solution at constant rotation speed for 2 h, and standing for 24 h at room temperature;
(2) Centrifuging the material obtained in the step (1) by a centrifuge to collect precipitate, and washing the precipitate with deionized water and ethanol for 3 times respectively; drying the obtained solid for 8 hours at 60 ℃ under vacuum condition to obtain white powder;
(3) Cu (NO) 3 ) 2 ·3H 2 O（0.1mol）、Co(NO 3 ) 2 ·6H 2 O (0.3 mol) and trimesic acid (H) 3 BTC) was dissolved in a mixed solution of acetyl Diamide (DMF) and ethanol, followed by addition of the white powder of (2) followed by stirring for 1 hour;
(4) Transferring the mixture stirred in the step (3) into a hydrothermal reaction kettle, and keeping the reaction temperature at 110 ℃ for reaction for 60 hours;
(5) The reaction product in (4) was washed three times with deionized water and ethanol, and the solid purified after filtration was collected and dried in a vacuum oven at 110℃for 8 hours.
ZnCoPBA/Cu prepared in example 3 0.25 -Co 0.75 -MOF composite application in styrene oxidation reaction:
into a 50ml round bottom flask was successively added 10mmol of styrene, 10ml of acetonitrile, 30mmol of t-butylhydroperoxide (TBHP), 60mg of ZnCoPBA/Cu 0.25 -Co 0.75 -MOF catalyst, the round bottom flask was placed in an oil bath, heated to 80 ℃, and reacted for 8 hours.
The reaction mixture was centrifuged to separate the product from the catalyst, and the collected product was subjected to gas chromatography to calculate the styrene conversion, and the result of the experiment was found that the styrene conversion was 97.81% and the ethylene oxide yield was 84.19%. ZnCoPBA/Cu after reaction 0.25 -Co 0.75 The MOF catalyst is recovered after washing and drying, and is continuously used as the catalyst in the styrene oxidation reaction, after repeated recovery and repeated application for 4 times, a small amount of reaction solution is taken, and the conversion rate of the styrene is measured to be 93.64%. Description of the modified ZnCoPBA/Cu according to the invention 0.25 -Co 0.75 The MOF catalyst still has good catalytic effect after being recovered for a plurality of times.
Claims (8)
1. Prussian blue analogue/Cu x -Co y -MOF composite, characterized in that: the composite material takes Prussian blue analogues as a matrix, and Cu x -Co y -MOF is an active component, x=0.25-0.75, y=1-x, the active component is loaded on the surface of the prussian blue analogue, and the preparation method of the composite material comprises the following steps: will K 3 [Co(CN) 6 ]Dropwise adding the solution into a metal salt solution, and stirring at room temperature; sequentially standing, washing and drying the stirred materials to obtain solid powder; cu (NO) 3 ) 2 ·3H 2 O、Co(NO 3 ) 2 ·6H 2 O and H 3 Dissolving BTC in a mixed solution of DMF and ethanol, adding the solid powder after ultrasonic treatment, and stirring; transferring the mixture into a hydrothermal reaction kettle for reaction, centrifuging, washing and vacuum-treating the reaction productAnd drying to obtain the composite material.
2. Prussian blue analogues/Cu according to claim 1 x -Co y -MOF composite, characterized in that: the Prussian blue analog is one of FeCoPBA, niCoPBA, znCoPBA or CoCoPBA.
3. Prussian blue analog/Cu as claimed in claim 1 x -Co y -a process for the preparation of a MOF composite, characterized in that: the method comprises the following steps: will K 3 [Co(CN) 6 ]Dropwise adding the solution into a metal salt solution, and stirring at room temperature; sequentially standing, washing and drying the stirred materials to obtain solid powder; cu (NO) 3 ) 2 ·3H 2 O、Co(NO 3 ) 2 ·6H 2 O and H 3 Dissolving BTC in a mixed solution of DMF and ethanol, adding the solid powder after ultrasonic treatment, and stirring; transferring the mixture into a hydrothermal reaction kettle for reaction, centrifuging, washing and vacuum drying the reaction product to obtain the composite material.
4. Prussian blue analogues/Cu according to claim 3 x -Co y -a process for the preparation of a MOF composite, characterized in that: the Cu (NO) 3 ) 2 ·3H 2 O and Co (NO) 3 ) 2 ·6H 2 The molar ratio of O is 1:3-3:1 respectively.
5. Prussian blue analogues/Cu according to claim 3 x -Co y -a process for the preparation of a MOF composite, characterized in that: the volume ratio of DMF to ethanol is 1:1-3.
6. Prussian blue analogues/Cu according to claim 3 x -Co y -a process for the preparation of a MOF composite, characterized in that: the hydrothermal reaction temperature is 90-110 ℃, the reaction time is 40-60 hours, and the vacuum drying temperature is 80-110 ℃.
7. Prussian blue analogues/Cu according to claim 3 x -Co y -a process for the preparation of a MOF composite, characterized in that: the metal salt is ZnCl 2 、Cu(NO 3 ) 2 、Co(NO 3 ) 2 Or FeSO 4 One of them.
8. Prussian blue analogues/Cu as claimed in any one of claims 1-2 x -Co y -the use of MOF composites in the catalytic oxidation of styrene.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102755905A (en) * | 2012-07-18 | 2012-10-31 | 兰州大学 | New application of prussian blue analogues |
| CN107876013A (en) * | 2016-09-29 | 2018-04-06 | 天津工业大学 | A kind of preparation method for the Prussian blue composite that MOF 199 is wrapped up |
| CN109174105A (en) * | 2018-10-11 | 2019-01-11 | 天津工业大学 | A kind of preparation method of magnetic catalyst derived from double MOFs |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102755905A (en) * | 2012-07-18 | 2012-10-31 | 兰州大学 | New application of prussian blue analogues |
| CN107876013A (en) * | 2016-09-29 | 2018-04-06 | 天津工业大学 | A kind of preparation method for the Prussian blue composite that MOF 199 is wrapped up |
| CN109174105A (en) * | 2018-10-11 | 2019-01-11 | 天津工业大学 | A kind of preparation method of magnetic catalyst derived from double MOFs |
Non-Patent Citations (1)
| Title |
|---|
| One-pot synthesis of bimetal MOFs as highly efficient catalysts for selective oxidation of styrene;KAI HUANG，et al;J. Chem. Sci.;第1-10页 * |
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