CN116586113A - Method for preparing dual-function heterogeneous catalyst and application thereof in catalyzing CO 2 Use in cycloaddition conversion with epoxides - Google Patents
Method for preparing dual-function heterogeneous catalyst and application thereof in catalyzing CO 2 Use in cycloaddition conversion with epoxides Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 30
- 150000002118 epoxides Chemical class 0.000 title claims abstract description 22
- 238000006352 cycloaddition reaction Methods 0.000 title claims abstract description 20
- 239000002638 heterogeneous catalyst Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 67
- 239000002608 ionic liquid Substances 0.000 claims abstract description 40
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 5
- 239000013256 coordination polymer Substances 0.000 claims description 44
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 19
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 claims description 14
- WTBYGXCRADGSLY-UHFFFAOYSA-N 1,4-bis(bromomethyl)-2,3,5,6-tetrafluorobenzene Chemical compound FC1=C(F)C(CBr)=C(F)C(F)=C1CBr WTBYGXCRADGSLY-UHFFFAOYSA-N 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 7
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- SDHKGYDQOGCLQM-UHFFFAOYSA-N [2,3,5,6-tetrafluoro-4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=C(F)C(F)=C(CO)C(F)=C1F SDHKGYDQOGCLQM-UHFFFAOYSA-N 0.000 claims description 5
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 230000009977 dual effect Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract description 20
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 abstract description 16
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 abstract description 16
- 238000011068 loading method Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 12
- 239000012621 metal-organic framework Substances 0.000 abstract description 10
- 150000005676 cyclic carbonates Chemical class 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 description 15
- 239000011148 porous material Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
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- 238000012512 characterization method Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- CPQRQKGHMZQPKV-UHFFFAOYSA-N 1H-pyrazole zinc Chemical compound [Zn].C=1C=NNC=1 CPQRQKGHMZQPKV-UHFFFAOYSA-N 0.000 description 2
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- -1 epoxyhexane Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- JBEGXWSLDJCTQZ-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol nickel Chemical compound [Ni].Oc1ccccc1C=NCCN=Cc1ccccc1O JBEGXWSLDJCTQZ-UHFFFAOYSA-N 0.000 description 1
- YGAILVDTGIMZAB-UHFFFAOYSA-N 3-pyrazol-3-ylidenepyrazole Chemical compound N1=NC=CC1=C1N=NC=C1 YGAILVDTGIMZAB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 238000004140 cleaning Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000013138 trimesic acid-based metal-organic framework Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000013094 zinc-based metal-organic framework Substances 0.000 description 1
Classifications
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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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
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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
- 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
- B01J2531/26—Zinc
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing a bifunctional heterogeneous catalyst, which loads ionic liquid onto ZIF-8 by a solid phase synthesis method to prepare an IL@MOF composite material, and is applied to CO 2 In cycloaddition with epoxide. Through comparison of the catalytic performances of ionic liquids with different loadings, the active effect is optimal when the loading is 1.0%, and the conversion rate of the cyclic carbonate is excellent under the conditions of no solvent and cocatalyst. Meanwhile, the synthesized composite material has larger specific surface area, better recoverability and good stability, and is a composite material catalyst of ionic liquid and MOF with excellent performance.
Description
Technical Field
The invention belongs to the technical field of industrial catalysts, and relates to a CO 2 The preparation method of catalyst for cycloaddition reaction with epoxide, in particular to a preparation method of double-function heterogeneous catalyst, and the prepared heterogeneous catalyst can catalyze CO 2 The method is applied to cycloaddition conversion with epoxide.
Background
Metal Organic Frameworks (MOFs) are unique porous crystalline materials assembled from coordination bonds of metal ions and organic ligands, and representative crystalline porous materials with high specific surface area, adjustable pore structure, diverse composition, etc. have been attracting attention as design efficient heterogeneous catalysts, while MOFs have been demonstrated in CO 2 Separation and CO 2 The capture aspect has wide application prospect, and the metal node provides acid or alkali sites and combines high porosity, so that the metal node is easier to attract CO 2 Isogas molecules, which are beneficial to CO 2 The addition produces a cyclic carbonate. MOF-type materials are therefore widely used as CO 2 Cycloaddition conversion catalyst. For example: cao et al synthesized a zinc pyrazole MOF consisting of Ni (salen) bipyrazole ligands and Zn clusters, zinc pyrazole linkages enabling the MOF to withstand acid and base treatments as well as boiling water, and the synthesized MOF exhibited high catalytic activity and excellent recyclability when applied to epoxide cycloaddition reactions. Under the reaction condition of adding a cocatalyst tetrabutylammonium bromide (TBAB) of 80 ℃ and 7MpaCO 2 Under pressure, styrene oxide is taken as a model substrate to research the catalytic activity, and the conversion rate of the cyclic carbonate can reach 99 percent. Rani et al synthesized a series of trimesic acid-based metal-organic frameworks by solvothermal methods, investigated in CO by introducing different transition metals (Co, ni, cu, zn) 2 Catalytic Properties in cycloaddition with epoxide at 120℃with 0.7MpaCO 2 The conversion of zinc-based MOF cyclic carbonate under pressure reached 94%.
The ionic liquid (Ionic liquid) is an organic salt which is formed by organic cations and inorganic or organic anions and is liquid at room temperature, and the ionic liquid is used as a novel polar solvent, has almost no vapor pressure, incombustibility, non-volatility, good chemical stability and thermal stability, can be recycled, is environment-friendly and is CO-friendly 2 Has excellent properties in absorption and conversion. However, most of ionic liquids are difficult to apply in industrial production due to the high cost price, and the formed homogeneous catalytic system is unfavorable for recycling treatment. In order to solve the problem, the combination of ionic liquid and metal organic frameworks to form a supported heterogeneous catalytic system is also the hot spot direction of research.
Disclosure of Invention
The invention aims to disclose a preparation method of a bifunctional heterogeneous catalyst, so as to realize the assembly of ionic liquid and a metal organic frame.
It is another object of the present invention to disclose the use of the above-described bi-functional heterogeneous catalyst for catalyzing the cycloaddition conversion of CO2 with epoxide.
1. Preparation of bifunctional heterogeneous catalysts
A method of preparing a dual function heterogeneous catalyst comprising the steps of:
1) Synthesis of tetrafluoro-1, 4-bis (bromomethyl) benzene
Stirring and reacting tetrafluoro-1, 4-bis (hydroxymethyl) benzene and carbon tetrabromide for 20-24 h at room temperature by taking methylene dichloride as a solvent and triphenylphosphine as an initiator, washing, filtering and vacuum drying to obtain tetrafluoro-1, 4-bis (bromomethyl) benzene; the molar ratio of tetrafluoro-1, 4-bis (hydroxymethyl) benzene to carbon tetrabromide is 1: (2-5), wherein the molar ratio of triphenylphosphine to carbon tetrabromide is 0.8: 1-1: 1.2.
2) Synthesis of F-IL-CP ionic liquid
Dissolving tetrafluoro-1, 4-di (bromomethyl) benzene and tricyclohexylphosphorus in dichloromethane, stirring at room temperature for reacting for 20-24 h, washing, filtering, and vacuum drying to obtain F-IL-CP ionic liquid; the molar ratio of tetrafluoro-1, 4-bis (bromomethyl) benzene to tricyclohexylphosphorus was 1:1.5 to 1:2.5.
the synthesis mechanism of F-IL-CP ionic liquid:
3) Synthesis of catalyst 1%F-IL-CP@ZIF-8
Grinding and mixing zinc oxide, 2-methylimidazole and F-IL-CP ionic liquid, reacting for 24 hours at 160 ℃, washing and drying to obtain the catalyst 1%F-IL-CP@ZIF-8. The mol ratio of zinc oxide to F-IL-CP ionic liquid is 40-60: 1, the mole ratio of zinc oxide to 2-methylimidazole is 1: 1.5-1: 2.5.
2-methylimidazole is used as an organic ligand, and N atoms which can be combined with metal on an imidazole ring are more.
2. Characterization of bifunctional heterogeneous catalysts
X-ray powder diffraction (XRD), thermogravimetric analysis (TGA), nitrogen adsorption and desorption and CO are respectively carried out on the synthesized 1%F-IL-CP@ZIF-8 catalyst 2 Adsorption, scanning Electron Microscopy (SEM), transmission Electron Microscopy (TEM), and the like.
1. SEM and TEM characterization
In order to know the morphology difference between ZIF-8 loaded with ionic liquid and ZIF-8 not loaded with ionic liquid, transmission electron microscopy and scanning electron microscopy detection are carried out on ZIF-8 and 1%F-IL-CP@ZIF-8, and the result is shown in figure 1. As can be seen from comparison of FIGS. 1 (b-d) and (a), the ZIF-8 loaded with the ionic liquid has a similar morphology with the ZIF-8 not loaded with the ionic liquid, and is a regular hexahedron, which indicates that the morphology of the ZIF-8 is not greatly changed after the ionic liquid is loaded, wherein partial structural change may be uneven during grinding, so that the structure is incomplete.
2. X-ray powder diffraction pattern analysis
To examine the crystallinity of the resulting samples, we performed X-ray powder diffraction analysis of the synthesized samples, the results of which are shown in fig. 2. As can be seen from fig. 2, the synthesized peaks of the ionic liquid catalysts with different loadings have good matching degree with the peak of the simulated and calculated ZIF-8, which indicates that the synthesized catalyst phase has good purity.
3. Thermogravimetric profile analysis
At N 2 TGA analysis was performed on 1%F-IL-cp@zif-8 catalysts under atmosphere to investigate the thermal stability of the catalysts. As shown in figure 3, the initial thermal decomposition temperature of the synthesized 1%F-IL@ZIF-8 catalyst reaches more than 250 ℃, which shows that the ionic liquid has good thermal stability, the ionic liquid starts to decompose at 250 ℃, and the main reason of weight loss is also the loss of the ionic liquid.
4、N 2 Adsorption-desorption curve and pore size distribution
The catalyst 1%F-IL-CP@ZIF-8 was subjected to a nitrogen adsorption and desorption test under the condition of 77K, and the result is shown in FIG. 4. From the figure, it can be seen that the adsorption isotherm is typical of type I isotherms, which is shown to be microporous adsorption, with pore size distribution between 0.8 and 1.3 nm. The specific surface area of the catalyst was tested to be about 1332m 2 g -1 By referring to the literature, the specific surface area of the conventional ZIF-8 is about 1800. 1800 m 2 g -1 About, the decrease in specific surface area may be due to the loading of the ionic liquid. For the nonporous ionic liquid, the composite material after the ionic liquid is loaded on the ZIF-8 still maintains the characteristic of large specific surface area of the ZIF-8, which is beneficial to the adsorption and catalytic reaction of gas.
5、CO 2 Adsorption test and equivalent heat of adsorption
CO is carried out on the catalyst 1%F-IL-CP@ZIF-8 under 298K and 273K conditions respectively 2 The adsorption and desorption test results are shown in fig. 5. From the figure it can be seen that the CO is at 298K and 273K 2 Is 14.9cm 3 g -1 And 28.6cm 3 g -1 Showing a better catalyst of CO 2 Adsorption performance. At the same time, a catalyst pair CO is explored 2 The affinity is calculated by a visual equation to calculate the CO of the catalyst 1%F-IL-CP@ZIF-8 2 The equivalent heat of adsorption Qst value of (2) reaches 17.45kJ/mol, indicating that the catalyst has low CO 2 Has strong physical adsorption capacity under coverage rate.
6. EDX energy spectrum analysis
EDX energy spectrum analysis of catalyst 1%F-IL-CP@ZIF-8 is shown in FIG. 6. The data obtained by the energy spectrometer are shown in table 1, and the content of each element can be seen, wherein the element comprises C, N, O, zn, br, F and the like.
TABLE 1 content of elements of 1% F-IL-CP@ZIF-8 catalyst
3. Catalytic CO 2 Investigation of cycloaddition reaction with epoxide
CO 2 The specific experimental process of the cycloaddition reaction with epoxide is as follows: the catalyst with the required dosage is taken and added into a Schlenk tube, then the gas in the tube is discharged for 3 times by vacuumizing, epichlorohydrin is slowly added into the Schlenk tube (0.925 g,10 mmol), a balloon (0.1 MPa) filled with CO2 is connected into a tube orifice, and the mixture is placed into an oil bath pot to be heated to the preheated temperature. After the reaction, the Schlenk tube was taken out of the oil bath, cooled to room temperature, and the remaining CO2 was discharged, and the product was taken out, and the nuclear magnetic peak area was quantitatively analyzed to calculate the cyclic carbonate conversion.
1. Catalytic performance of ionic liquid catalysts of different loadings
To investigate the catalytic performance of the catalyst, CO was used 2 And Epichlorohydrin (ECH) as model compounds, epichlorohydrin (0.925 g,10 mmol), CO 2 Cycloaddition reaction is carried out under the conditions of 0.1Mpa of air pressure, 80 ℃ and no solvent and cocatalyst to screen out the catalyst with optimal performance, and the catalytic activity is shown in figure 7. Experimental data show that when ZIF-8 is directly used as a catalyst, the catalytic activity is only 27%, and the activity is low. When different loadings are usedAfter the ionic liquid catalyst, a loading of 1% was found. The catalytic performance of the catalyst can reach 97.4%, the activity of the catalyst is basically stable along with the increase of the load, and the activity of the catalyst is obviously reduced when the load is 10%, and the reason is probably that the pore canal and the active site of ZIF-8 are blocked after the load of the ionic liquid is excessive. In summary, we selected a catalyst with a loading of 1% as the optimal catalyst.
2. Influence of the reaction temperature
CO is carried out by using the screened optimal catalyst 1%F-IL-CP@ZIF-8 at different reaction temperatures 2 The cycloaddition reaction is shown in FIG. 8. From the data on the graph, the catalytic activity was also increasing with increasing temperature, and the reactivity reached a maximum when the temperature reached 80 ℃. After the temperature continued to rise, it was found that there was substantially no change in activity, and therefore, the reaction temperature of 80℃was the optimum reaction temperature.
3. Influence of the reaction time
CO is carried out by using the screened optimal catalyst 1%F-IL-CP@ZIF-8 at different reaction times 2 The cycloaddition reaction is shown in FIG. 9. From the data on the graph, the catalytic activity was also improved with time, and the maximum value of the catalytic activity was reached when the reaction time reached 48 hours. As the reaction time continued to increase, there was found to be substantially no change in activity, so a reaction time of 48h was the optimal reaction time.
4. Investigation of the applicability of different epoxide substrates
By screening the catalyst and optimizing various reaction conditions, 1%F-IL-CP@ZIF-8 is selected as an optimal catalyst. By 5 different epoxides such as epoxyhexane, epoxybutane, phenyl glycidyl ether, butyl glycidyl ether, styrene oxide and the like and CO 2 The experiment of cycloaddition reaction to form cyclic carbonate was conducted to investigate the substrate adaptation of 1%F-IL-CP@ZIF-8 catalyst, and the results are shown in Table 2 below. Experimental results show that the 1%F-IL-CP@ZIF-8 catalyst can obtain better activity for different substrate yields, but the yield of the epoxide with larger steric hindrance is lower due to the enhancement of the conjugation effect of the epoxide.
TABLE 2 1% F-IL-CP@ZIF-8 catalyst vs. CO 2 Effects of cycloaddition with different epoxides
5. Investigation of catalyst stability
At a reaction temperature of 80 ℃ for 48h and CO 2 The optimal catalyst 1%F-IL-CP@ZIF-8 was subjected to cyclic testing at a pressure of 0.1MPa as shown in FIG. 10. And (3) recovering the reacted catalyst through centrifugation, repeatedly flushing with methanol, carrying out suction filtration and drying, and then continuously using. After the catalyst is recycled for 5 times, the activity of the catalyst is not obviously reduced, which indicates that the catalyst has better stability. A significant decrease in activity was found at cycle 6, which may be due to plugging, slumping, etc. of the channels after repeated use of the catalyst.
The catalytic mechanism of the catalyst 1%F-IL-CP@ZIF-8 is as follows:
first, the lewis acidic sites of the catalyst electrophilically activate epoxide rings, resulting in epoxide ring opening. Next, br anions pair CO 2 Nucleophilic attack of oxygen atoms and bonding with the epoxide carbon to form an intermediate metal species. Finally, oxyanions and CO 2 Intramolecular cyclization of carbon atoms to form cyclic carbonates, with catalyst regeneration, which is recycled to the next reaction.
In conclusion, the invention prepares the IL@MOF composite material by loading the ionic liquid onto ZIF-8 by a solid phase synthesis method, and applies the IL@MOF composite material to CO 2 In cycloaddition with epoxide. Through comparison of the catalytic performances of ionic liquids with different loadings, the active effect is optimal when the loading is 1.0%, and the conversion rate of the cyclic carbonate is excellent under the conditions of no solvent and cocatalyst. Meanwhile, the synthesized composite material has larger specific surface area, better recoverability and good stability, and is a kind of materialA composite catalyst of ionic liquid and MOF with excellent performance.
Drawings
FIG. 1 is a diagram showing the morphology of a 1%F-IL-CP@ZIF-8 catalyst prepared by the method, wherein (a) is a transmission electron microscope image of ZIF-8, (b) is a transmission electron microscope image of 1%F-IL-CP@ZIF-8, (c) is a scanning electron microscope image with a magnification of 1%F-IL-CP@ZIF-8 of 10 μm, and (d) is a scanning electron microscope image with a magnification of 1%F-IL-CP@ZIF-8 of 5 μm;
FIG. 2 is an X-ray powder diffraction pattern of ZIF-8 catalysts prepared according to the present invention with different ionic liquid loadings;
FIG. 3 is a thermogram of a 1%F-IL-CP@ZIF-8 catalyst prepared according to the invention;
FIG. 4 shows N of a 1%F-IL-CP@ZIF-8 catalyst prepared by the invention under the condition of 77K 2 Adsorption-desorption curve and pore size distribution diagram, wherein (a) is N 2 An adsorption-desorption curve, (b) is a pore size distribution diagram;
FIG. 5 is a graph showing the CO of a 1%F-IL-CP@ZIF-8 catalyst prepared according to the invention under the conditions of 298K and 273K 2 Adsorption-desorption curve and equivalent adsorption heat curve, wherein (a) is CO 2 Adsorption and desorption curves, (b) is CO 2 Equivalent heat of adsorption curve;
FIG. 6 is an EDX energy spectrum of a 1%F-IL-CP@ZIF-8 catalyst prepared by the invention;
FIG. 7 is a graph comparing catalytic performance of ionic liquid catalysts prepared according to the present invention at different loadings;
FIG. 8 is a graph showing the relationship between the catalytic performance of the 1%F-IL-CP@ZIF-8 catalyst prepared by the invention and the change of temperature;
FIG. 9 is a graph showing the relationship between the catalytic performance of the 1%F-IL-CP@ZIF-8 catalyst prepared according to the invention and the change with time;
FIG. 10 is a graph showing the results of a cyclic test of 1%F-IL-CP@ZIF-8 catalyst prepared according to the present invention.
Detailed Description
The synthesis method of the 1%F-IL-CP@ZIF-8 catalyst comprises the following steps:
synthesis of tetrafluoro-1, 4-bis (bromomethyl) benzene: 1.2g (5.71 mmol) of tetrafluoro-1, 4-bis (hydroxymethyl) benzene was placed in a 100ml round bottom flask, 50ml of dichloromethane after distillation was added and cooled in an ice bath. 3.74g (14.26 mmol) triphenylphosphine and 4.73g (14.26 mmol) carbon tetrabromide were slowly added, the mixture was taken out of the ice bath and heated to room temperature, stirred slowly, the color was observed to change from orange to black to pale yellow, then stirring was started up, stirring was continued at room temperature for 24h, and the progress of the reaction was monitored by TLC plates during the reaction. After stirring was stopped, the solvent was removed from the crude product by rotary evaporation, and then the crude product was purified by column chromatography with pure petroleum ether as developing solvent, and the product was repeatedly washed with dichloromethane, filtered, and dried under vacuum overnight to give white crystals. (yield: 1.4g, 76%)
Synthesis of catalyst F-IL-CP: 1.34g (4 mmol) of tetrafluoro-1, 4-bis (bromomethyl) benzene and 2.24g (8 mmol) of tricyclohexylphosphorus were added to a 100ml round bottom flask, after which 60ml of distilled dichloromethane was added and the mixture was stirred at room temperature for 24h and the progress of the reaction was monitored by TLC plate during the reaction. After stirring was stopped, the resulting crude product was freed from the solvent by a rotary evaporator, the residue was collected and washed 3 times with diethyl ether to remove unreacted materials, filtered and dried under vacuum at 50 ℃ overnight to give a white solid. (yield: 2.3g, 65%)
Synthesis of catalyst 1%F-IL-CP@ZIF-8: zinc oxide (12.5 mmol,1 g), 2-methylimidazole (26.7 mmol,2.2 g) and ionic liquid F-IL-CP (27.5 mg) were placed in a mortar by solid phase synthesis, and thoroughly ground with a mortar pestle to mix them uniformly. Then, the ground mixture is poured into a reaction kettle with a polytetrafluoroethylene liner, put into an oven, and subjected to reaction at a temperature of between 160 ℃ and 24 and h. And taking out the reaction kettle after the reaction is finished, taking out the solid in the liner after the temperature is cooled to room temperature, cleaning the solid with methanol for 3 times, and finally putting the solid in an oven for drying overnight to obtain white solid 2.26 g. By adjusting the mass of ionic liquid added, MOFs of different loadings can be formed.
The structural characterization and performance evaluation are shown in fig. 1-10.
Claims (6)
1. A process for preparing a dual function heterogeneous catalyst comprising the steps of:
1) Synthesis of tetrafluoro-1, 4-bis (bromomethyl) benzene
Stirring and reacting tetrafluoro-1, 4-bis (hydroxymethyl) benzene and carbon tetrabromide for 20-24 h at room temperature by taking methylene dichloride as a solvent and triphenylphosphine as an initiator, washing, filtering and vacuum drying to obtain tetrafluoro-1, 4-bis (bromomethyl) benzene;
2) Synthesis of F-IL-CP ionic liquid
Dissolving tetrafluoro-1, 4-di (bromomethyl) benzene and tricyclohexylphosphorus in dichloromethane, stirring at room temperature for reacting for 20-24 h, washing, filtering, and vacuum drying to obtain F-IL-CP ionic liquid;
3) Synthesis of catalyst 1%F-IL-CP@ZIF-8
And grinding and mixing zinc oxide, 2-methylimidazole and F-IL-CP ionic liquid, reacting for 20-24 hours at 150-170 ℃, washing and drying to obtain the catalyst 1%F-IL-CP@ZIF-8.
2. A method for preparing a dual function heterogeneous catalyst according to claim 1, wherein in step 1), the molar ratio of tetrafluoro-1, 4-bis (hydroxymethyl) benzene to carbon tetrabromide is 1: (2-5), wherein the molar ratio of triphenylphosphine to carbon tetrabromide is 0.8: 1-1: 1.2.
3. a process for preparing a bifunctional heterogeneous catalyst according to claim 1, wherein in step 2) the molar ratio of tetrafluoro-1, 4-bis (bromomethyl) benzene to tricyclohexylphosphorus is 1:1.5 to 1:2.5.
4. the method for preparing the dual-function heterogeneous catalyst according to claim 1, wherein in the step 3), the molar ratio of zinc oxide to F-IL-CP ionic liquid is 40-60: 1, the mole ratio of zinc oxide to 2-methylimidazole is 1: 1.5-1: 2.5.
5. the bi-functional heterogeneous catalyst prepared by the method of claim 1 for catalyzing CO 2 Use in cycloaddition conversion with epoxides.
6. The dual function multi-phase catalyst of claim 5Catalyst for catalyzing CO 2 Use in cycloaddition conversion with an epoxide, characterized in that: 1%F-IL-CP@ZIF-8 is used as a catalyst, and CO 2 Cycloaddition reaction with epoxide at 80 ℃ for 48h.
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