CN114957695A - Bimetal MOFs material and preparation method and application thereof - Google Patents
Bimetal MOFs material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 71
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000013246 bimetallic metal–organic framework Substances 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 238000006352 cycloaddition reaction Methods 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 15
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 2
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 22
- 239000013346 indium-based metal-organic framework Substances 0.000 abstract description 3
- 238000005580 one pot reaction Methods 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 116
- 229910002092 carbon dioxide Inorganic materials 0.000 description 58
- 239000001569 carbon dioxide Substances 0.000 description 58
- 239000007789 gas Substances 0.000 description 14
- 238000001179 sorption measurement Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 150000002924 oxiranes Chemical class 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
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- 238000010586 diagram Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- -1 cyclic carbonic acidEsters Chemical class 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
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- 239000013122 aluminium-based metal-organic framework Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 239000012847 fine chemical Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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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
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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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/31—Aluminium
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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
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/33—Indium
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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
Abstract
The invention relates to a bimetal MOFs material and a preparation method and application thereof. Al metal is introduced into an In-MOFs frame through simple one-pot reaction to synthesize bimetallic MOFs materials with different proportions, and the bimetallic MOFs materials are applied to catalyzing low-concentration CO 2 And (3) performing cycloaddition reaction. The bimetallic MOFs material provided by the invention can be used for treating low-concentration CO 2 The (10% concentration) reaction showed good catalytic performance.
Description
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a preparation method of a bimetallic MOFs material and a method for efficiently catalyzing low-concentration CO under the mild condition without solvent 2 Application in cycloaddition reactions.
Background
With carbon dioxide (CO) 2 ) The artificial emission of greenhouse gases as a major component is considered to be a major cause of global warming and ocean acidification. Although it has an adverse effect, CO 2 Is really a cheap, abundant, renewable and nontoxic C1 resource, and can generate various value-added chemical raw materials. In CO 2 In the immobilization strategy, an epoxide is reacted with CO 2 Cycloaddition to form cyclic carbonic acidEsters are the most promising ones, which have a high atom economy, are green reactions and are able to produce structurally diverse products which can be further converted into fine chemicals with high added value. Residential CO 2 CO in emissions, industrial gases (mainly associated with steam production or heat generation in industrial processes) and flue gases of coal-fired power plants 2 The contents of (A) are 5%, 13.8% and 31%, respectively. If at such a low CO 2 The conversion is realized under the concentration, and CO which is emitted by houses, power plants and industries and has a prospect can be developed 2 Direct conversion techniques. Therefore, an efficient catalytic system is sought, which can directly convert CO 2 The flue gas is converted into the chemical raw material with high added value, so that the high cost and high energy consumption of an additional technology can be avoided, and the method has important significance to the human society.
The Metal Organic Frameworks (MOFs) are porous materials with large specific surface area and high-density coordination unsaturated metal sites and are rich in selective adsorption of CO 2 And activating the epoxy compound and CO 2 High density active sites of the molecule, are catalytic to low concentrations of CO 2 Ideal material for chemical conversion. MOFs have the advantage of a wide range of different chemical compositions and topological features compared to traditional heterogeneous catalysts. Therefore, MOFs can be prepared by using different metal ions and different coordination environments, so that MOFs have a proper catalytic active site for catalyzing the chemical conversion of carbon dioxide. Furthermore, MOFs with the same framework type can be obtained using different metal elements, so that the properties of the material can vary depending on the metal atoms selected while maintaining the same structural characteristics. Recently, it has also been demonstrated in the literature that different metal atoms can be incorporated in the same MOFs, occupying equivalent positions in the crystal framework. In terms of catalysis, bimetallic systems generally exhibit higher catalytic activity than the monometallic counterparts. Although multimetallic systems offer great opportunities in the field of catalysis, many solutions to multimetallic MOFs as heterogeneous catalysts have hitherto been to complex in-frame materials incorporating secondary metal sites, usually in the form of metal complexes or nanoparticles, embedded in the MOFs pores, and this process existsPoor circulation stability, partial occupied pore canal volume and the like. Thus, the introduction of appropriate proportions of various metal atoms into the metal nodes that make up the framework enhances the MOFs material to CO 2 The selective capture capability and the catalytic activity are a method with great development prospect.
Disclosure of Invention
The invention aims to synthesize a bimetallic MOFs material by a hydrothermal synthesis method, and the bimetallic MOFs material is used as a catalyst for low-concentration CO 2 Catalytic properties of cycloaddition reactions.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of the bimetal MOFs material comprises the following steps: taking 1,2,4-H 3 btc, anhydrous piperazine, in (NO) 3 ·4H 2 O、Al(NO) 3 ·9H 2 And O and deionized water are stirred and mixed uniformly, then the mixture is placed in a reaction kettle for hydrothermal reaction and centrifugation, and the obtained solid is washed and dried to obtain the bimetallic MOFs material.
Preferably, in the bimetallic MOFs material, the hydrothermal reaction is carried out at 180 ℃ for 72 hours.
Preferably, the bimetallic MOFs material is 1,2,4-H in molar ratio 3 btc anhydrous piperazine in (NO) 3 ·4H 2 O and Al (NO) 3 ·9H 2 Molar sum of O is 1.5:2: 0.5.
Preferably, the bimetallic MOFs material is prepared by mixing in (NO) 3 ·4H 2 O:Al(NO) 3 ·9H 2 O＝1-9:1。
The bimetallic MOFs material provided by the invention is used as a catalyst to catalyze CO in the absence of a solvent 2 Application in preparing cyclic carbonate by cycloaddition reaction.
Preferably, the method comprises adding bimetallic MOFs material and TBAB into a container containing epoxy compound, and introducing CO 2 Stirring, and heating at 40-100 deg.C for 24 hr.
Preferably, CO 2 The concentration of (B) is 10-100% by volume.
Preferably, CO 2 The concentration of (2) is 10% by volume.
Preferably, the epoxy compound is epichlorohydrin.
The invention has the beneficial effects that: the bimetallic MOFs material provided by the invention can efficiently catalyze low-concentration CO under the mild condition without solvent 2 Cycloaddition reaction with an epoxide. The preparation method of the bimetal MOFs material provided by the invention is simple and has a great application prospect.
Drawings
FIG. 1 shows PXRD spectra of four ratios of bimetallic MOFs prepared by the present invention.
FIG. 2 is a thermogram of four ratios of bimetallic MOFs prepared by the present invention.
FIG. 3a is a diagram of the bimetallic MOFs material (In) prepared by the present invention 0.298 Al 0.702 -MOFs).
FIG. 3b is a diagram of the bimetallic MOFs material (In) prepared by the present invention 0.196 Al 0.804 -MOFs).
FIG. 3c shows the dual metal MOFs material (In) prepared by the present invention 0.097 Al 0.903 -MOFs).
FIG. 3d is a diagram of the bimetallic MOFs materials (In) prepared by the present invention 0.054 Al 0.946 -MOFs).
FIG. 4 shows that the bimetal MOFs material with four proportions prepared by the invention is in CO 2 /N 2 Mixed gas (v: v ═ 10:90) in
IAST selectivity at 298K.
Detailed Description
Example 1 bimetallic MOFs materials (one) bimetallic MOFs materials (In) 0.298 Al 0.702 -MOFs) was prepared as follows:
1,2,4-H is added into a 23mL reaction kettle in sequence 3 btc (1.5mmol), anhydrous piperazine (2mmol), in (NO) 3 ·4H 2 O(0.45mmol)、Al(NO) 3 ·9H 2 O (0.05mmol) and 10mL of deionized water are mixed uniformly and then placed in an oven, and the temperature rise rate is 10 ℃ min -1 Heating to 180 ℃, carrying out hydrothermal reaction for 72h at 180 ℃, and then naturally cooling to room temperature to obtain the productYellow rod-shaped crystals. Washing with DMF for several times until the solution becomes colorless, washing with deionized water for several times, and drying In air to obtain bimetallic MOFs material with In-Al molar ratio of 0.298:0.702, and the label is In 0.298 Al 0.702 -MOFs。
Bimetallic MOFs Material (In) 0.196 Al 0.804 -MOFs) was prepared as follows:
1,2,4-H is added into a 23mL reaction kettle in sequence 3 btc (1.5mmol), anhydrous piperazine (2mmol), in (NO) 3 ·4H 2 O(0.40mmol)、Al(NO) 3 ·9H 2 O (0.10mmol) and 10mL of deionized water are mixed uniformly and then placed in an oven, and the temperature rise rate is 10 ℃ min -1 Heating to 180 ℃, carrying out hydrothermal reaction for 72h at 180 ℃, and then naturally cooling to room temperature to obtain light yellow rod-shaped crystals. Washing with DMF for several times until the solution becomes colorless, washing with deionized water for several times, and drying In air to obtain bimetallic MOFs material with In-Al molar ratio of 0.196:0.804, and labeled as In 0.196 Al 0.804 -MOFs。
(III) bimetallic MOFs Material (In) 0.097 Al 0.903 -MOFs) was prepared as follows:
1,2,4-H is added into a 23mL reaction kettle in sequence 3 btc (1.5mmol), anhydrous piperazine (2mmol), in (NO) 3 ·4H 2 O(0.30mmol)、Al(NO) 3 ·9H 2 O (0.20mmol) and 10mL of deionized water are mixed uniformly and then placed in an oven, and the temperature rise rate is 10 ℃ min -1 Heating to 180 ℃, carrying out hydrothermal reaction for 72h at 180 ℃, and then naturally cooling to room temperature to obtain light yellow rod-shaped crystals. Washing with DMF for several times until the solution becomes colorless, washing with deionized water for several times, and drying In air to obtain bimetallic MOFs material with In-to-Al molar ratio of 0.097:0.903, labeled as In 0.097 Al 0.903 -MOFs。
(IV) bimetallic MOFs Material (In) 0.054 Al 0.946 -MOFs) was prepared as follows:
1,2,4-H is added into a 23mL reaction kettle in sequence 3 btc (1.5mmol), anhydrous piperazine (2mmol), in (NO) 3 ·4H 2 O(0.25mmol)、Al(NO) 3 ·9H 2 O (0.25mmol) and 10mL of deionized water are mixed uniformly and then placed in an oven, and the temperature rise rate is 10 ℃ min -1 Heating to 180 ℃, carrying out hydrothermal reaction for 72h at 180 ℃, and then naturally cooling to room temperature to obtain light yellow rod-shaped crystals. Washing with DMF for several times until the solution becomes colorless, washing with deionized water for several times, and drying In air to obtain bimetallic MOFs material with In-Al molar ratio of 0.054:0.946, labeled as In 0.054 Al 0.946 -MOFs。
(V) detection
In order to detect whether the bimetallic MOFs material prepared by different In and Al molar ratios successfully introduces another metal element, element analysis tests are carried out on the bimetallic MOFs material with four ratios. The results are shown in Table 1.
TABLE 1 ICP-OES testing of In/Al-MOFs materials
As can be seen from Table 1, in the MOFs synthesized by the invention, the second metal element aluminum is successfully introduced, and the bimetallic MOFs with different proportions are synthesized.
FIG. 1 shows PXRD spectrograms of four proportions of bimetallic MOFs materials prepared by the invention. As shown In fig. 1, the peak of the bimetallic MOFs materials with four ratios is very consistent with the peak of the simulated In-MOF, which proves that the bimetallic MOFs materials with four ratios are successfully synthesized after the second metal element aluminum is introduced, the original structure is still maintained, and the synthesized bimetallic MOFs materials with four ratios have better phase purity.
FIG. 2 is a thermogram of four ratios of bimetallic MOFs prepared by the present invention. Thermal stability tests were performed on the bimetallic MOFs materials in four ratios. As shown in fig. 2, the weight loss in the temperature range of 25-150 ℃ corresponds to the loss of water molecules. The framework structure of the entire MOFs began to collapse around 300 ℃, indicating that the organic ligands began to carbonize. The four proportions of the bimetallic MOFs material are proved to have good thermal stability.
FIGS. 3a-d are the present inventionThe adsorption isotherms of the prepared bimetallic MOFs materials with four proportions are shown. As shown in FIGS. 3a-d, four ratios of bimetallic MOFs to CO 2 Has excellent adsorption capacity. Four MOFs to N 2 Exhibits a substantially non-adsorbing condition with respect to CO 2 The material shows better adsorption performance, which is probably caused by the bimetallic synergy of four MOFs materials, under the conditions of 273K and 101KPa, In 0.298 Al 0.702 -MOFs、In 0.196 Al 0.804 -MOFs、In 0.097 Al 0.903 -MOFs and In 0.054 Al 0.946 CO of MOFs 2 The adsorption capacity is 71.847, 65.4646, 67.7505 and 67.0307cm respectively 3 g -1 。
FIG. 4 shows that the four-ratio bimetallic MOFs material prepared by the invention is in CO 2 /N 2 IAST selectivity of mixed gas (v: v ═ 10:90) at 298K. Adsorption of the binary mixture was predicted from the experimental pure gas isotherm using the Ideal Adsorption Solution Theory (IAST). By utilizing adsorption data under 298K, the CO pair of four MOFs materials is calculated 2 /N 2 Mixed gas (V: 10:90) to CO 2 IAST Selectivity of, as shown in FIG. 4, four MOFs materials vs. CO 2 All have better selectivity, In 0.196 Al 0.804 MOFs show optimal CO 2 The selectivity of (c) can reach 47.875 at 100 Kpa.
Example 2 bimetallic MOFs materials on Low concentration CO 2 Catalytic function of cycloaddition reaction (I) bimetallic MOFs material to pure CO 2 Catalytic ability of cycloaddition reaction
The method comprises the following steps: adding a certain mass of bimetal MOFs material and TBAB into a catalytic tube for reaction, adding epoxide, sealing, and introducing pure CO into the catalytic tube by using a balloon 2 Gas replacement is carried out repeatedly for three times, reaction is carried out for 24 hours at a certain temperature, and the yield is detected by gas chromatography. The reaction procedure is shown below, and the reaction conditions were optimized by studying the influence of various reaction parameters.
The reaction formula is as follows:
1. reaction temperature for catalyzing CO by bimetal MOFs material 2 Effect of the cycloaddition reaction
The method comprises the following steps: 25mg of bimetallic MOFs material (In) 0.097 Al 0.903 -MOFs) and 0.5mmol TBAB in a reaction catalytic tube, adding 10mmol epichlorohydrin, sealing, and introducing pure CO with a balloon 2 The gas was repeatedly subjected to gas exchange three times, and the reaction was carried out at 25 ℃, 40 ℃, 60 ℃, 80 ℃ and 100 ℃ for 24 hours, and the yield was determined by gas chromatography, and the results are shown in Table 2.
TABLE 2 temperature vs. catalytic CO 2 Cycloaddition reaction a
a Reaction conditions are as follows: 10mmol of epoxy chloropropane, 0.5mmol of TBAB and 24 hours of reaction time; b the final yield was determined by GC.
As can be seen from Table 2, for CO 2 The reaction temperature of the cycloaddition reaction was investigated and experiments showed that the yield of the reaction increased continuously with increasing temperature from room temperature 25 c, reaching a maximum of 90.92% at 80 c and starting to decrease as the temperature continued to increase. Indicating that the optimum reaction temperature for the reaction was 80 ℃.
2. Adding amount of bimetallic MOFs material to catalyze CO 2 Effect of the cycloaddition reaction
The method comprises the following steps: respectively taking 10mg, 25mg, 35mg, 50mg and 70mg of bimetal MOFs material (In) 0.097 Al 0.903 -MOFs) and 0.5mmol TBAB in a reaction catalytic tube, adding 10mmol epichlorohydrin, sealing, and introducing pure CO with a balloon 2 The reaction was carried out at 80 ℃ for 24 hours by gas replacement repeatedly three times, and the yield was measured by gas chromatography, and the results are shown in Table 3.
TABLE 3 In 0.097 Al 0.903 Different variable pairs catalyze CO 2 Cycloaddition reaction a
a Reaction conditions are as follows: 10mmol of epoxy chloropropane, 0.5mmol of TBAB and 24 hours of reaction time; b the final yield was determined by GC.
As can be seen from Table 3, the optimum reaction temperature was 80 ℃ for the In catalyst 0.097 Al 0.903 The amount of the catalyst is studied, and experiments show that when the amount of the catalyst is increased from 10mg to 70mg, the reaction yield is increased and then reduced, and the optimal reaction amount is 25 mg.
3. Catalysis of CO by different bimetallic MOFs materials 2 Effect of the cycloaddition reaction
The method comprises the following steps: 25mg of In were taken separately 0.298 Al 0.702 -MOFs、In 0.196 Al 0.804 -MOFs、In 0.097 Al 0.903 -MOFs、In 0.054 Al 0.946 -MOFs and 0.5mmol TBAB are put into a reaction catalytic tube, 10mmol epichlorohydrin is added, the tube is sealed, and pure CO is introduced into the tube by a balloon 2 The reaction was carried out at 80 ℃ for 24 hours by gas replacement repeatedly three times, and the yield was measured by gas chromatography, and the results are shown in Table 4.
TABLE 4 different catalyst pairs catalyze CO 2 Cycloaddition reaction a
a The reaction conditions comprise 10mmol of epoxy chloropropane, 0.5mmol of TBAB and 24h of reaction time; b the final yield was determined by GC.
As shown In Table 4, four materials were compared under the same reaction conditions, In 0.097 Al 0.903 The optimal reaction performance is shown, and the reaction yield can reach 90.92%.
Bimetallic MOFs materials for low concentration of CO 2 Catalytic ability of cycloaddition reaction
The method comprises the following steps: 25mg of In were taken separately 0.298 Al 0.702 -MOFs、In 0.196 Al 0.804 -MOFs、In 0.097 Al 0.903 -MOFs、In 0.054 Al 0.946 -MOFs and 0.5mmol TBAB in a reaction catalytic tube, adding 10mmol epichlorohydrin, sealing, and introducing 10% CO by volume percentage with a balloon 2 Gas (10% CO by volume) 2 Gas and 90% N 2 Gas composition), gas substitution was repeated three times, reaction was carried out at 80 ℃ for 24 hours, and the yield was examined by gas chromatography, the results are shown in Table 5.
TABLE 5 Effect of different catalysts on the cycloaddition reaction at low carbon dioxide concentrations a
a Reaction conditions are as follows: 10mmol of epoxy chloropropane, 0.5mmol of TBAB and 24 hours of reaction time; b the final yield was checked by GC; C no TBAB.
Through experiments, the optimal pure concentration of CO is found out 2 Under the reaction conditions of the cycloaddition reaction of (2), low concentration of CO is carried out 2 The cycloaddition reaction of (3). As can be seen from Table 5, under this optimum reaction condition, under conditions simulating flue gas (CO) 2 /N 2 10:90), cycloaddition reactions were performed on four different ratios of bimetallic MOFs materials. Experiments have shown that In is In four materials 0.097 Al 0.903 Shows the optimal reaction catalytic performance at lower CO 2 At the concentration, 76.95% can be achieved for the catalytic yield. At a lower CO 2 Under the concentration, the better catalytic yield of the four materials is probably because different synergistic effects are generated between indium and aluminum metals in the MOFs through a compact integration form after second metals with different concentrations are introduced into the frame, so that the porosity, adsorption sites and the like of the MOFs are influenced, and the bimetallic MOFs material can further exert a better catalytic yield on CO 2 The adsorption quantity, the selectivity and the adsorption heat of the four kinds of bimetal MOFs with different proportions are influenced, so that the four kinds of bimetal MOFs with different proportions are subjected to low-concentration CO 2 To CO under the conditions of 2 The selective capture and adsorption performance is influenced, and on the other hand, the bimetallic centers with different proportions have an influence on CO 2 And activation of the epoxide plays a key role. The interaction between the two aspects enables bimetallic MOFs to be used at low concentrations of CO 2 The catalyst shows excellent catalytic performance in cycloaddition reaction.
Claims (9)
1. The preparation method of the bimetal MOFs material is characterized by comprising the following steps of: taking 1,2,4-H 3 btc, anhydrous piperazine, in (NO) 3 ·4H 2 O、Al(NO) 3 ·9H 2 And O and deionized water are stirred and mixed uniformly, then the mixture is placed in a reaction kettle for hydrothermal reaction and centrifugation, and the obtained solid is washed and dried to obtain the bimetallic MOFs material.
2. The bimetallic MOFs material according to claim 1, wherein said hydrothermal reaction is carried out at 180 ℃ for 72 h.
3. The bimetallic MOFs material according to claim 1, wherein the molar ratio is 1,2,4-H 3 btc anhydrous piperazine in (NO) 3 ·4H 2 O and Al (NO) 3 ·9H 2 Molar sum of O is 1.5:2: 0.5.
4. The dual-metal MOFs according to claim 3, wherein in (NO) is added to 3 ·4H 2 O:Al(NO) 3 ·9H 2 O＝1-9:1。
5. The bimetallic MOFs material of any one of claims 1 to 4 as a catalyst for catalyzing CO in the absence of a solvent 2 Application in preparing cyclic carbonate by cycloaddition reaction.
6. The use according to claim 5, characterized in that the method comprises charging a container containing an epoxy compound with a bimetallic MOFs material and TBAB, introducing CO 2 Stirring the mixtureStirring, and heating at 40-100 deg.C for reaction for 24 hr.
7. Use according to claim 6, characterized in that CO 2 The concentration of (B) is 10-100% by volume.
8. Use according to claim 7, wherein CO is 2 The concentration of (2) is 10% by volume.
9. Use according to claim 6, 7 or 8, characterized in that the epoxy compound is epichlorohydrin.
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