CN114957695B - Bimetallic MOFs material and preparation method and application thereof - Google Patents
Bimetallic MOFs material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 67
- 239000013246 bimetallic metal–organic framework Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 238000006352 cycloaddition reaction Methods 0.000 claims abstract description 21
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- 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
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 4
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 21
- 229910052751 metal Inorganic materials 0.000 abstract description 14
- 239000002184 metal Substances 0.000 abstract description 13
- 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 114
- 229910002092 carbon dioxide Inorganic materials 0.000 description 57
- 239000001569 carbon dioxide Substances 0.000 description 57
- 239000007789 gas Substances 0.000 description 14
- 238000001179 sorption measurement Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 150000002924 oxiranes Chemical class 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 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
- 239000011148 porous material Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000013122 aluminium-based metal-organic framework Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010348 incorporation Methods 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
- 230000003993 interaction Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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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]
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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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- 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
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- 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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- 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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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Abstract
The invention relates to a bimetal MOFs material and a preparation method and application thereof. Al metal is introduced into an In-MOFs framework through a 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 Cycloaddition reaction. The bimetallic MOFs material provided by the invention has the advantages of low concentration CO 2 The (10% strength) reaction shows good catalytic performance.
Description
Technical Field
The invention belongs to the technical field of catalysis, and in particular relates to a preparation method of a bimetal MOFs material and a method for efficiently catalyzing low-concentration CO under the condition of no solvent and mild condition 2 Use in cycloaddition reactions.
Background
With carbon dioxide (CO) 2 ) The artificial emission of greenhouse gases as a main component is considered to be a main cause of global warming and marine acidification. Despite its adverse effects, CO 2 Indeed an inexpensive, abundant, renewable, non-toxic C1 resource that can produce a variety of value-added chemical feedstocks. In CO 2 In the immobilization strategy, epoxy compound and CO 2 Cycloaddition to form cyclic carbonates is one of the most promising, this reaction has a high atom economy, is a green reaction and is capable of producing products of various structures, which can be further converted into various fine chemicals with high added value. In-house CO 2 Emissions, industrial gases (primarily associated with steam production or heat generation in industrial processes), and CO in flue gases from coal-fired power plants 2 The content of (2) was 5%, 13.8% and 31%, respectively. If at such low CO 2 Conversion at concentration can be achieved, and promising CO emissions from residential, power plant and industry can be developed 2 Direct conversion techniques. Thus, the search for an effective catalytic system allows direct CO conversion 2 The conversion from flue gas to high value-added chemical raw materials can not only avoid the high cost and high energy consumption of additional technology, but also has important significance for human society.
Metal Organic Frameworks (MOFs) are porous with large specific surface area and high density of coordinated unsaturated metal sitesThe material is rich in selective adsorption of CO 2 And activating epoxy compounds and CO 2 The high density active site of the molecule is the catalytic low concentration CO 2 Ideal materials for chemical conversion. MOFs have the advantage of a wide range of different chemical compositions and topological features compared to conventional heterogeneous catalysts. Therefore, MOFs can be prepared with different metal ions and different coordination environments, so that MOFs have suitable catalytic active sites for catalyzing the chemical conversion of carbon dioxide. In addition, MOFs having the same frame type can be obtained using different metal elements, so that the properties of the material will vary depending on the metal atoms selected while maintaining the same structural characteristics. Recently, it has also been demonstrated 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 single metal counterparts. Although multimetal systems offer great opportunities in the catalytic field, many of the proposals to date for multimetal MOFs as heterogeneous catalysts have been to incorporate materials of the second metal site in-frame, usually embedded in MOFs pores in the form of metal complexes or nanoparticles, which suffer from poor cycling stability and occupy part of the pore volume. Thus, incorporation of appropriate proportions of various metal atoms into the metal nodes that make up the framework enhances the CO-pair of MOFs materials 2 The selective capturing 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 performance of cycloaddition reactions.
In order to achieve the above purpose, the invention adopts the following technical scheme: a preparation method of the bimetallic MOFs material comprises the following steps: 1,2,4-H is taken 3 btc, anhydrous piperazine, in (NO) 3 ·4H 2 O、Al(NO) 3 ·9H 2 O and deionized water are stirred and mixed uniformly and then are placed in a reaction kettle for hydrothermal reaction, and the obtained solid is washed and dried to obtain the bimetallic MOFs material.
Preferably, the bimetallic MOFs material is prepared by hydrothermal reaction at 180 ℃ for 72 hours.
Preferably, the bimetallic MOFs material has a molar ratio of 1,2,4-H 3 btc Anhydrous piperazine In (NO) 3 ·4H 2 O and Al (NO) 3 ·9H 2 O molar sum = 1.5:2:0.5.
Preferably, a bimetallic MOFs material as described above, in molar ratio, 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 solvent 2 The application of cycloaddition reaction in preparing cyclic carbonate.
Preferably, the method is as follows, adding bimetallic MOFs material and TBAB into a container containing epoxy compound, introducing CO 2 Stirring and heating at 40-100deg.C for 24 hr.
Preferably, CO 2 The concentration of (2) is 10-100% by volume.
Preferably, CO 2 The concentration of (2) is 10% by volume.
Preferably, the epoxy compound is epichlorohydrin.
The beneficial effects of the invention are as follows: the bimetallic MOFs material provided by the invention realizes efficient catalysis of low-concentration CO under the mild condition without solvent 2 Cycloaddition reaction with epoxide. The preparation method of the bimetal MOFs material provided by the invention is simple, and has a great application prospect.
Drawings
FIG. 1 is a PXRD spectrum of four ratio bimetallic MOFs materials prepared in accordance with the present invention.
FIG. 2 is a thermogravimetric plot of four proportions of bimetallic MOFs material prepared in accordance with the present invention.
FIG. 3a shows the results of the preparation of bimetallic MOFs material (In 0.298 Al 0.702 -MOFs).
FIG. 3b shows the results of the preparation of the bimetallic MOFs material (In 0.196 Al 0.804 -MOFs) of the formulaAdsorption isotherms.
FIG. 3c shows the results of the preparation of the bimetallic MOFs material (In 0.097 Al 0.903 -MOFs).
FIG. 3d shows the results of the preparation of the bimetallic MOFs material (In 0.054 Al 0.946 -MOFs).
FIG. 4 shows the presence of four proportions of bimetallic MOFs in CO prepared in accordance with the present invention 2 /N 2 The mixed gas (v: v=10:90) is as follows
IAST selectivity at 298K.
Detailed Description
Example 1 bimetallic MOFs Material (one) bimetallic MOFs Material (In 0.298 Al 0.702 -MOFs) is prepared as follows:
sequentially adding 1,2,4-H into a 23mL reaction kettle 3 btc (1.5 mmol), anhydrous piperazine (2 mmol), in (NO) 3 ·4H 2 O(0.45mmol)、Al(NO) 3 ·9H 2 O (0.05 mmol) and 10mL deionized water are mixed uniformly and then placed in an oven at a heating rate of 10 ℃ for min -1 Heating to 180 ℃, carrying out hydrothermal reaction for 72h at 180 ℃, and then naturally cooling to room temperature to obtain pale 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 0.298:0.702, labeled as In 0.298 Al 0.702 -MOFs。
(II) bimetallic MOFs Material (In 0.196 Al 0.804 -MOFs) is prepared as follows:
sequentially adding 1,2,4-H into a 23mL reaction kettle 3 btc (1.5 mmol), anhydrous piperazine (2 mmol), in (NO) 3 ·4H 2 O(0.40mmol)、Al(NO) 3 ·9H 2 O (0.10 mmol) and 10mL deionized water are mixed uniformly and then placed in an oven at a heating rate of 10 ℃ min -1 Heating to 180 ℃, carrying out hydrothermal reaction for 72h at 180 ℃, and then naturally cooling to room temperature to obtain pale 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 a molar ratio of In to Al of 0.196:0.804Is labeled In 0.196 Al 0.804 -MOFs。
(III) bimetallic MOFs Material (In 0.097 Al 0.903 -MOFs) is prepared as follows:
sequentially adding 1,2,4-H into a 23mL reaction kettle 3 btc (1.5 mmol), anhydrous piperazine (2 mmol), in (NO) 3 ·4H 2 O(0.30mmol)、Al(NO) 3 ·9H 2 O (0.20 mmol) and 10mL deionized water are mixed uniformly and then placed in an oven at a heating rate of 10 ℃ min -1 Heating to 180 ℃, carrying out hydrothermal reaction for 72h at 180 ℃, and then naturally cooling to room temperature to obtain pale 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) is prepared as follows:
sequentially adding 1,2,4-H into a 23mL reaction kettle 3 btc (1.5 mmol), anhydrous piperazine (2 mmol), in (NO) 3 ·4H 2 O(0.25mmol)、Al(NO) 3 ·9H 2 O (0.25 mmol) and 10mL deionized water are mixed uniformly and then placed in an oven at a heating rate of 10 ℃ min -1 Heating to 180 ℃, carrying out hydrothermal reaction for 72h at 180 ℃, and then naturally cooling to room temperature to obtain pale 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 0.054:0.946, labeled as In 0.054 Al 0.946 -MOFs。
(fifth) detection
In order to detect whether the bimetallic MOFs materials prepared by different In and Al molar ratios successfully introduce another metal element, elemental analysis tests were performed on the four-ratio bimetallic MOFs materials. The results are shown in Table 1.
TABLE 1 ICP-OES test of In/Al-MOFs materials
As can be seen from Table 1, in the MOFs materials synthesized by the present invention, the second metal element aluminum was successfully incorporated, and MOFs materials with different proportions of bimetal were synthesized.
FIG. 1 is a PXRD spectrum of four ratio bimetallic MOFs materials prepared in accordance with the present invention. As shown In FIG. 1, the peaks of the four-proportion bimetallic MOFs are very consistent with the peaks of the simulated In-MOFs, and the fact that the four-proportion bimetallic MOFs are successfully synthesized after the second metal element aluminum is introduced, the original structure is still maintained, and the four-proportion bimetallic MOFs have better phase purity.
FIG. 2 is a thermogravimetric plot of four proportions of bimetallic MOFs material prepared in accordance with the present invention. Thermal stability tests were performed on four proportions of bimetallic MOFs. 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 at around 300 ℃, indicating that the organic ligands began to carbonize. The four proportion bimetallic MOFs materials are proved to have good thermal stability.
FIGS. 3a-d are adsorption isotherms for four proportions of bimetallic MOFs materials prepared in accordance with the present invention. As shown in FIGS. 3a-d, four ratio bimetallic MOFs vs. CO 2 Has excellent adsorption capacity. Four MOFs to N 2 Exhibit a substantially unadsorbed state to CO 2 Exhibits good adsorption performance, which is probably caused by the synergistic effect of the bimetallic of four MOFs, in under the conditions of 2793K, 101KPa 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 Adsorption capacity is 71.847, 65.4646, 67.7505 and 67.0307cm respectively 3 g -1 。
FIG. 4 shows the presence of four proportions of bimetallic MOFs in CO prepared in accordance with the present invention 2 /N 2 IAST selectivity of the mixed gas (v: v=10:90) at 298K. Prediction of binary mixtures from experimentally pure gas isotherms using Ideal Adsorption Solution Theory (IAST)And (5) adsorption. Four MOFs material pairs, CO, were calculated using the adsorption data at 298K 2 /N 2 CO under mixed gas (V: V=10:90) 2 As shown in FIG. 4, four MOFs material pair CO 2 Has better selectivity, wherein In 0.196 Al 0.804 MOFs showed optimal CO 2 Can reach 47.875 at 100 Kpa.
Example 2 bimetallic MOFs materials for low concentration CO 2 Catalytic function of cycloaddition (one) bimetallic MOFs materials for pure CO 2 Catalytic capability of cycloaddition reactions
The method comprises the following steps: adding bimetallic MOFs material and TBAB in certain weight into a catalytic tube, adding epoxide, sealing, and introducing pure CO into the catalytic tube with a balloon 2 The gas was repeatedly replaced three times, reacted at a certain temperature for 24 hours, and the yield was checked by gas chromatography. The reaction process is shown below, and the reaction conditions are optimized by studying the influence of various reaction parameters.
The reaction formula is as follows:
1. the reaction temperature catalyzes CO for the bimetallic MOFs material 2 Influence of cycloaddition reaction
The method comprises the following steps: 25mg of a bimetallic MOFs material (In 0.097 Al 0.903 -MOFs) and 0.5mmol TBAB in a reaction catalytic tube, adding epichlorohydrin 10mmol, sealing, and introducing pure CO thereto with a balloon 2 The gas was repeatedly subjected to gas displacement three times, and the reaction was carried out at 25℃and 40℃and 60℃and 80℃and 100℃for 24 hours, and the yield was measured by gas chromatography, and the results are shown in Table 2.
TABLE 2 temperature vs. catalytic CO 2 Cycloaddition reaction a
a Reaction conditions: epoxy chloropropane 10mmol,TBAB 0.5mmolThe reaction time is 24 hours; b the final yield was checked 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 as the temperature increased from room temperature 25 ℃, the yield of the reaction increased continuously, reaching a maximum of 90.92% at 80 ℃ and as the temperature continued to increase, the yield began to decrease. Indicating an optimum reaction temperature for the reaction of 80 ℃.
2. The addition amount of the bimetallic MOFs material is used for catalyzing CO 2 Influence of cycloaddition reaction
The method comprises the following steps: 10mg, 25mg, 35mg, 50mg, 70mg of the bimetallic MOFs material (In 0.097 Al 0.903 -MOFs) and 0.5mmol TBAB in a reaction catalytic tube, adding epichlorohydrin 10mmol, sealing, and introducing pure CO thereto with a balloon 2 The gas displacement was repeated three times, and the reaction was carried out at 80℃for 24 hours, 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: epichlorohydrin 10mmol,TBAB 0.5mmol, reaction time 24h; b the final yield was checked by GC.
As can be seen from Table 3, the catalyst In was prepared at 80℃as the optimum reaction temperature 0.097 Al 0.903 The amount of catalyst was investigated and experiments showed that the reaction yield increased from 10mg to 70mg, and then decreased, with an optimal reaction amount of 25mg.
3. Different bimetallic MOFs material pair for catalyzing CO 2 Influence of cycloaddition reaction
The method comprises the following steps: 25mg In was 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 is put into a reaction catalytic tube, 10mmol of epichlorohydrin is added, the mixture is sealed, and pure CO is introduced into the mixture by a balloon 2 The gas displacement was repeated three times, and the reaction was carried out at 80℃for 24 hours, and the yield was measured by gas chromatography, and the results are shown in Table 4.
TABLE 4 different catalyst pairs catalyzing CO 2 Cycloaddition reaction a
a The reaction condition is epoxy chloropropane 10mmol,TBAB 0.5mmol, and the reaction time is 24 hours; b the final yield was checked 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%.
(II) bimetallic MOFs Material for Low concentration CO 2 Catalytic capability of cycloaddition reactions
The method comprises the following steps: 25mg In was 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 placed in a reaction catalytic tube, 10mmol of epichlorohydrin is added, the mixture is sealed, and CO with the volume percentage concentration of 10% is introduced into the mixture by a balloon 2 Gas (by volume percentage from 10% CO 2 Gas and 90% N 2 Gas composition), gas displacement was repeated three times, and the reaction was carried out at 80℃for 24 hours, and the yield was measured by gas chromatography, and the results are shown in Table 5.
TABLE 5 influence of different catalysts on cycloaddition reactions under low carbon dioxide concentration conditions a
a Reaction conditions: epichlorohydrin 10mmol,TBAB 0.5mmol, reactionTime 24h; 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 cycloaddition reaction, low concentration of CO is carried out 2 Is added to the reaction mixture. As can be seen from Table 5, under this optimum reaction conditions, under conditions simulating flue gas (CO 2 /N 2 =10:90), cycloaddition reactions were performed on four different proportions of bimetallic MOFs material. Experiments show that In four materials 0.097 Al 0.903 Exhibits optimal catalytic performance of the reaction at lower CO 2 At the concentration, the catalyst yield can reach 76.95 percent. At a lower CO 2 Under the concentration, the four materials show better catalytic yield, on one hand, probably due to the fact that after the second metals with different concentrations are introduced into the framework, different synergistic effects are generated between the indium and the aluminum through a compact integrated form in the MOFs, the porosity, the adsorption sites and the like of the MOFs can be influenced, and further, the bimetallic MOFs material is influenced by CO 2 Adsorption quantity, selectivity and adsorption heat influence, resulting in four different proportions of bimetallic MOFs at low concentrations of CO 2 Under the condition of (2) for CO 2 The selective capturing and adsorption performance are influenced, on the other hand, the bimetallic centers with different proportions are used for CO 2 And epoxide activation. The two aspects of interaction enable the bimetallic MOFs to work at low concentrations of CO 2 The cycloaddition reaction shows excellent catalytic performance.
Claims (7)
1. The preparation method of the bimetal MOFs material is characterized by comprising the following steps of: 1,2,4-H is taken 3 btc, anhydrous piperazine, in (NO) 3 •4H 2 O、Al(NO) 3 •9H 2 O and deionized water are stirred and mixed uniformly and then are placed in a reaction kettle for hydrothermal reaction, and the obtained solid is washed and dried to obtain the bimetallic MOFs material;
in a molar ratio of 1,2,4-H 3 btc Anhydrous piperazine In (NO) 3 •4H 2 O and Al (NO) 3 •9H 2 O molar sum = 1.5:2:0.5;
in (NO) In molar ratio 3 •4H 2 O : Al(NO) 3 •9H 2 O=1-9 : 1。
2. The bi-metallic MOFs material according to claim 1, wherein the hydrothermal reaction is a hydrothermal reaction 72h at 180 ℃.
3. The bimetallic MOFs material of claim 1 or 2 as a catalyst for catalyzing CO in the absence of solvent 2 The application of cycloaddition reaction in preparing cyclic carbonate.
4. The method according to claim 3, wherein the method comprises adding a bimetallic MOFs material and TBAB to a container containing an epoxy compound, introducing CO 2 Stirring and heating reaction 24h at 40-100deg.C.
5. The use according to claim 4, wherein the CO is 2 The concentration of (2) is 10-100% by volume.
6. The use according to claim 5, wherein the CO 2 The concentration of (2) is 10% by volume.
7. The use according to claim 4, 5 or 6, characterized in that the epoxy compound is epichlorohydrin.
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