CN114939431A - CN@ZrO 2 Composite material and application thereof in catalyzing CO 2 Application in cycloaddition reaction with epoxide - Google Patents
CN@ZrO 2 Composite material and application thereof in catalyzing CO 2 Application in cycloaddition reaction with epoxide Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000006352 cycloaddition reaction Methods 0.000 title claims abstract description 23
- 150000002118 epoxides Chemical class 0.000 title 1
- 239000013207 UiO-66 Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000001816 cooling Methods 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 11
- 239000013110 organic ligand Substances 0.000 claims abstract description 11
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- AETJTBDBQRMLLQ-UHFFFAOYSA-N 4-chloro-5-methyl-1,3-dioxolan-2-one Chemical compound CC1OC(=O)OC1Cl AETJTBDBQRMLLQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 4
- HSBMPUYCFQSKRP-UHFFFAOYSA-N 1-bromoimidazole Chemical compound BrN1C=CN=C1 HSBMPUYCFQSKRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 80
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 22
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 22
- 238000001291 vacuum drying Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229910007926 ZrCl Inorganic materials 0.000 claims description 11
- 229960000583 acetic acid Drugs 0.000 claims description 11
- 239000012362 glacial acetic acid Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- YMBWNYKEVPQWII-UHFFFAOYSA-N [Br].N1C=NC=C1 Chemical compound [Br].N1C=NC=C1 YMBWNYKEVPQWII-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 15
- 150000002924 oxiranes Chemical class 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 150000002500 ions Chemical class 0.000 abstract description 2
- 230000000269 nucleophilic effect Effects 0.000 abstract description 2
- 239000002841 Lewis acid Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 150000007517 lewis acids Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 14
- 238000005303 weighing Methods 0.000 description 9
- 239000012621 metal-organic framework Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000002149 hierarchical pore Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- VWUCIBOKNZGWLX-UHFFFAOYSA-N 1h-imidazol-1-ium;bromide Chemical compound [Br-].C1=C[NH+]=CN1 VWUCIBOKNZGWLX-UHFFFAOYSA-N 0.000 description 1
- GJOWSEBTWQNKPC-UHFFFAOYSA-N 3-methyloxiran-2-ol Chemical compound CC1OC1O GJOWSEBTWQNKPC-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
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- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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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- Chemical Kinetics & Catalysis (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses CN @ ZrO 2 Composite material and application thereof in catalyzing CO 2 Application in cycloaddition reaction with epoxide, CN @ ZrO 2 The preparation method of the composite material comprises the following steps: respectively dissolving metal salt and an organic ligand in a solvent to obtain a metal salt solution and an organic ligand solution; mixing an organic ligand solution and a metal salt solution, adding acid serving as a regulator, carrying out oil bath reaction for a period of time, cooling to room temperature, centrifuging, washing and drying to obtain UiO-66; dissolving imidazole bromide and UiO-66 powder in a solvent, stirring, vacuumizing, and drying to obtain an imidazole bromide @ UiO-66 composite material; calcining the obtained imidazole bromide @ UiO-66 composite material in inert atmosphere to obtain CN @ ZrO 2 A composite material. CN @ ZrO prepared according to the invention 2 The composite material has Lewis acid sites (ZrO) 2 ) And nucleophilic sites (Br ions) for unpromotive catalysisCO of the agent 2 The catalyst is reacted with epichlorohydrin to prepare the chloropropylene carbonate through cycloaddition, and shows excellent catalytic performance.
Description
Technical Field
The invention relates to the field of preparation and application of composite materials, in particular to CN @ ZrO 2 Preparation method of composite material and application of composite material in CO catalysis 2 The application in cycloaddition reaction with epoxide.
Background
The rapidly developing modern industry causes a great deal of carbon emissions, which exacerbates global warming and ocean acidification, seriously threatening human survival and development. Although having an adverse effect, CO 2 Is a cheap, rich, renewable and nontoxic carbon resource, and can be fixed in various value-added chemical raw materials. In all CO 2 In a fixed strategy, CO 2 Cycloaddition with epoxides to form cyclic carbonates is considered one of the most promising approaches, because it has the advantages of high atom economy (100%), more environmental protection and various structures, and can be further converted into various fine chemicals, creating nearly thousand times of economic benefit. In addition, with other CO such as urea and fertilizer 2 Based on the product, with CO 2 Synthesis of cyclic carbonates from raw materials CO can be introduced 2 Long-term fixation, and meets the requirements of green environmental protection chemistry. Therefore, there is an urgent need to find a catalyst capable of catalyzing CO with high efficiency 2 Materials which cycloaddition react with epoxides.
Among all potential functional materials, metal-organic frameworks (MOFs) are excellent CO due to their adjustable pore size, easy functionalization 2 Adsorption capacity, etc., and is considered to be CO 2 Good catalysts for cycloaddition with epoxides. For example, Yanghao et al prepared a series of Ce-UiO-66-X (X ═ F, H, Me, OMe) ligands with varying concentrations of defects by modifying functional groups on the linker under the same conditions (1bar CO) 2 TBAB as CO-catalyst at 60 ℃ for 6 h), Ce-UiO-66-F on CO 2 The catalytic yield of cycloaddition reaction with epoxypropanol was highest (96%) (Ynag, Q.H.; Wang, Y.M.; Tang, X.; Zhang, Q.J.; Dai, S.; Peng, H.T.; Lin, Y.C.; Tian, Z.Q.; Lu, Z.Y.; Chen, L.ligand sensitivity regulation in metal-organic frames by functional group aggregation on linkers.NaLett., 2022,22, 8)38-845.). Dae-Won Park et al synthesized defective MOF-801(D) in CO using a solvothermal and preparative method 2 The catalyst shows excellent catalytic performance when undergoing cycloaddition reaction with epichlorohydrin, and the yield of the propylene carbonate reaches 92.4% (0.1MPa CO) 2 80 ℃,15h, TBAB as co-catalyst), but if no TBAB is present in the catalytic system, the reaction hardly occurs (3.08% yield) (Gu, y.j.; anjali, b.a.; yoon, s.; choe, y.; chung, y.g.; park, D.W.Defect-engineered MOF-801for cyclic addition of CO 2 with epoxides, J.Mater.chem.A,2022,10, 10051-10061.). In summary, most current MOFs require a promoter (e.g., TBAB) to support the CO reaction 2 The excellent catalytic efficiency in cycloaddition reactions with epoxides would undoubtedly generate additional waste, leading to catalyst leaching and environmental pollution, while increasing the practical difficulty of product isolation. Therefore, the catalyst is designed and prepared to efficiently catalyze CO under the condition of no cocatalyst 2 MOFs-based catalysts for cycloaddition reactions with epoxides are necessary but still challenging.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to develop the method for efficiently catalyzing CO under the condition of no cocatalyst 2 MOFs-based catalysts for cycloaddition reactions with epoxides.
The invention is realized by the following technical scheme:
CN@ZrO 2 the preparation method of the composite material comprises the following steps:
s1, respectively dissolving metal salt and an organic ligand in a solvent to obtain a metal salt solution and an organic ligand solution;
s2, mixing the organic ligand solution and the metal salt solution, adding acid as a regulator, carrying out oil bath reaction for a period of time, cooling to room temperature, centrifuging, washing and drying to obtain UiO-66;
s3, dissolving imidazole bromide and UiO-66 powder in a solvent, stirring, vacuumizing, and drying to obtain the imidazole bromide @ UiO-66 composite material;
s4, calcining the imidazole bromine salt @ UiO-66 composite material in inert atmosphere to obtain nitrogen-doped porous carbon and ZrO 2 Composite material CN @ ZrO 2 。
Preferably, the metal salt in the step S1 is ZrCl 4 The organic ligand is terephthalic acid, and the solvent is N, N-dimethylformamide.
Preferably, the acid in the step S2 is glacial acetic acid, the oil bath temperature is 100-130 ℃, and the reaction time is 4 hours.
Preferably, the imidazole bromide salt in step S3 is one or more of BmimBr, EmimBr, and OmimBr, and the solvent is methanol and/or ethanol.
Preferably, the inert gas in step S4 is N 2 The calcination temperature is 500-1000 ℃, the calcination time is 1-4 hours, and the heating rate is 2-10 ℃/min.
Preferably, in the step S2, the washing process is performed by using methanol and/or ethanol and/or N, N-dimethylformamide, the drying method is vacuum drying, the drying temperature is 60 to 120 ℃, and the drying time is 10 to 18 hours.
Preferably, in the step S3, the mass ratio of the imidazole bromine salt to the UiO-66 powder is 0.25-1.00, the stirring temperature is 20-40 ℃, the stirring time is 12-48 hours, the vacuumizing temperature is 50-80 ℃, the vacuumizing time is 2-6 hours, the drying is vacuum drying for 10-18 hours, and the drying temperature is 40-80 ℃.
CN@ZrO 2 A composite material prepared according to any one of the methods.
CN@ZrO 2 Application method of composite material in catalysis of CO 2 Cycloaddition reaction with epoxy chloropropane to prepare the chloropropylene carbonate.
Preferably, the method comprises the following steps: epichlorohydrin, CN @ ZrO 2 The composite and N, N-dimethylformamide were added to a Schlenk tube and CO was connected 2 Balloon, evacuating the Schlenk tube and CO 2 And exchanging gas, heating and stirring for reaction, wherein the reaction temperature is 80-120 ℃, and the reaction time is 10-15 hours.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the preparation method disclosed by the invention is simple and rapid to operate, green and environment-friendly and low in cost.
2. The invention adopts ionic liquid @ MOFs composite material to prepare the derivative, compared with MOFs direct pyrolysis, the derivative has more dispersed ZrO 2 The nano particles and the hierarchical pore structure have good practical application value.
3. CN @ ZrO prepared by adopting preparation method 2 Composite material having Lewis acidic site (ZrO) 2 ) And nucleophilic sites (Br ions) in CO without a cocatalyst 2 The catalyst shows excellent catalytic performance in cycloaddition reaction with epichlorohydrin.
4. The invention can efficiently catalyze CO for preparing the cocatalyst-free catalyst 2 Heterogeneous MOFs-based catalysts that cycloaddition react with epoxides provide the idea.
Drawings
FIG. 1 shows 4# CN @ ZrO obtained in example 4 2 XRD pattern of (a);
FIG. 2 shows 4# CN @ ZrO obtained in example 4 2 SEM picture of (1);
FIG. 3 shows ZrO obtained in comparative example 2 And 4# CN @ ZrO obtained in example 4 2 N of (A) 2 Adsorption and desorption isotherm diagrams;
FIG. 4 is the result of example 4 showing 4# CN @ ZrO 2 In CO 2 And (3) a performance diagram in the reaction of cycloaddition with epichlorohydrin for preparing the chloropropylene carbonate.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The following examplesCN @ ZrO of 2 The composite material is nitrogen-doped porous carbon and ZrO 2 The composite material of (1), wherein CN is imidazole bromine salt (BmimBr or EmimBr or OmimBr) which is obtained by high-temperature pyrolysis.
Example 1
This example used the process of the invention to prepare CN @ ZrO 2 The composite material is implemented as follows:
(1) reacting ZrCl 4 (0.615mmol) was dissolved in 25mL of DMF, and terephthalic acid (0.615mmol) was dissolved in 25mL of DMF;
(2) mixing the two solutions in the step (1), adding 8mL of glacial acetic acid as a regulator, carrying out oil bath reaction at 120 ℃ for 4 hours, cooling to room temperature, centrifuging, washing with DMF, and vacuum-drying at 100 ℃ for 12 hours to obtain UiO-66;
(3) dissolving BmimBr (50mg) and UiO-66(200mg) powder in 40mL of methanol, stirring at room temperature for 24 hours, vacuumizing at 80 ℃ for 3 hours, and vacuum drying at 60 ℃ for 12 hours to obtain a 1# BmimBr @ UiO-66 composite material;
(4) weighing the 1# BmimBr @ UiO-66(200mg) obtained in the step (3), feeding the 1# BmimBr @ UiO-66 into a tube furnace, calcining the mixture in a nitrogen atmosphere at the heating rate of 5 ℃/min at the constant temperature of 600 ℃ for 2 hours, cooling the mixture to room temperature, and taking the cooled mixture out to obtain the 1# CN @ ZrO 2 The material can be applied directly.
Example 2
This example used the process of the invention to prepare CN @ ZrO 2 The composite material is implemented as follows:
(1) ZrCl 4 (0.615mmol) was dissolved in 25ml of DMF, and terephthalic acid (0.615mmol) was dissolved in 25ml of DMF;
(2) mixing the two solutions in the step (1), adding 8mL of glacial acetic acid as a regulator, carrying out oil bath reaction at 120 ℃ for 4 hours, cooling to room temperature, centrifuging, washing with DMF, and vacuum-drying at 100 ℃ for 12 hours to obtain UiO-66;
(3) dissolving BmimBr (100mg) and UiO-66(200mg) powder in 40mL of methanol, stirring at room temperature for 24 hours, vacuumizing at 80 ℃ for 3 hours, and vacuum drying at 60 ℃ for 12 hours to obtain a 2# BmimBr @ UiO-66 composite material;
(4) weighing the 2# BmimBr @ UiO-66(200mg) obtained in the step (3) and feeding the weighed material into a tube furnaceCalcining in nitrogen atmosphere at a heating rate of 5 ℃/min at a constant temperature of 600 ℃ for 2 hours, cooling to room temperature, and taking out to obtain 2# CN @ ZrO 2 The material can be applied directly.
Example 3
This example used the process of the invention to prepare CN @ ZrO 2 The composite material is implemented as follows:
(1) reacting ZrCl 4 (0.615mmol) was dissolved in 25mL of DMF, and terephthalic acid (0.615mmol) was dissolved in 25mL of DMF;
(2) mixing the two solutions in the step (1), adding 8mL of glacial acetic acid as a regulator, carrying out oil bath reaction at 120 ℃ for 4 hours, cooling to room temperature, centrifuging, washing with DMF, and vacuum-drying at 100 ℃ for 12 hours to obtain UiO-66;
(3) dissolving BmimBr (150mg) and UiO-66(200mg) powder in 40mL of methanol, stirring at room temperature for 24 hours, vacuumizing at 80 ℃ for 3 hours, and vacuum drying at 60 ℃ for 12 hours to obtain a 3# BmimBr @ UiO-66 composite material;
(4) weighing the 3# BmimBr @ UiO-66(200mg) obtained in the step (3), feeding the mixture into a tube furnace, calcining the mixture in a nitrogen atmosphere at the heating rate of 5 ℃/min at the constant temperature of 600 ℃ for 2 hours, cooling the mixture to room temperature, and taking the cooled mixture out to obtain the 3# CN @ ZrO 2 The material can be applied directly.
Example 4
This example used the process of the invention to prepare CN @ ZrO 2 The composite material is implemented as follows:
(1) reacting ZrCl 4 (0.615mmol) was dissolved in 25mL of DMF, and terephthalic acid (0.615mmol) was dissolved in 25mL of DMF;
(2) mixing the two solutions in the step (1), adding 8mL of glacial acetic acid as a regulator, carrying out oil bath reaction at 120 ℃ for 4 hours, cooling to room temperature, centrifuging, washing with DMF, and vacuum-drying at 100 ℃ for 12 hours to obtain UiO-66;
(3) dissolving BmimBr (200mg) and UiO-66(200mg) powder in 20mL of methanol, stirring for 24 hours at room temperature, vacuumizing for 3 hours at 80 ℃, and drying for 12 hours at 60 ℃ in vacuum to obtain a 4# BmimBr @ UiO-66 composite material;
(4) weighing the 4# BmimBr @ UiO-66(200mg) obtained in the step (3), feeding the 4# BmimBr @ UiO-66 into a tube furnace, and introducing the tube furnace into nitrogenCalcining in gas atmosphere at the heating rate of 5 ℃/min at the constant temperature of 600 ℃ for 2 hours, cooling to room temperature, and taking out to obtain the 4# CN @ ZrO 2 2 The material can be applied directly.
Example 5
This example used the process of the invention to prepare CN @ ZrO 2 The composite material is implemented as follows:
(1) reacting ZrCl 4 (0.615mmol) was dissolved in 25ml of DMF, and terephthalic acid (0.615mmol) was dissolved in 25ml of DMF;
(2) mixing the two solutions in the step (1), adding 8mL of glacial acetic acid as a regulator, carrying out oil bath reaction at 120 ℃ for 4 hours, cooling to room temperature, centrifuging, washing with DMF, and vacuum-drying at 100 ℃ for 12 hours to obtain UiO-66;
(3) dissolving BmimBr (200mg) and UiO-66(200mg) powder in 40mL of methanol, stirring for 24 hours at 25 ℃, vacuumizing for 3 hours at 80 ℃, and vacuum drying for 12 hours at 60 ℃ to obtain a 5# BmimBr @ UiO-66 composite material;
(4) weighing the 5# BmimBr @ UiO-66(200mg) obtained in the step (3), feeding the 5# BmimBr @ UiO-66 into a tube furnace, calcining the 5# BmimBr @ UiO-66 in a nitrogen atmosphere at the heating rate of 5 ℃/min at the constant temperature of 500 ℃ for 2 hours, cooling the 5# BmimBr @ UiO-66 to room temperature, and taking the 5# CN @ ZrO-66 out 2 The material can be applied directly.
Example 6
This example used the process of the invention to prepare CN @ ZrO 2 The composite material is implemented as follows:
(1) ZrCl 4 (0.615mmol) was dissolved in 25mL of DMF, and terephthalic acid (0.615mmol) was dissolved in 25mL of DMF;
(2) mixing the two solutions in the step (1), adding 8mL of glacial acetic acid serving as a regulator, carrying out oil bath reaction at 120 ℃ for 4 hours, cooling to room temperature, centrifuging, washing with DMF, and carrying out vacuum drying at 100 ℃ for 12 hours to obtain UiO-66;
(3) dissolving BmimBr (200mg) and UiO-66(200mg) powder in 40mL of methanol, stirring at room temperature for 24 hours, vacuumizing at 80 ℃ for 3 hours, and vacuum drying at 60 ℃ for 12 hours to obtain a 6# BmimBr @ UiO-66 composite material;
(4) weighing the No. 6 BmimBr @ UiO-66(200mg) obtained in the step (3), feeding the mixture into a tube furnace, and introducing the mixture into nitrogen gasCalcining at the temperature rising rate of 5 ℃/min under the atmosphere, keeping the temperature at 700 ℃ for 2 hours, cooling to the room temperature, and taking out to obtain the 6# CN @ ZrO 2 The material can be applied directly.
Example 7
This example used the process of the invention to prepare CN @ ZrO 2 The composite material is implemented as follows:
(1) reacting ZrCl 4 (0.615mmol) was dissolved in 25mL of DMF, and terephthalic acid (0.615mmol) was dissolved in 25mL of DMF;
(2) mixing the two solutions in the step (1), adding 8mL of glacial acetic acid as a regulator, carrying out oil bath reaction at 120 ℃ for 4 hours, cooling to room temperature, centrifuging, washing with DMF, and vacuum-drying at 100 ℃ for 12 hours to obtain UiO-66;
(3) dissolving BmimBr (200mg) and UiO-66(200mg) powder in 40mL of methanol, stirring at room temperature for 24 hours, vacuumizing at 80 ℃ for 3 hours, and vacuum drying at 60 ℃ for 12 hours to obtain a 7# BmimBr @ UiO-66 composite material;
(4) weighing the 7# BmimBr @ UiO-66(200mg) obtained in the step (3), feeding the 7# BmimBr @ UiO-66 into a tube furnace, calcining the 7# BmimBr @ UiO-66 in a nitrogen atmosphere at the heating rate of 5 ℃/min at the constant temperature of 600 ℃ for 1 hour, cooling the mixture to room temperature, and taking the cooled mixture out to obtain the 7# CN @ ZrO 2 The material can be applied directly.
Example 8
This example used the process of the invention to prepare CN @ ZrO 2 The composite material is implemented as follows:
(1) reacting ZrCl 4 (0.615mmol) was dissolved in 25mL of DMF, and terephthalic acid (0.615mmol) was dissolved in 25mL of DMF;
(2) mixing the two solutions in the step (1), adding 8mL of glacial acetic acid serving as a regulator, carrying out oil bath reaction at 120 ℃ for 4 hours, cooling to room temperature, centrifuging, washing with DMF, and carrying out vacuum drying at 100 ℃ for 12 hours to obtain UiO-66;
(3) dissolving BmimBr (200mg) and UiO-66(200mg) powder in 20mL of methanol, stirring at room temperature for 24 hours, vacuumizing at 80 ℃ for 3 hours, and vacuum drying at 60 ℃ for 12 hours to obtain an 8# BmimBr @ UiO-66 composite material;
(4) weighing the 8# BmimBr @ UiO-66(200mg) obtained in the step (3), feeding the weighed material into a tube furnace in a nitrogen atmosphereCalcining at the heating rate of 5 ℃/min at the constant temperature of 600 ℃ for 3 hours, cooling to room temperature, and taking out to obtain the 8# CN @ ZrO 2 The material can be applied directly.
Comparative example 1
This example used the process of the invention to prepare ZrO 2 The material is implemented as follows:
(1) reacting ZrCl 4 (0.615mmol) was dissolved in 25mL of DMF, and terephthalic acid (0.615mmol) was dissolved in 25mL of DMF;
(2) mixing the two solutions in the step (1), adding 8mL of glacial acetic acid as a regulator, carrying out oil bath reaction at 120 ℃ for 4 hours, cooling to room temperature, centrifuging, washing with DMF, and vacuum-drying at 100 ℃ for 12 hours to obtain UiO-66;
(3) weighing the UiO-66(200mg) obtained in the step (2), feeding the obtained product into a tube furnace, calcining the product in a nitrogen atmosphere at the heating rate of 5 ℃/min at the constant temperature of 600 ℃ for 2 hours, cooling the product to room temperature, and taking out the product to obtain the ZrO 2 The material can be applied directly.
For 4# CN @ ZrO obtained in example 4 2 Composite material and ZrO obtained in comparative example 1 2 Subjecting the material to powder diffraction (XRD), Scanning Electron Microscope (SEM), N 2 And (4) adsorption and desorption isotherm testing.
The XRD test result shows (figure 1), 4# CN @ ZrO 2 Characteristic peak of (b) and ZrO 2 Is consistent with the standard card, the material after pyrolysis is ZrO 2 . SEM results (FIG. 2) show that 4# CN @ ZrO prepared by the present invention 2 The rhombic dodecahedron shape of the original UiO-66 is still maintained. The results of the nitrogen adsorption and desorption experiments show (FIG. 3) that the 4# CN @ ZrO prepared by the invention 2 Composite material in P/P 0 At 0.5-1, there is a significant hysteresis loop, which can be classified as a combination of type I and type IV isotherms, indicating that the material is rich in micropores and mesopores, and compared to the comparative ZrO 2 Compared with the 4# CN @ ZrO prepared by the invention 2 The specific surface area is large. 4# CN @ ZrO 2 The hierarchical pore structure and the larger specific surface area in the composite material are beneficial to CO 2 And cycloaddition reaction with epoxy chloropropane.
CN @ ZrO obtained in examples 1 to 8 2 Composite materialAnd ZrO obtained by comparative example 2 Application of material in catalyzing CO 2 The reaction with cycloaddition of epichlorohydrin to produce cyclochloropropene carbonate gave the results shown in Table 1.
TABLE 1
| Sample (I) | Epichlorohydrin conversion (%) | Selectivity (%) for chloropropylene carbonate |
| 1#CN@ZrO 2 | 35 | 85 |
| 2#CN@ZrO 2 | 62 | 87 |
| 3 |
80 | 90 |
| 4#CN@ZrO 2 | 95 | 90 |
| 5 |
80 | 88 |
| 6#CN@ZrO 2 | 84 | 88 |
| 7 |
70 | 90 |
| 8#CN@ZrO 2 | 87 | 90 |
| Comparative example ZrO 2 | 21 | 14 |
Wherein, the experimental conditions of the catalytic reaction are as follows: epichlorohydrin (0.1mmol), N, N-dimethylformamide (DMF,2mL), catalyst (10mg), CO 2 Balloon, 100 ℃ for 12 h. Adding epichlorohydrin, catalyst and N, N-dimethylformamide to a Schlenk tube and connecting the CO 2 Balloon, Schlenk tube evacuated and CO performed 3 times 2 And (3) exchanging gas, placing the mixture into an oil bath kettle, stirring the mixture, centrifuging the mixture after the reaction is finished, collecting a supernatant, and analyzing the supernatant by using GC-FID (FULI,9790), wherein the reaction temperature is 100 ℃, and the reaction time is 12 hours.
As can be seen from the data in Table 1, CN @ ZrO prepared in accordance with the invention 2 The composite material is high-efficiency CO 2 Cycloaddition catalyst with epoxy chloropropane. Wherein 4# CN @ ZrO obtained in example 4 2 The catalytic effect is best (figure 4), 95 percent conversion rate and 90 percent selectivity (propylene carbonate) can be achieved within 12h, which shows CN @ ZrO 2 Highly dispersed ZrO in materials 2 The catalytic activity and selectivity can be obviously improved by doping the nano particles and Br. CN @ ZrO prepared by adopting preparation method 2 Composite material of in CO 2 Has excellent catalytic performance in the cycloaddition reaction with the epoxy chloropropane, and not only is CO 2 Provides a method for stably producing high value-added chemicalsEfficient and sustainable process, and highly efficient catalysis of CO for preparation of CO-catalyst free 2 Heterogeneous MOFs-based catalysts that cycloaddition react with epoxides provide the idea.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.
Claims (10)
1.CN@ZrO 2 The preparation method of the composite material is characterized by comprising the following steps:
s1, respectively dissolving metal salt and an organic ligand in a solvent to obtain a metal salt solution and an organic ligand solution;
s2, mixing the organic ligand solution and the metal salt solution, adding acid as a regulator, carrying out oil bath reaction for a period of time, cooling to room temperature, centrifuging, washing and drying to obtain UiO-66;
s3, dissolving imidazole bromide and UiO-66 powder in a solvent, stirring, vacuumizing, and drying to obtain an imidazole bromide @ UiO-66 composite material;
s4, calcining the imidazole bromine salt @ UiO-66 composite material in inert atmosphere to obtain nitrogen-doped porous carbon and ZrO 2 Composite material CN @ ZrO 2 。
2. The CN @ ZrO according to claim 1 2 The preparation method of the composite material is characterized by comprising the following steps: the metal salt in the step S1 is ZrCl 4 The organic ligand is terephthalic acid, and the solvent is N, N-dimethylformamide.
3. The CN @ ZrO of claim 2 2 The preparation method of the composite material is characterized by comprising the following steps: said step (c) isAcid in the S2 is glacial acetic acid, the oil bath temperature is 100-130 ℃, and the reaction time is 4 hours.
4. The CN @ ZrO of claim 3 2 The preparation method of the composite material is characterized by comprising the following steps: in the step S3, the imidazole bromine salt is one or more of BmimBr, EmimBr and OmimBr, and the solvent is methanol and/or ethanol.
5. CN @ ZrO according to any one of claims 1 to 4 2 The preparation method of the composite material is characterized by comprising the following steps: in the step S4, the inert gas is N 2 The calcination temperature is 500-1000 ℃, the calcination time is 1-4 hours, and the heating rate is 2-10 ℃/min.
6. CN @ ZrO according to claim 5 2 The preparation method of the composite material is characterized by comprising the following steps: in the step S2, methanol and/or ethanol and/or N, N-dimethylformamide are adopted for washing in the washing process, the drying method is vacuum drying, the drying temperature is 60-120 ℃, and the drying time is 10-18 hours.
7. The CN @ ZrO of claim 6 2 The preparation method of the composite material is characterized by comprising the following steps: in the step S3, the mass ratio of the imidazole bromine salt to the UiO-66 powder is 0.25-1.00, the stirring temperature is 20-40 ℃, the stirring time is 12-48 hours, the vacuumizing temperature is 50-80 ℃, the vacuumizing time is 2-6 hours, the drying is vacuum drying for 10-18 hours, and the drying temperature is 40-80 ℃.
8.CN@ZrO 2 A composite material characterized by: prepared by the process according to any one of claims 1 to 7.
9.CN@ZrO 2 The application method of the composite material is characterized by being applied to catalyzing CO 2 Cycloaddition reaction with epoxy chloropropane to prepare the chloropropylene carbonate.
10. The CN @ ZrO of claim 9 2 The application method of the composite material is characterized by comprising the following steps: epichlorohydrin, CN @ ZrO 2 The composite and N, N-dimethylformamide were added to a Schlenk tube and CO was connected 2 Balloon, Schlenk tube evacuated and CO added 2 And exchanging gas, heating and stirring for reaction, wherein the reaction temperature is 80-120 ℃, and the reaction time is 10-15 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115869932A (en) * | 2022-10-31 | 2023-03-31 | 浙江工业大学 | UIO-66 derived carbon material catalyst, preparation method thereof and application thereof in catalyzing carbon dioxide desorption |
| CN116459823A (en) * | 2023-03-13 | 2023-07-21 | 华南理工大学 | MOFs-derived ordered mesoporous cerium-zirconium composite oxide and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115869932A (en) * | 2022-10-31 | 2023-03-31 | 浙江工业大学 | UIO-66 derived carbon material catalyst, preparation method thereof and application thereof in catalyzing carbon dioxide desorption |
| CN116459823A (en) * | 2023-03-13 | 2023-07-21 | 华南理工大学 | MOFs-derived ordered mesoporous cerium-zirconium composite oxide and preparation method and application thereof |
| CN116459823B (en) * | 2023-03-13 | 2024-05-31 | 华南理工大学 | MOFs-derived ordered mesoporous cerium-zirconium composite oxide and preparation method and application thereof |
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