CN111939985A - Core-shell type composite catalytic material and preparation method thereof - Google Patents
Core-shell type composite catalytic material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 46
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 239000011258 core-shell material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 239000013147 Cu3(BTC)2 Substances 0.000 claims abstract description 38
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 22
- 239000013309 porous organic framework Substances 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 55
- 239000000243 solution Substances 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 21
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000012265 solid product Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- BHIFXIATEXVOQA-UHFFFAOYSA-N 1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene Chemical compound CC1=C(CBr)C(C)=C(CBr)C(C)=C1CBr BHIFXIATEXVOQA-UHFFFAOYSA-N 0.000 claims description 11
- 239000007983 Tris buffer Substances 0.000 claims description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- -1 1-imidazolyl phenyl Chemical group 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- 239000012046 mixed solvent Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 12
- 239000004593 Epoxy Substances 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 230000002195 synergetic effect Effects 0.000 abstract description 6
- 239000002841 Lewis acid Substances 0.000 abstract description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 150000005676 cyclic carbonates Chemical class 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 19
- 230000001588 bifunctional effect Effects 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- UGVVUGWVKZVBGQ-UHFFFAOYSA-N NC1=CC=C(C2(C=CC=CC2)C2=NC=CN2)C=C1 Chemical compound NC1=CC=C(C2(C=CC=CC2)C2=NC=CN2)C=C1 UGVVUGWVKZVBGQ-UHFFFAOYSA-N 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000006352 cycloaddition reaction Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 150000007517 lewis acids Chemical class 0.000 description 4
- 238000002336 sorption--desorption measurement Methods 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 230000000269 nucleophilic effect Effects 0.000 description 3
- 239000011257 shell material Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- WBLIXGSTEMXDSM-UHFFFAOYSA-N chloromethane Chemical group Cl[CH2] WBLIXGSTEMXDSM-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—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
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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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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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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Abstract
The invention provides a core-shell type composite catalytic material and a preparation method thereof, belonging to the field of preparation methods of composite materials. The preparation method of the core-shell composite catalytic material comprises the steps of firstly preparing a metal organic framework material Cu with an open metal center as Lewis acid3(BTC)2Is a 'nucleus', and then is subjected to an ionic porous organic framework material iPOF-TB-Br‑Coating and providing bromide anion sites. The core-shell composite catalytic material of the invention also has Cu3(BTC)2And iPOF-TB-Br‑The advantages of the two materials can be used for efficiently catalyzing CO in the absence of homogeneous synergistic catalyst2Reacting with epoxy compound to generate cyclic carbonate; the preparation method of the core-shell composite catalytic material is simple and easy to operate, and the catalytic reaction productHigh efficiency, expandable reaction substrate types and good catalytic performance reproducibility.
Description
Technical Field
The invention relates to the cross technical field of organic chemistry, material chemistry, catalytic chemistry and the like, in particular to a core-shell type composite catalytic material formed by coating and packaging a metal organic framework material by an ionic porous organic framework material and a preparation method thereof.
Background
Along with the massive combustion of fossil energy, CO in the air is generated2The gas concentration increases, which is a major cause of global warming. CO 22Excessive discharge of gasHas adverse effect on the environment, but is also a C1 resource which is abundant, nontoxic and renewable, and can be converted into various industrial products with economic value through chemical reaction. Therefore, compared with pure CO2Adsorption vs storage, using CO2The raw materials are subjected to chemical reaction, so that CO in the air can be reduced2The concentration can also realize sustainable and economical utilization of C1 resources, thereby having better application prospect. CO 22The cycloaddition reaction of the cyclic carbonate with epoxide is to realize CO2One of the successful reactions of resource utilization.
Due to CO2Intrinsic thermodynamic and kinetic stability, activation of CO under mild conditions, in particular at low temperatures and pressures2And the conversion is difficult to realize, so the use of the catalyst in the reaction is very important. Metal-organic frameworks (MOFs) have the characteristics of high specific surface area, adjustable pore structure and the like, and the introduction of unsaturated Metal central sites into the MOFs can improve CO2Gas adsorption capacity and can be used as a high-efficiency Lewis acid catalytic site for CO2And (3) performing cycloaddition reaction. However, such MOFs with single sites typically require the addition of a homogeneous cocatalyst with nucleophilic sites to achieve catalytic conversion. In order to overcome the defect, nucleophilic halogen anions are provided by introducing ionic liquid functional groups through post-modification of MOFs catalysts with Lewis acid sites, so that CO-catalysis by the bifunctional sites can be realized2And (3) performing cycloaddition reaction. However, the currently used post-synthesis modification methods all have some disadvantages, such as: the post-modification process requires a complex experimental process; the modified MOFs must have specific active groups (such as amino, bromo, imidazolyl, etc.) so as to carry out ionic liquid site grafting on the MOFs; the modified MOFs are required to have ultrahigh physical stability, chemical stability and the like. Therefore, a simple, mild and universal modification method is developed, and a novel bifunctional synergistic catalyst is obtained for efficiently catalyzing CO under the mild condition without the existence of the synergistic catalyst2The transformation is of very practical significance.
Disclosure of Invention
The invention aims to solve the problem of the prior catalyst for catalyzing CO2The synthesis method of the difunctional metal organic framework material of the cycloaddition reaction is complex, and the requirements on the metal organic framework material are strict, thereby providing the difunctional core-shell type composite catalytic material and the preparation method thereof.
The invention adopts the technical scheme that a core-shell type composite catalytic material is provided, which is characterized in that an ionic porous organic framework material is used as a shell to coat and encapsulate a core of a metal organic framework material to obtain the difunctional core-shell type composite catalytic material with Lewis acid active sites and nucleophilic bromide active sites.
The preparation method of the bifunctional core-shell composite catalytic material comprises the following steps:
the method comprises the following steps: adding Cu (NO)3)2·3H2Dissolving O in deionized water to prepare a solution, and adding trimesic acid into absolute ethyl alcohol to prepare a solution; slowly mixing the two, keeping stirring, transferring the mixture into a reaction kettle after uniform mixing, and reacting for 12 hours at the temperature of 110 ℃; cooling to room temperature, filtering to obtain a solid product, washing with deionized water and absolute ethyl alcohol for 3-5 times, and drying at 60-100 ℃ for 10-12 hours under the condition that the vacuum degree is 133Pa to obtain the metal organic framework material Cu3(BTC)2；Cu(NO3)2·3H2The molar ratio of O, deionized water, trimesic acid and absolute ethyl alcohol is 1: 80-100: 0.5-0.7: 25-35;
step two: at room temperature, the metal organic framework material Cu is prepared3(BTC)2Dispersing in acetonitrile, adding 1,3, 5-tri (bromomethyl) -2,4, 6-trimethylbenzene under the condition of stirring, and continuously stirring for 10 minutes to prepare a solution A; in addition, tris [4- (1-imidazolyl phenyl)]Dissolving aniline in N, N' -dimethyl formamide solution to obtain solution B. Slowly dripping the solution B into the solution A, and then heating to 50-80 ℃ for reaction for 6-12 hours; cooling to room temperature, washing the filtered solid product with N, N' -dimethylformamide, acetonitrile and acetone for 3-5 times, and drying at 60-100 ℃ for 10-12 hours under the condition that the vacuum degree is 133Pa to obtain the core shellComposite catalytic material Cu3(BTC)2@iPOF-TB-Br-；Cu3(BTC)2Acetonitrile, 1,3, 5-tris (bromomethyl) -2,4, 6-trimethylbenzene, tris [4- (1-imidazolylphenyl)]-molar ratio of aniline to N, N' -dimethylformamide of 1: 200-500: 0.1-0.2: 0.1-0.2: 50 to 100.
The Cu3(BTC)2The solvent used for the dispersion is preferably acetonitrile.
The preferable concentration of the 1,3, 5-tri (bromomethyl) -2,4, 6-trimethylbenzene in the acetonitrile solution is 0.004 mol/L-0.02 mol/L.
The concentration of the tris [4- (1-imidazolyl phenyl) ] -aniline in the N, N' -dimethylformamide solution is preferably 0.02mol/L to 0.08 mol/L.
The bifunctional core-shell type composite catalytic material Cu3(BTC)2@iPOF-TB-Br-Catalysis of CO2The general reaction with epoxy compounds is:
wherein R is CH3，CH3CH2，ClCH2Or CH2＝CHCH2OCH2
The bifunctional core-shell type composite catalytic material Cu prepared by the method3(BTC)2@iPOF-TB-Br-Has a high specific surface area of 927m2Per g and a higher carbon dioxide adsorption capacity of 220cm3(273K). Simultaneously has an open metal center as a Lewis acid site and a bromine anion as a nucleophilic reagent site, and can catalyze CO under the mild condition without the existence of a homogeneous synergistic catalyst2And a cycloaddition reaction is carried out with an epoxy compound to generate a cyclic carbonate. In addition, the catalyst has better stability, and the catalytic performance of the catalyst is not obviously reduced after the catalyst is recycled for more than 5 times.
In conclusion, the bifunctional core-shell type composite catalytic material Cu provided by the invention3(BTC)2@iPOF-TB-Br-For catalyzing CO2By reaction with epoxy compoundsThe cyclic carbonate compound is generated, the reaction condition is mild, a synergistic catalyst is not needed, and the method has the advantages of high activity, easiness in separation, economy, environmental friendliness and the like. And the design and synthesis method of the composite material is ingenious and easy to realize.
Drawings
FIG. 1 Cu prepared in example 13(BTC)2And Cu3(BTC)2@iPOF-TB-Br-An infrared spectrum of (1);
FIG. 2 Cu prepared in example 13(BTC)2And Cu3(BTC)2@iPOF-TB-Br-XRD spectrum of (1);
FIG. 3 Cu prepared in example 13(BTC)2And Cu3(BTC)2@iPOF-TB-Br-Scanning an electron microscope image;
FIG. 4 Cu prepared in example 13(BTC)2@iPOF-TB-Br-Nitrogen adsorption-desorption attached figure measured at 77K and 0-1 atmospheric pressure;
FIG. 5 Cu prepared in example 13(BTC)2@iPOF-TB-Br-The carbon dioxide adsorption-desorption attached figure is measured at 273K and under the atmospheric pressure of 0-1;
FIG. 6 Cu prepared in example 13(BTC)2@iPOF-TB-Br-The X-ray photoelectron energy spectrum of the medium bromine element.
Detailed Description
The invention will be described in further detail with reference to the drawings and examples, which are provided for better understanding of the invention and are not intended to limit the scope of the invention.
Example 1
The method comprises the following steps: 2.5mmol of Cu (NO)3)2·3H2Dissolving O in 5mL of deionized water to prepare a solution, and adding 1.6mmol of trimesic acid into 5mL of absolute ethyl alcohol to prepare a solution; slowly mixing the two, keeping stirring, transferring the mixture into a reaction kettle after uniform mixing, and reacting for 12 hours at the temperature of 110 ℃; cooling to room temperature, filtering to obtain solid product, washing with deionized water and anhydrous ethanol for 5 times, and drying at 60 deg.C under vacuum degree of 133Pa for 12 hr to obtain metal organic framework materialCu material3(BTC)2。
Step two: 500mg of dried Cu was added at room temperature3(BTC)2Dispersing in 20mL of acetonitrile, adding 0.2mmol of 1,3, 5-tri (bromomethyl) -2,4, 6-trimethylbenzene under the condition of stirring, and continuing to stir for 10 minutes to prepare a mixed solution A; 0.2mmol of tris [4- (1-imidazolylphenyl)]-aniline was dissolved in 5mL of N, N' -dimethylformamide to prepare solution B. Slowly dripping the solution B into the solution A, and then heating to 50 ℃ for reaction for 12 hours; cooling to room temperature, washing the filtered solid product with N, N' -dimethylformamide, acetonitrile and acetone for 3 times, and drying at 60 ℃ for 12 hours under the condition that the vacuum degree is 133Pa to obtain the core-shell composite catalytic material Cu3(BTC)2@iPOF-TB-Br-。
For Cu synthesized in example 13(BTC)2And Cu3(BTC)2@iPOF-TB-Br-The structure of (2) is characterized.
FIG. 1 shows Cu prepared in example 13(BTC)2And Cu3(BTC)2@iPOF-TB-Br-Comparing the infrared spectrogram; as can be seen from FIG. 1, in Cu3(BTC)2@iPOF-TB-Br-Middle Cu3(BTC)2The characteristic peak of (A) is completely retained at 1508cm-1And 1070cm-1A new infrared absorption peak is caused by the vibration of an imidazole ring in the ionic porous organic framework shell material; 1272cm-1A new infrared absorption peak appears and is attributed to C-N stretching vibration in the ionic porous organic framework shell material.
FIG. 2 shows Cu prepared in example 13(BTC)2And Cu3(BTC)2@iPOF-TB-Br-XRD spectrum of (1) shows that Cu is contained3(BTC)2@iPOF-TB-Br-Still maintain Cu3(BTC)2The crystallinity of (2).
FIG. 3 shows Cu prepared in example 13(BTC)2And Cu3(BTC)2@iPOF-TB-Br-Scanning an electron microscope image; as can be seen from the figure, Cu3(BTC)2Has a regular octahedral structure with a smooth and regular surface; ionic porous organic framework packageAfter wrapping, Cu3(BTC)2@iPOF-TB-Br-The regular octahedral structure is still maintained, but the surface becomes relatively rough, which proves that the ionic porous organic framework is successfully wrapped in Cu3(BTC)2A surface.
FIG. 4 shows Cu prepared in example 13(BTC)2@iPOF-TB-Br-The nitrogen adsorption-desorption diagram is measured at 77K and 0-1 atmospheric pressure, and a typical I-type adsorption isotherm illustrates Cu3(BTC)2@iPOF-TB-Br-Has microporous structure and specific surface area of 927m2/g。
FIG. 5 shows Cu prepared in example 13(BTC)2@iPOF-TB-Br-The carbon dioxide adsorption-desorption attached figure is measured at 273K and 0-1 atmospheric pressure, and the adsorption capacity reaches 220cm3G, evidence of Cu3(BTC)2@iPOF-TB-Br-To CO2The gas has good adsorption performance.
FIG. 6 shows Cu prepared in example 13(BTC)2@iPOF-TB-Br-The existence of bromide anion is proved by the X-ray photoelectron spectrum of the medium bromine element.
Study of Cu provided in example 13(BTC)2@iPOF-TB-Br-To CO2Catalytic performance; the reaction conditions were as follows: cu3(BTC)2@iPOF-TB-Br -100 mg; 2mL of epoxy compound; reaction temperature: 60 ℃; CO 22Pressure: 0.5MPa and 24 hours of reaction time. Catalysis of CO2The general reaction with epoxy compounds is:
wherein R is CH3，CH2CH3，CH2Cl or CH2OCH2CH＝CH2
In which R is CH3The reaction yield was 94.5%;
in which R is CH2CH3The reaction yield was 82.5%;
in which R is CH2When Cl, the reaction yield is 95.1%;
in which R is CH2OCH2CH＝CH2The reaction yield was 95.7%; the above results show that the bifunctional core-shell composite catalytic material Cu provided in example 13(BTC)2@iPOF-TB-Br-Can catalyze various epoxy compounds and CO under mild conditions without a homogeneous synergistic catalyst2The reaction has good catalytic property.
Example 2
The method comprises the following steps: 2.5mmol of Cu (NO)3)2·3H2Dissolving O in 6mL of deionized water to prepare a solution, and adding 1.6mmol of trimesic acid into 6mL of absolute ethyl alcohol to prepare a solution; slowly mixing the two, keeping stirring, transferring the mixture into a reaction kettle after uniform mixing, and reacting for 12 hours at the temperature of 110 ℃; cooling to room temperature, filtering to obtain solid product, washing with deionized water and anhydrous ethanol for 5 times, and drying at 60 deg.C under vacuum degree of 133Pa for 12 hr to obtain metal organic framework material Cu3(BTC)2。
Step two: 500mg of dried Cu was added at room temperature3(BTC)2Dispersing in 20mL of acetonitrile, adding 0.2mmol of 1,3, 5-tri (bromomethyl) -2,4, 6-trimethylbenzene under the condition of stirring, and continuing to stir for 10 minutes to prepare a mixed solution A; 0.2mmol of tris [4- (1-imidazolylphenyl)]-aniline was dissolved in 5mL of N, N' -dimethylformamide to prepare solution B. Slowly dripping the solution B into the solution A, and then heating to 60 ℃ for reaction for 10 hours; cooling to room temperature, washing the filtered solid product with N, N' -dimethylformamide, acetonitrile and acetone for 3 times, and drying at 60 ℃ for 12 hours under the condition that the vacuum degree is 133Pa to obtain the core-shell composite catalytic material Cu3(BTC)2@iPOF-TB-Br-。
Study of Cu provided in example 23(BTC)2@iPOF-TB-Br-To CO2Catalytic performance; the reaction conditions were the same as in example 1.
In which R is CH3The reaction yield was 95.4%;
in which R is CH2CH3The reaction yield was 83.1%;
in which R is CH2When Cl, the reaction yield is 94.7%;
in which R is CH2OCH2CH＝CH2The reaction yield was 94.9%.
Example 3
The method comprises the following steps: 2.5mmol of Cu (NO)3)2·3H2Dissolving O in 6mL of deionized water to prepare a solution, and adding 1.8mmol of trimesic acid into 6mL of absolute ethyl alcohol to prepare a solution; slowly mixing the two, keeping stirring, transferring the mixture into a reaction kettle after uniform mixing, and reacting for 12 hours at the temperature of 110 ℃; cooling to room temperature, filtering to obtain solid product, washing with deionized water and anhydrous ethanol for 3 times, and drying at 60 deg.C under vacuum degree of 133Pa for 12 hr to obtain metal organic framework material Cu3(BTC)2。
Step two: 500mg of dried Cu was added at room temperature3(BTC)2Dispersing in 20mL of acetonitrile, adding 0.25mmol of 1,3, 5-tri (bromomethyl) -2,4, 6-trimethylbenzene under the condition of stirring, and continuing to stir for 10 minutes to prepare a mixed solution A; 0.25mmol of tris [4- (1-imidazolylphenyl)]-aniline was dissolved in 6mL of N, N' -dimethylformamide to prepare solution B. Slowly dripping the solution B into the solution A, and then heating to 70 ℃ for reaction for 8 hours; cooling to room temperature, washing the filtered solid product with N, N' -dimethylformamide, acetonitrile and acetone for 3 times, and drying at 60 ℃ for 12 hours under the condition that the vacuum degree is 133Pa to obtain the core-shell composite catalytic material Cu3(BTC)2@iPOF-TB-Br-。
Study of Cu provided in example 33(BTC)2@iPOF-TB-Br-To CO2Catalytic performance; the reaction conditions were the same as in example 1.
In which R is CH3The reaction yield was 92.1%;
in which R is CH2CH3The reaction yield was 81.0%;
in which R is CH2When Cl, the reaction yield is 91.4%;
in which R is CH2OCH2CH＝CH2The reaction yield was 92.3%.
Example 4
The method comprises the following steps: 2.5mmol of Cu (NO)3)2·3H2Dissolving O in 6mL of deionized water to prepare a solution, and adding 1.8mmol of trimesic acid into 6mL of absolute ethyl alcohol to prepare a solution; slowly mixing the two, keeping stirring, transferring the mixture into a reaction kettle after uniform mixing, and reacting for 12 hours at the temperature of 110 ℃; cooling to room temperature, filtering to obtain solid product, washing with deionized water and anhydrous ethanol for 3 times, and drying at 60 deg.C under vacuum degree of 133Pa for 12 hr to obtain metal organic framework material Cu3(BTC)2。
Step two: 500mg of dried Cu was added at room temperature3(BTC)2Dispersing in 20mL of acetonitrile, adding 0.27mmol of 1,3, 5-tri (bromomethyl) -2,4, 6-trimethylbenzene under the condition of stirring, and continuing to stir for 10 minutes to prepare a mixed solution A; 0.27mmol of tris [4- (1-imidazolylphenyl)]-aniline was dissolved in 6mL of N, N' -dimethylformamide to prepare solution B. Slowly dripping the solution B into the solution A, and then heating to 70 ℃ for reaction for 8 hours; cooling to room temperature, washing the filtered solid product with N, N' -dimethylformamide, acetonitrile and acetone for 3 times, and drying at 80 ℃ for 12 hours under the condition that the vacuum degree is 133Pa to obtain the core-shell composite catalytic material Cu3(BTC)2@iPOF-TB-Br-。
Study of Cu provided in example 43(BTC)2@iPOF-TB-Br-To CO2Catalytic performance; the reaction conditions were the same as in example 1.
In which R is CH3The reaction yield was 93.2%;
in which R is CH2CH3The reaction yield was 82.1%;
in which R is CH2When Cl, the reaction yield is 92.2%;
in which R is CH2OCH2CH＝CH2The reaction yield was 94.9%.
Example 5
The method comprises the following steps: 2.5mmol of Cu (NO)3)2·3H2Dissolving O in 6mL deionized water to obtain a solution, and adding 1.8mmol of trimesic acid to 6mLPreparing a solution in absolute ethyl alcohol; slowly mixing the two, keeping stirring, transferring the mixture into a reaction kettle after uniform mixing, and reacting for 12 hours at the temperature of 110 ℃; cooling to room temperature, filtering to obtain solid product, washing with deionized water and anhydrous ethanol for 3 times, and drying at 100 deg.C under vacuum degree of 133Pa for 10 hr to obtain metal organic framework material Cu3(BTC)2。
Step two: 500mg of dried Cu was added at room temperature3(BTC)2Dispersing in 20mL of acetonitrile, adding 0.27mmol of 1,3, 5-tri (bromomethyl) -2,4, 6-trimethylbenzene under the condition of stirring, and continuing to stir for 10 minutes to prepare a mixed solution A; 0.27mmol of tris [4- (1-imidazolylphenyl)]-aniline was dissolved in 6mL of N, N' -dimethylformamide to prepare solution B. Slowly dripping the solution B into the solution A, and then heating to 80 ℃ for reaction for 6 hours; cooling to room temperature, washing the filtered solid product with N, N' -dimethylformamide, acetonitrile and acetone for 3 times, and drying at 100 ℃ for 10 hours under the condition that the vacuum degree is 133Pa to obtain the core-shell composite catalytic material Cu3(BTC)2@iPOF-TB-Br-。
Study of Cu provided in example 53(BTC)2@iPOF-TB-Br-To CO2Catalytic performance; the reaction conditions were the same as in example 1.
In which R is CH3The reaction yield was 90.7%;
in which R is CH2CH3The reaction yield was 81.3%;
in which R is CH2When Cl, the reaction yield is 91.4%;
in which R is CH2OCH2CH＝CH2The reaction yield was 92.7%.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. It should be understood by those skilled in the art that various changes and substitutions may be made in accordance with the technical solution and the inventive concept of the present invention, and the same properties or uses should be considered as the protection scope of the present invention.
Claims (6)
1. A core-shell composite catalytic material is characterized by being an ionic porous organic framework material iPOF-TB-Br-Coating packaging metal organic frame material Cu3(BTC)2Formed core-shell Cu3(BTC)2@iPOF-TB-Br-A composite material.
2. The method for preparing the core-shell composite catalytic material of claim 1, characterized by comprising the steps of:
the method comprises the following steps: adding Cu (NO)3)2·3H2Dissolving O in deionized water to prepare a solution, and adding trimesic acid into absolute ethyl alcohol to prepare a solution; slowly mixing the two, keeping stirring, transferring the mixture into a reaction kettle after uniform mixing, and reacting for 12 hours at the temperature of 110 ℃; cooling to room temperature, filtering to obtain a solid product, washing with deionized water and absolute ethyl alcohol for 3-5 times, and drying at 60-100 ℃ for 10-12 hours under the condition that the vacuum degree is 133Pa to obtain the metal organic framework material Cu3(BTC)2；Cu(NO3)2·3H2The molar ratio of O, deionized water, trimesic acid and absolute ethyl alcohol is 1: 80-100: 0.5-0.7: 25-35;
step two: the metal organic framework material Cu is mixed at room temperature3(BTC)2Dispersing into acetonitrile, adding 1,3, 5-tri (bromomethyl) -2,4, 6-trimethylbenzene under the condition of stirring, and continuously stirring for 10 minutes to prepare a solution A; in addition, tris [4- (1-imidazolyl phenyl)]Dissolving aniline in N, N' -dimethyl formamide solution to obtain solution B. Slowly dripping the solution B into the solution A, and then heating to 50-80 ℃ for reaction for 6-12 hours; cooling to room temperature, washing the filtered solid product with N, N' -dimethylformamide, acetonitrile and acetone for 3-5 times, and drying at 60-100 ℃ for 10-12 hours under the condition that the vacuum degree is 133Pa to obtain the core-shell composite catalytic material Cu3(BTC)2@iPOF-TB-Br-；Cu3(BTC)2Acetonitrile, 1,3, 5-tris (bromomethyl) -2,4, 6-trimethylbenzene, tris [4- (1-imidazolylphenyl)]-molar ratio of aniline to N, N' -dimethylformamide of 1: 200-500: 0.1-0.2: 0.1～0.2：50～100。
3. the method for preparing the core-shell composite catalytic material of claim 2, wherein the reaction solvent in the first step is a mixed solvent of deionized water and absolute ethyl alcohol.
4. The method of claim 2, wherein said step II is Cu3(BTC)2The molar ratio to acetonitrile was 1: 200 to 500.
5. The method of claim 2, wherein said step II is Cu3(BTC)2And 1,3, 5-tris (bromomethyl) -2,4, 6-trimethylbenzene in a molar ratio of 1: 0.1 to 0.2.
6. The method of claim 2, wherein said step II is Cu3(BTC)2With tris [4- (1-imidazolylphenyl)]-molar ratio of aniline of 1: 0.1 to 0.2.
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