CN116637602B - MOF/COF composite material for adsorbing benzene pollutants and preparation method thereof - Google Patents
MOF/COF composite material for adsorbing benzene pollutants and preparation method thereof Download PDFInfo
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 11
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 21
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 claims abstract description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 16
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 9
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims abstract description 9
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 2
- 229940078552 o-xylene Drugs 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims 5
- 238000001179 sorption measurement Methods 0.000 abstract description 38
- 239000000463 material Substances 0.000 abstract description 11
- 238000010438 heat treatment Methods 0.000 abstract description 7
- XDIQTPZOIIYCTR-GRFIIANRSA-N [[(2r,3s,4r,5r)-5-(6-aminopurin-9-yl)-4-hydroxy-3-phosphonooxyoxolan-2-yl]methoxy-hydroxyphosphoryl] [(3r)-3-hydroxy-2,2-dimethyl-4-oxo-4-[[3-oxo-3-[2-(3,3,3-trifluoro-2-oxopropyl)sulfanylethylamino]propyl]amino]butyl] hydrogen phosphate Chemical compound O[C@@H]1[C@H](OP(O)(O)=O)[C@@H](COP(O)(=O)OP(O)(=O)OCC(C)(C)[C@@H](O)C(=O)NCCC(=O)NCCSCC(=O)C(F)(F)F)O[C@H]1N1C2=NC=NC(N)=C2N=C1 XDIQTPZOIIYCTR-GRFIIANRSA-N 0.000 abstract 8
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 239000012621 metal-organic framework Substances 0.000 description 67
- 230000000052 comparative effect Effects 0.000 description 16
- 230000003068 static effect Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 4
- 150000001555 benzenes Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000013177 MIL-101 Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 208000007443 Neurasthenia Diseases 0.000 description 1
- 206010029350 Neurotoxicity Diseases 0.000 description 1
- 208000013738 Sleep Initiation and Maintenance disease Diseases 0.000 description 1
- 206010044221 Toxic encephalopathy Diseases 0.000 description 1
- 208000007502 anemia Diseases 0.000 description 1
- 206010003549 asthenia Diseases 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 231100000025 genetic toxicology Toxicity 0.000 description 1
- 230000001738 genotoxic effect Effects 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 206010022437 insomnia Diseases 0.000 description 1
- 208000032839 leukemia Diseases 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 210000003141 lower extremity Anatomy 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000228 neurotoxicity Toxicity 0.000 description 1
- 230000007135 neurotoxicity Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920000779 poly(divinylbenzene) Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7027—Aromatic hydrocarbons
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of new materials, in particular to a MOF/COF composite material for adsorbing benzene pollutants and a preparation method thereof. The method comprises the following steps: a. the method comprises the steps of preparing the COF by a solvothermal method, dissolving melamine, terephthalaldehyde and 4-formylbenzoic acid serving as raw materials in dimethyl sulfoxide, putting the dimethyl sulfoxide into a polytetrafluoroethylene high-pressure reaction kettle, heating the mixture at 180 ℃ for 14 hours, and then purifying the mixture to obtain the COF; b. adding sodium hydroxide, chromium nitrate nonahydrate, terephthalic acid and COF into deionized water, mixing to obtain MOF precursor solution, placing into a polytetrafluoroethylene high-pressure reaction kettle, heating at 170 ℃ for 24 hours, and purifying to obtain MOF/COF. The preparation method of the MOF/COF composite material provided by the invention is simple and convenient, the connection between the MOF and the COF is stable, and the MOF/COF composite material has good adsorption performance on benzene pollutants.
Description
Technical Field
The invention relates to the field of new materials, in particular to a MOF/COF composite material for adsorbing benzene pollutants and a preparation method thereof.
Background
Benzene-based compounds are toxic to organisms and can create a direct hazard to human health. Through researches, BTEX has neurotoxicity (causing symptoms such as neurasthenia, headache, insomnia, dizziness, lower limb fatigue and the like) and genotoxicity (destroying DNA), and long-term contact can cause anemia and leukemia of human body. Metal Organic Frameworks (MOFs) are inorganic-organic composite porous adsorbent materials. The metal organic frame also has the characteristics of ultrahigh specific surface area and porosity, which is definitely a great advantage for gas adsorption, wherein the MIL-101 material has extremely high adsorption rate on VOCs, for example, chinese patent literature (application number 202110417409.3) discloses an MIL-101/PDVB composite material for adsorbing benzene gas, which has certain adsorption performance on benzene, toluene and o-xylene, but the adsorption capacity still needs to be improved.
Disclosure of Invention
The invention aims to provide a preparation method of a MOF/COF composite material for adsorbing benzene pollutants. The MOF/COF composite material has the characteristics of simple synthesis, no toxicity, low cost, high adsorption capacity and the like. The COF and the MOF are bonded, so that the stability of the material is enhanced, and the pi-pi interaction of the material is enhanced in the MOF compounded with the COF, so that the material becomes an adsorbent for benzene pollutants.
The preparation method of the MOF/COF composite material for adsorbing benzene pollutants comprises the following steps of:
a. monomer melamine, terephthalaldehyde and 4-formylbenzoic acid are taken as raw materials, the molar ratio of 3:3-3.8:0.9-2 (preferably 3:3.2-3.6:1.1-1.6) is dissolved in dimethyl sulfoxide, and the mixture is put into a polytetrafluoroethylene high-pressure reaction kettle to fully react (generally react for about 14 hours) at 180+/-10 ℃ to obtain unpurified COF;
b. fully washing the unpurified COF with acetone, dichloromethane and ethanol to obtain purified COF;
c. uniformly mixing chromium nitrate nonahydrate, terephthalic acid, sodium hydroxide and deionized water according to a molar ratio of 1:1:1:278-300 to obtain MOF precursor solution, adding the prepared COF of b, and carrying out ultrasonic mixing at normal temperature to obtain MOF/COF precursor solution;
d. transferring the MOF/COF precursor solution into a polytetrafluoroethylene high-pressure reaction kettle, placing the high-pressure reaction kettle into a baking oven, and preserving heat at 160-180 ℃ for 16-48 h to obtain an unpurified MOF/COF;
e. the purified MOF/COF was obtained by washing the unpurified MOF/COF with N, N-dimethylformamide and ethanol.
Compared with the prior art, the invention has the following characteristics:
1. according to the preparation method of the MOF/COF composite material, the common post-synthesis compounding is changed into pre-synthesis compounding, so that the synthesis time is greatly reduced.
2. The MOF/COF composite material provided by the invention has extremely high adsorption sites in pore channels, and the pi-pi interaction of the material is enhanced, so that the material has good adsorption performance.
3. Compared with other materials, the material and the synthesis method are environment-friendly, have lower raw material cost, and belong to the environment-friendly medicines.
Drawings
FIG. 1 shows XRD diffraction patterns of MOF/COF composite material prepared in example III and MOF prepared in comparative example I;
FIG. 2 is a SEM photograph of the MOF/COF composite material prepared in example III and the MOF prepared in comparative example I;
FIG. 3 is an infrared spectrum of the MOF/COF composite material prepared in example III and the MOF prepared in comparative example I;
FIG. 4 shows the MOF/COF composite material prepared in example III, and the N of the MOF prepared in comparative example I 2 Adsorption and desorption isothermal curves;
FIG. 5 is a graph showing the static benzene gas adsorption curves of the MOF/COF composite material prepared in example III, the MOF prepared in comparative example I, and the COF prepared in comparative example II.
Detailed Description
The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in various other embodiments according to the present invention, or simply change or modify the design structure and thought of the present invention, which fall within the protection scope of the present invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention is further described in detail below in connection with the examples:
example 1
a. Dissolving 0.4g of melamine, 0.32g of terephthalaldehyde and 0.36g of 4-formylbenzoic acid in 25mL of dimethyl sulfoxide, putting into a polytetrafluoroethylene high-pressure reaction kettle, and heating at 180 ℃ for 14h to obtain an unpurified COF;
b. fully washing the unpurified COF with acetone, dichloromethane and ethanol to obtain purified COF;
c. uniformly mixing 2g of chromium nitrate nonahydrate, 0.83g of terephthalic acid, 0.2g of sodium hydroxide and 25mL of deionized water to obtain MOF precursor solution, adding 0.1451g of COF, and carrying out ultrasonic mixing at normal temperature to obtain MOF/COF precursor solution;
d. transferring the MOF/COF precursor solution into a polytetrafluoroethylene high-pressure reaction kettle, placing the high-pressure reaction kettle into a baking oven, and preserving heat for 24 hours at 170 ℃ to obtain an unpurified MOF/COF;
e. the purified MOF/COF was obtained by washing the unpurified MOF/COF with N, N-dimethylformamide and ethanol.
The MOF/COF composite material for benzene gas adsorption prepared in the example is used for measuring the adsorption quantity of benzene gas by a static drier method under the conditions that the ambient temperature is 25 ℃, the initial concentration of benzene is 3g/L and the adsorption time is 24 hours, and the adsorption quantity is 1800mg/g.
Example two
a. Dissolving 0.4g of melamine, 0.43g of terephthalaldehyde and 0.24g of 4-formylbenzoic acid in 25mL of dimethyl sulfoxide, putting into a polytetrafluoroethylene high-pressure reaction kettle, and heating at 180 ℃ for 14h to obtain an unpurified COF;
b. fully washing the unpurified COF with acetone, dichloromethane and ethanol to obtain purified COF;
c. uniformly mixing 2g of chromium nitrate nonahydrate, 0.83g of terephthalic acid, 0.2g of sodium hydroxide and 25mL of deionized water to obtain MOF precursor solution, adding 0.1451g of COF, and carrying out ultrasonic mixing at normal temperature to obtain MOF/COF precursor solution;
d. transferring the MOF/COF precursor solution into a polytetrafluoroethylene high-pressure reaction kettle, placing the high-pressure reaction kettle into a baking oven, and preserving heat for 24 hours at 170 ℃ to obtain an unpurified MOF/COF;
e. the purified MOF/COF was obtained by washing the unpurified MOF/COF with N, N-dimethylformamide and ethanol.
The MOF/COF composite material for benzene gas adsorption prepared in the example was subjected to measurement of the adsorption amount of benzene gas by a static drier method under the conditions of an ambient temperature of 25 ℃ and an initial benzene concentration of 3g/L and an adsorption time of 24 hours, and the adsorption amount was measured to be 2100mg/g.
Example III
a. Dissolving 0.4g of melamine, 0.48g of terephthalaldehyde and 0.18g of 4-formylbenzoic acid in 25mL of dimethyl sulfoxide, putting into a polytetrafluoroethylene high-pressure reaction kettle, and heating at 180 ℃ for 14h to obtain an unpurified COF;
b. fully washing the unpurified COF with acetone, dichloromethane and ethanol to obtain purified COF;
c. uniformly mixing 2g of chromium nitrate nonahydrate, 0.83g of terephthalic acid, 0.2g of sodium hydroxide and 25mL of deionized water to obtain MOF precursor solution, adding 0.1451g of COF, and carrying out ultrasonic mixing at normal temperature to obtain MOF/COF precursor solution;
d. transferring the MOF/COF precursor solution into a polytetrafluoroethylene high-pressure reaction kettle, placing the high-pressure reaction kettle into a baking oven, and preserving heat for 24 hours at 170 ℃ to obtain an unpurified MOF/COF;
e. the purified MOF/COF was obtained by washing the unpurified MOF/COF with N, N-dimethylformamide and ethanol.
The MOF/COF composite material for benzene gas adsorption prepared in the example was subjected to measurement of the adsorption amount of benzene gas by a static drier method under the conditions of an ambient temperature of 25 ℃ and an initial benzene concentration of 3g/L and an adsorption time of 24 hours, and the adsorption amount was 2321mg/g.
Example IV
a. Dissolving 0.4g of melamine, 0.51g of terephthalaldehyde and 0.14g of 4-formylbenzoic acid in 25mL of dimethyl sulfoxide, putting into a polytetrafluoroethylene high-pressure reaction kettle, and heating at 180 ℃ for 14h to obtain an unpurified COF;
b. fully washing the unpurified COF with acetone, dichloromethane and ethanol to obtain purified COF;
c. uniformly mixing 2g of chromium nitrate nonahydrate, 0.83g of terephthalic acid, 0.2g of sodium hydroxide and 25mL of deionized water to obtain MOF precursor solution, adding 0.1451g of COF, and carrying out ultrasonic mixing at normal temperature to obtain MOF/COF precursor solution;
d. transferring the MOF/COF precursor solution into a polytetrafluoroethylene high-pressure reaction kettle, placing the high-pressure reaction kettle into a baking oven, and preserving heat for 24 hours at 170 ℃ to obtain an unpurified MOF/COF;
e. the purified MOF/COF was obtained by washing the unpurified MOF/COF with N, N-dimethylformamide and ethanol.
The MOF/COF composite material for benzene gas adsorption prepared in the example is used for measuring the adsorption quantity of benzene gas by a static drier method under the conditions that the ambient temperature is 25 ℃, the initial concentration of benzene is 3g/L and the adsorption time is 24 hours, and the adsorption quantity is 1862mg/g.
Comparative example one
a. Uniformly mixing 2g of chromium nitrate nonahydrate, 0.83g of terephthalic acid, 0.2g of sodium hydroxide and 25mL of deionized water to obtain a MOF precursor solution;
b. transferring the MOF precursor solution into a polytetrafluoroethylene high-pressure reaction kettle, placing the high-pressure reaction kettle into a baking oven, and preserving heat for 24 hours at 170 ℃ to obtain an unpurified MOF; c. the purified MOF was obtained after washing the unpurified MOF with N, N-dimethylformamide, ethanol.
The MOF for benzene gas adsorption prepared in this example was measured for adsorption amount of benzene gas by a static drier method under the conditions of an ambient temperature of 25℃and an initial benzene concentration of 3g/L and an adsorption time of 24 hours, and the adsorption amount was measured to be 906mg/g.
Comparative example two
a. Dissolving 0.4g of melamine, 0.51g of terephthalaldehyde and 0.14g of 4-formylbenzoic acid in 25mL of dimethyl sulfoxide, putting into a polytetrafluoroethylene high-pressure reaction kettle, and heating at 180 ℃ for 14h to obtain an unpurified COF; b. fully washing the unpurified COF with acetone, dichloromethane and ethanol to obtain purified COF; the COF composite material for benzene gas adsorption prepared in the example is used for measuring the adsorption quantity of the benzene gas by a static drier under the conditions that the ambient temperature is 25 ℃, the initial concentration of the benzene is 3g/L and the adsorption time is 24 hours, and the adsorption quantity is 794mg/g.
FIG. 1 shows XRD diffraction patterns of the MOF/COF composite material prepared in example III and the MOF prepared in comparative example I.
FIG. 2 (a) is an SEM photograph of the MOF obtained in comparative example one, and (b) is a MOF/COF composite material obtained in example three.
FIG. 3 shows FT-IR spectra of samples obtained in comparative example one and example three.
FIG. 4 shows N of samples obtained in comparative example one and example three 2 Adsorption-desorption curves.
FIG. 5 shows the static adsorption curves of the samples of comparative example I, comparative example II and example III, wherein the saturated benzene gas adsorption amount of the MOF/COF composite material of example III is 2321mg/g, the saturated benzene gas adsorption amount of the MOF of comparative example I is 906mg/g, and the saturated benzene gas adsorption amount of the COF composite material of comparative example II is 794mg/g.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (6)
1. A preparation method of a MOF/COF composite material for adsorbing benzene pollutants is characterized by comprising the following steps: the method comprises the following steps:
a. dissolving monomer melamine, terephthalaldehyde and 4-formylbenzoic acid as raw materials in a molar ratio of 3:3-3.8:0.9-2 in dimethyl sulfoxide, putting the mixture into a polytetrafluoroethylene high-pressure reaction kettle, and fully reacting at 170-190 ℃ to obtain an unpurified COF;
b. fully washing the unpurified COF with acetone, dichloromethane and ethanol to obtain purified COF;
c. uniformly mixing chromium nitrate nonahydrate, terephthalic acid, sodium hydroxide and deionized water according to a molar ratio of 1:1:1:278-300 to obtain MOF precursor solution, adding the purified COF prepared in step b, and performing ultrasonic mixing at normal temperature to obtain MOF/COF precursor solution;
d. transferring the MOF/COF precursor solution into a polytetrafluoroethylene high-pressure reaction kettle, placing the high-pressure reaction kettle into a baking oven, and preserving heat at 160-180 ℃ for 16-48 h to obtain an unpurified MOF/COF; the purified MOF/COF was obtained by washing the unpurified MOF/COF with N, N-dimethylformamide and ethanol.
2. The method for preparing the MOF/COF composite material for adsorbing benzene contaminants according to claim 1, wherein: melamine, terephthalaldehyde and 4-formylbenzoic acid are used as raw materials according to a molar ratio of 3:3.2-3.6:1.1-1.6.
3. The method for preparing the MOF/COF composite material for adsorbing benzene contaminants according to claim 1, wherein: the reaction temperature in step a was 180℃and the heat-retaining temperature in step d was 170 ℃.
4. A MOF/COF composite for adsorbing benzene contaminants prepared by the method of claim 1 or 2.
5. Use of the MOF/COF composite for adsorbing benzene contaminants according to claim 4, characterized in that: is used for adsorbing benzene pollutants.
6. The use of the MOF/COF composite for adsorbing benzene contaminants according to claim 5, characterized in that: the benzene pollutants are one or more of benzene, toluene and o-xylene.
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| CN113145084A (en) * | 2021-04-16 | 2021-07-23 | 常州大学 | MIL-101/PDVB composite material for adsorbing benzene gas and preparation method and application thereof |
| CN115090273A (en) * | 2022-07-18 | 2022-09-23 | 常州大学 | MIL-101/NPAN composite material for adsorbing benzene gas and preparation method thereof |
| CN115106069A (en) * | 2022-07-20 | 2022-09-27 | 常州大学 | MIL-101/P (St-MMA-MAA) composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112604659A (en) * | 2020-11-27 | 2021-04-06 | 嘉兴哲夫埃特环保科技有限公司 | Chiral ligand exchange type COF @ MOF/L composite material and preparation method thereof |
| CN113145084A (en) * | 2021-04-16 | 2021-07-23 | 常州大学 | MIL-101/PDVB composite material for adsorbing benzene gas and preparation method and application thereof |
| CN115090273A (en) * | 2022-07-18 | 2022-09-23 | 常州大学 | MIL-101/NPAN composite material for adsorbing benzene gas and preparation method thereof |
| CN115106069A (en) * | 2022-07-20 | 2022-09-27 | 常州大学 | MIL-101/P (St-MMA-MAA) composite material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| "A MOF@COF Composite with Enhanced Uptake through Interfacial Pore Generation";Luis Garzln-Tovar et al.;《Angewandte Chemie》;第131卷;第9612-9616页 * |
| "Adsorption and Diffusion of Benzene on Chromium-Based Metal Organic Framework MIL-101 Synthesized by Microwave Irradiation";Zhenxia Zhao et al.;《Industrial & Engineering Chemistry Research》;第50卷;第2254-2261页 * |
| "Preparation of MIL-101-NH2 MOF/triazine based covalent organic framework hybrid and its application in acid blue 9 removals";Mohammad Dinari et al.;《Polymer》;第215卷;第1-9页 * |
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