CN115106069B - MIL-101/P (St-MMA-MAA) composite material and preparation method thereof - Google Patents
MIL-101/P (St-MMA-MAA) composite material and preparation method thereof Download PDFInfo
- Publication number
- CN115106069B CN115106069B CN202210851326.XA CN202210851326A CN115106069B CN 115106069 B CN115106069 B CN 115106069B CN 202210851326 A CN202210851326 A CN 202210851326A CN 115106069 B CN115106069 B CN 115106069B
- Authority
- CN
- China
- Prior art keywords
- maa
- mma
- mil
- composite material
- benzene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000013177 MIL-101 Substances 0.000 title claims abstract description 110
- 239000002131 composite material Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 159
- 238000001179 sorption measurement Methods 0.000 claims abstract description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 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 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 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 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 229920005604 random copolymer Polymers 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 6
- 229940078552 o-xylene Drugs 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 47
- 239000002243 precursor Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000004887 air purification Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 11
- 230000003068 static effect Effects 0.000 description 8
- 238000000746 purification Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 3
- 230000002860 competitive effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- CLANNGNFKWVXHA-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;2-methylprop-2-enoic acid;styrene Chemical compound CC(=C)C(O)=O.COC(=O)C(C)=C.C=CC1=CC=CC=C1 CLANNGNFKWVXHA-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- 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
- 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
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
- B01D2253/202—Polymeric adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
- B01D2253/204—Metal organic frameworks (MOF's)
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to the field of air purification materials, in particular to an MIL-101/P (St-MMA-MAA) composite material and a preparation method thereof, wherein the composite material comprises a porous random copolymer material P (St-MMA-MAA), metal organic framework materials MIL-101 are uniformly distributed on the porous random copolymer material P through chemical bond connection, and the porous random copolymer material is connected with the metal organic framework materials through chemical bonds; the mass percent of P (St-MMA-MAA) in the MIL-101/P (St-MMA-MAA) composite material is 3-10wt%. The preparation method comprises mixing sodium hydroxide, chromium nitrate nonahydrate, terephthalic acid and water of P (St-MMA-MAA), performing hydrothermal reaction, purifying, and drying. The MIL-101/P (St-MMA-MAA) composite material has good adsorption performance on benzene, toluene and o-xylene.
Description
Technical Field
The invention belongs to the field of air purification, and relates to an MIL-101/P (St-MMA-MAA) composite material and a preparation method thereof.
Background
In recent years, volatile Organic Compounds (VOCs) have attracted considerable attention due to their adverse effects on human health. Among them, benzene compounds have strong carcinogenic action, and long-term exposure to benzene gas environment can cause acute and chronic benzene poisoning, cancer and a series of hematopathy. Currently, purification treatment methods for VOCs include adsorption methods, condensation purification methods, high-temperature combustion methods, and catalytic oxidation methods. The adsorption method has the remarkable advantages of low energy consumption, environmental friendliness, high removal efficiency and the like.
MIL-101 material has the advantages of high specific surface area, good aperture adjustability, modifier and the like, has stronger adsorption capacity to VOCs, but MIL-101 has a large number of hydrophilic sites, and when the adsorption environment has the condition that water vapor exists, water molecules and benzene gas are subjected to competitive adsorption on the surface of MIL-101, so that the adsorption capacity of MIL-101 is easier to saturate.
Disclosure of Invention
In order to improve the adsorption performance of MIL-101 on benzene gas in the presence of water vapor, the invention provides an MIL-101/P (St-MMA-MAA) composite material and a preparation method thereof. The composite material takes porous random copolymer poly (styrene-methyl methacrylate-methacrylic acid) (P (St-MMA-MAA)) as a carrier; octahedral nano-sized MIL-101 is dispersed on P (St-MMA-MAA) to form MIL-101/P (St-MMA-MAA) composite; MIL-101/P (St-MMA-MAA) composite material has the characteristics of high specific surface area and large pore volume of MIL-101 and rich phenyl functional groups of P (St-MMA-MAA), so that the adsorption capacity of benzene gas is increased; meanwhile, the P (St-MMA-MAA) also has an ester group structure, has excellent hydrophobicity, and greatly improves the competitive adsorption capacity of the MIL-101/P (St-MMA-MAA) composite material on benzene gas in the environment with water vapor.
MIL-101/P (St-MMA-MAA) composite material consists of metal-organic framework material MIL-101 and porous random copolymer material P (St-MMA-MAA), wherein the porous random copolymer is connected with the metal-organic framework material through chemical bonds.
The mass percentage of the P (St-MMA-MAA) in the MIL-101/P (St-MMA-MAA) composite material is 3-10wt%.
Preferably, the mass percentage of the P (St-MMA-MAA) in the MIL-101/P (St-MMA-MAA) composite material is 3-10wt% of the MIL-101 material;
the preparation method of the MIL-101/P (St-MMA-MAA) composite material for adsorbing benzene gas comprises the following steps: and adding the P (St-MMA-MAA) serving as a carrier into the MIL-101 precursor solution, uniformly mixing to obtain the MIL-101/P (St-MMA-MAA) precursor solution, and then preparing the MIL-101/P (St-MMA-MAA) precursor solution by a hydrothermal method.
More specifically, the method comprises the following steps:
a. styrene, methyl methacrylate and methacrylic acid are uniformly dissolved in a certain amount of toluene according to a certain proportion; azobisisobutyronitrile was added and degassed under vacuum. Fully reacting at 60-80 ℃ to obtain the porous random copolymer P (St-MMA-MAA);
b. uniformly mixing chromium nitrate nonahydrate, sodium hydroxide, terephthalic acid and deionized water according to the molar ratio of 1:1:1 (278-300) to obtain an MIL-101 precursor solution, adding the P (St-MMA-MAA) prepared in the step a, stirring at normal temperature, and performing ultrasonic treatment to obtain the MIL-101/P (St-MMA-MAA) precursor solution;
c. pouring the MIL-101/P (St-MMA-MAA) precursor solution into a polytetrafluoroethylene hydrothermal reaction kettle, and placing the kettle in an oven to keep the temperature at 160-180 ℃ for 18-24 hours to obtain an unpurified MIL-101/P (St-MMA-MAA) composite material;
d. adding N, N-dimethylformamide and hot ethanol into the obtained unpurified MIL-101/P (St-MMA-MAA) composite material for purification to obtain a purified MIL-101/P (St-MMA-MAA) composite material;
e. drying the purified MIL-101/P (St-MMA-MAA) composite material to obtain the MIL-101/P (St-MMA-MAA) composite material.
The application of the MIL-101/P (St-MMA-MAA) composite material for adsorbing benzene gas as a gas adsorbent, wherein the benzene gas is one or more of benzene, toluene and o-xylene;
compared with the prior art, the invention has the following beneficial effects:
the invention provides an MIL-101/P (St-MMA-MAA) composite material, which uses Cr 3+ One end of the MIL-101/P (St-MMA-MAA) is bonded with P (St-MMA-MAA) through coordination bond, and the other end of the MIL-101/P (St-MMA-MAA) is bridged together to form an MIL-101/P (St-MMA-MAA) composite material, so that the adsorption performance of the MIL-101 material on benzene, toluene, o-xylene and other benzene gases can be improved;
according to the invention, based on MIL-101, P (St-MMA-MAA) is introduced, so that the prepared MIL-101/P (St-MMA-MAA) composite material has excellent pore volume and good gas transmission channel;
the invention takes P (St-MMA-MAA) as a carrier, and MIL-101 is loaded on the surface of the carrier. Experiments prove that the invention has good adsorption capacity to benzene gas.
Drawings
FIG. 1 shows XRD patterns of MIL-101, P (St-MMA-MAA) and MIL-101/P (St-MMA-MAA) of example two, respectively.
FIG. 2 shows benzene gas adsorption curves of MIL-101, MIL-101/P (St-MMA-MAA) of example IV and MIL-101/P (St-MMA-MAA) of example II, respectively.
FIG. 3 is an SEM image of MIL-101/P (St-MMA-MAA) of example II.
Detailed Description
The invention is further described in detail below in connection with the examples:
embodiment one is a preferred embodiment based on the technical scheme of the invention, but is not limited to the preferred embodiment.
Embodiment one:
a. 10.43g of styrene, 3.00g of methyl methacrylate and 1.60g of methacrylic acid are homogeneously mixed in 50ml of toluene at room temperature; 0.1g of azobisisobutyronitrile was added and degassed under vacuum. Reacting at 70deg.C for 24 hr, drying, grinding to obtain P (St-MMA-MAA) powder;
b. mixing 0.091g (P (St-MMA-MAA) material in 3wt% in MIL-101/P (St-MMA-MAA) composite material for adsorbing benzene gas), 2g chromium nitrate nonahydrate, 0.2g sodium hydroxide, 0.83g terephthalic acid, 25ml ionized water, and ultrasonic to obtain precursor solution, namely MIL-101/P (St-MMA-MAA) precursor solution;
c. pouring the precursor solution into a polytetrafluoroethylene hydrothermal reaction kettle, and placing the kettle in an oven at 170 ℃ for 18-24 hours to obtain an unpurified MIL-101/P (St-MMA-MAA) composite material;
d. adding N, N-dimethylformamide and hot ethanol into the obtained unpurified MIL-101/P (St-MMA-MAA) composite material for purification to obtain a purified MIL-101/P (St-MMA-MAA) composite material;
e. washing the purified MIL-101/P (St-MMA-MAA) composite material with distilled water and ethanol, and drying to obtain the MIL-101/P (St-MMA-MAA) composite material for adsorbing benzene gas.
The MIL-101/P (St-MMA-MAA) composite material for adsorbing benzene gas prepared in this example was measured for the adsorption amount of benzene gas by a static drier method at an ambient temperature of 25℃and an initial benzene gas concentration of 2g/L for 24 hours, and the adsorption amount was 1338mg/g (i.e., 1338mg of benzene gas was adsorbed per 1g of MIL-101/P (St-MMA-MAA) composite material for adsorbing benzene gas, hereinafter the same shall apply).
Embodiment two:
this embodiment is substantially the same as the first embodiment except that: 0.152g of P (St-MMA-MAA) (P (St-MMA-MAA) material in an MIL-101/P (St-MMA-MAA) composite for adsorbing benzene gas in an amount of 5 wt%), 2g of chromium nitrate nonahydrate, 0.2g of sodium hydroxide, 0.83g of terephthalic acid, 25ml of ionized water were mixed and sonicated, concretely as follows:
a. this step is the same as that of the first embodiment;
b. mixing and sonicating 0.303g of P (St-MMA-MAA) in an MIL-101/P (St-MMA-MAA) composite material for adsorbing benzene gas, wherein the P (St-MMA-MAA) material accounts for 5wt%, 2g of chromium nitrate nonahydrate, 0.2g of sodium hydroxide, 0.83g of terephthalic acid and 25ml of ionized water to obtain a precursor solution, namely an MIL-101/P (St-MMA-MAA) precursor solution;
c. this step is the same as that of the first embodiment;
d. this step is the same as that of the first embodiment;
e. this step is the same as that of the first embodiment;
MIL-101/P (St-MMA-MAA) composite material for adsorbing benzene gas prepared in the example is subjected to measurement on the adsorption quantity of benzene gas by a static drier method under the condition that the ambient temperature is 25 ℃ and the initial concentration of benzene gas is 2g/L and the adsorption time is 24 hours, and the adsorption quantity is 1826mg/g.
Embodiment III:
this embodiment is substantially the same as the first embodiment except that: 0.303g of P (St-MMA-MAA) (P (St-MMA-MAA) material in an MIL-101/P (St-MMA-MAA) composite for adsorbing benzene gas in an amount of 10 wt%), 2g of chromium nitrate nonahydrate, 0.2g of sodium hydroxide, 0.83g of terephthalic acid, 25ml of ionized water were mixed and sonicated, concretely as follows:
a. this step is the same as that of the first embodiment;
b. mixing and sonicating 0.303g of P (St-MMA-MAA) in an MIL-101/P (St-MMA-MAA) material for adsorbing benzene gas at a ratio of 10wt%), 2g of chromium nitrate nonahydrate, 0.2g of sodium hydroxide, 0.83g of terephthalic acid and 25ml of ionized water to obtain a precursor solution C, namely an MIL-101/P (St-MMA-MAA) precursor solution;
c. this step is the same as that of the first embodiment;
d. this step is the same as that of the first embodiment;
e. this step is the same as that of the first embodiment;
MIL-101/P (St-MMA-MAA) composite material for adsorbing benzene gas prepared in the example is subjected to measurement on the adsorption quantity of benzene gas by a static drier method under the condition that the ambient temperature is 25 ℃ and the initial concentration of benzene gas is 2g/L and the adsorption time is 24 hours, and the adsorption quantity is 1258mg/g.
Example IV
MIL-101/P (St-MMA-MAA) composite material was prepared as follows
a. 10.00g of styrene, 1.50g of methyl methacrylate and 1.60g of methacrylic acid are homogeneously mixed in 50ml of toluene at room temperature; 0.2g of azobisisobutyronitrile was added and degassed under vacuum. The mixture was reacted at 70℃for 24 hours, and after drying and grinding, P (St-MMA-MAA) powder was obtained.
b. 0.152g (P (St-MMA-MAA) material in an MIL-101/P (St-MMA-MAA) composite material for adsorbing benzene gas in an amount of 5 wt%), 2g chromium nitrate nonahydrate, 0.2g sodium hydroxide, 0.83g terephthalic acid, 25ml ionized water were mixed and sonicated to obtain a precursor solution, namely an MIL-101/P (St-MMA-MAA) precursor solution;
c. pouring the precursor solution into a polytetrafluoroethylene hydrothermal reaction kettle, and placing the kettle in an oven at 170 ℃ for 18-24 hours to obtain an unpurified MIL-101/P (St-MMA-MAA) composite material;
d. adding N, N-dimethylformamide and hot ethanol into the obtained unpurified MIL-101/P (St-MMA-MAA) composite material for purification to obtain a purified MIL-101/P (St-MMA-MAA) composite material;
e. washing the purified MIL-101/P (St-MMA-MAA) composite material with distilled water and ethanol, and drying to obtain the MIL-101/P (St-MMA-MAA) composite material for adsorbing benzene gas.
The MIL-101/P (St-MMA-MAA) composite material for adsorbing benzene gas prepared in this comparative example was measured for the adsorption amount of benzene gas by a static drier method under the conditions of an ambient temperature of 25℃and an initial concentration of benzene gas of 2g/L for 24 hours, and the adsorption amount was 1663mg/g (i.e., 1663mg of benzene gas was adsorbed per 1g of MIL-101/P (St-MMA-MAA) composite material for adsorbing benzene gas, hereinafter the same shall apply).
Comparative example one
MIL-101 was prepared as follows
a. Mixing 0.83g of terephthalic acid, 2g of chromium nitrate nonahydrate, 0.2g of sodium hydroxide and 25ml of deionized water, mixing and carrying out ultrasonic treatment to obtain a precursor solution A, wherein A is MIL-101 precursor solution;
b. pouring the precursor solution A into a polytetrafluoroethylene hydrothermal reaction kettle, and placing the kettle in a vacuum drying oven to keep the temperature at 170 ℃ for 24 hours to obtain solution B;
c. adding the obtained product B into a certain amount of N, N-dimethylformamide and hot ethanol for purification;
d. and (3) cleaning the purified product with ethanol and drying to obtain the MIL-101 material.
MIL-101 material prepared in this example was subjected to measurement of adsorption amount of benzene gas by a static drier method under conditions of an ambient temperature of 25 ℃ and an initial benzene gas concentration of 2g/L and an adsorption time of 24 hours, and the adsorption amount was 914mg/g.
FIG. 1 shows XRD diffraction patterns of P (St-MMA-MAA), MIL-101 prepared in comparative example I and MIL-101/P (St-MMA-MAA) composite material prepared in example II, respectively (abbreviated as MIL-101/P (St-MMA-MAA)). MIL-101/P (St-MMA-MAA) is consistent with the characteristic diffraction peak of MIL-101, and MIL-101/P (St-MMA-MAA) composite material does not change the crystal form of MIL-101, and meanwhile the structure of MIL-101 is completely reserved.
FIG. 2 is a data graph showing static benzene adsorption of MIL-101 prepared in comparative example I, MIL-101/P (St-MMA-MAA) composite prepared in example IV, and MIL-101/P (St-MMA-MAA) composite prepared in example II, respectively. As can be seen from the graph, the static benzene adsorption amount of MIL-101 was 914mg/g, the static benzene adsorption amount of the MIL-101/P (St-MMA-MAA) composite material prepared in example four was increased, the adsorption amount was 1663mg/g, and the adsorption amount of the MIL-101/P (St-MMA-MAA) composite material prepared in example two was 1826mg/g.
FIG. 3 is an SEM image of MIL-101/P (St-MMA-MAA) of example II, which has a polyhedron with a grain size of 50-100nm, and MIL-101 is supported on P (St-MMA-MAA).
The invention takes P (St-MMA-MAA) as a carrier and adopts a hydrothermal method to synthesize and prepare MIL-101/P (St-MMA-MAA) complex with a multistage pore structureAnd (5) synthesizing materials. The composite material takes P (St-MMA-MAA) as a matrix, MIL-101 with a micropore structure is introduced, and MIL-101/P (St-MMA-MAA) composite material molecules and pore structures are constructed under the conditions of high temperature and high pressure; the composite material is Cr 3+ Is centered, one end is bonded with-COOH in P (St-MMA-MAA) through coordination bond, and the other end forms coordination bond with terephthalic acid, and is bridged together to form MIL-101/P (St-MMA-MAA) composite material; the composite material maintains the micropore structure of MIL-101, the benzene ring structure of P (St-MMA-MAA) enhances the binding capacity of the composite material with benzene gas molecules, and the hydrophobic property of the composite material is enhanced through ester functional groups. The invention has the characteristics of easy acquisition, high efficiency, low cost and low pollution when treating benzene gas.
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 (4)
1. An application of MIL-101/P (St-MMA-MAA) composite material in adsorbing benzene gas is characterized in that: the composite material comprises a porous random copolymer material P (St-MMA-MAA), wherein a metal organic framework material MIL-101 is uniformly distributed on the porous random copolymer material, the porous random copolymer material is connected with the metal organic framework material MIL-101 through a chemical bond, and the composite material is prepared by Cr 3+ Is the center;
the mass percentage of P (St-MMA-MAA) in the MIL-101/P (St-MMA-MAA) composite material is 3-10wt%;
the preparation of MIL-101/P (St-MMA-MAA) composite material comprises the following steps: adding P (St-MMA-MAA) serving as a carrier into an MIL-101 precursor solution, uniformly mixing to obtain a composite material precursor solution, and preparing the composite material precursor solution by a hydrothermal method;
the preparation of the P (St-MMA-MAA) comprises the following steps: styrene, methyl methacrylate and methacrylic acid are dissolved in toluene according to the mass ratio of 10:1.5-5:1-1.6, and azodiisobutyronitrile is added for heating reaction to obtain the catalyst.
2. Use of MILs-101/P (St-MMA-MAA) composite material according to claim 1, for the adsorption of benzene gases, characterized in that: the hydrothermal reaction temperature of the hydrothermal method is 160-180 ℃, the reaction time is 18-24h, and after the reaction is finished, the MIL-101/P (St-MMA-MAA) composite material for adsorbing benzene gas is obtained by cleaning and drying sequentially with N, N dimethylformamide and hot ethanol.
3. Use of MILs-101/P (St-MMA-MAA) composite material according to claim 1, for the adsorption of benzene gases, characterized in that: the MIL-101 precursor solution is a stable mixture of chromium nitrate nonahydrate, sodium hydroxide, terephthalic acid and deionized water in a molar ratio of 1:1:1:278-300.
4. Use of MILs-101/P (St-MMA-MAA) composite material according to claim 1, for the adsorption of benzene gases, characterized in that: the benzene gas is one or more of benzene, toluene and o-xylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210851326.XA CN115106069B (en) | 2022-07-20 | 2022-07-20 | MIL-101/P (St-MMA-MAA) composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210851326.XA CN115106069B (en) | 2022-07-20 | 2022-07-20 | MIL-101/P (St-MMA-MAA) composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115106069A CN115106069A (en) | 2022-09-27 |
| CN115106069B true CN115106069B (en) | 2024-02-20 |
Family
ID=83334258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210851326.XA Active CN115106069B (en) | 2022-07-20 | 2022-07-20 | MIL-101/P (St-MMA-MAA) composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115106069B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116637602B (en) * | 2023-06-30 | 2024-02-13 | 常州大学 | MOF/COF composite material for adsorbing benzene pollutants and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391602A (en) * | 2011-09-28 | 2012-03-28 | 河北工业大学 | High-heat-resistance polymethyl methacrylate (PMMA) resin and preparation method thereof |
| CN108530574A (en) * | 2018-04-18 | 2018-09-14 | 西安交通大学 | Reduction prepares poly-（Styrene methyl methacrylate-methylallyl alcohol）The method of glassy polymers |
| CN110467707A (en) * | 2018-05-10 | 2019-11-19 | 北京工业大学 | A kind of method of modifying effectively improving MOFs water stability and ammonia gas absorption performance |
| 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 |
| WO2022052069A1 (en) * | 2020-09-11 | 2022-03-17 | 中国科学院大连化学物理研究所 | Adsorbent and application thereof |
-
2022
- 2022-07-20 CN CN202210851326.XA patent/CN115106069B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391602A (en) * | 2011-09-28 | 2012-03-28 | 河北工业大学 | High-heat-resistance polymethyl methacrylate (PMMA) resin and preparation method thereof |
| CN108530574A (en) * | 2018-04-18 | 2018-09-14 | 西安交通大学 | Reduction prepares poly-（Styrene methyl methacrylate-methylallyl alcohol）The method of glassy polymers |
| CN110467707A (en) * | 2018-05-10 | 2019-11-19 | 北京工业大学 | A kind of method of modifying effectively improving MOFs water stability and ammonia gas absorption performance |
| WO2022052069A1 (en) * | 2020-09-11 | 2022-03-17 | 中国科学院大连化学物理研究所 | Adsorbent and application 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 |
Non-Patent Citations (1)
| Title |
|---|
| Fabrication of hierarchical porous polymer particles via blending strategy of water and polymer mixture;Bin Wang et al.;《Polym Int》;第71卷;第921-930页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115106069A (en) | 2022-09-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109232781B (en) | Preparation method of nitrogen-containing porous organic polymer | |
| CN109759035B (en) | NOxAdsorbent and preparation method and application thereof | |
| CN115106069B (en) | MIL-101/P (St-MMA-MAA) composite material and preparation method thereof | |
| CN112295395B (en) | Flue gas desulfurizer as well as preparation method and application thereof | |
| CN113145084A (en) | MIL-101/PDVB composite material for adsorbing benzene gas and preparation method and application thereof | |
| CN114588879B (en) | IL@MOFs composite material and preparation method and application thereof | |
| CN115475604B (en) | Manufacturing method of composite multifunctional adsorbent based on cork activated carbon and amino carbon quantum dots | |
| CN110787584A (en) | Application of cerium-based metal organic framework structure material in CO2Adsorption separation application of | |
| CN115155306B (en) | Efficient remover for indoor formaldehyde and organic volatile matters, preparation method and application | |
| CN112371083A (en) | Method for compounding hydrophobic coating on surface of activated carbon | |
| CN115364868A (en) | Catalyst for catalytic decomposition of ozone and preparation method thereof | |
| CN110090624B (en) | Preparation method and application of magnetic covalent organic framework material | |
| CN112588257B (en) | Ordered mesoporous silicon-glass fiber paper composite material and preparation method and application thereof | |
| CN113967482A (en) | Method for preparing bimetallic hexahedral nanosheet Ti-Ni-MOF catalyst through mesoscale regulation and control and application | |
| CN115090273B (en) | MIL-101/NPAN composite material for adsorbing benzene gas and preparation method thereof | |
| CN116637630B (en) | Sulfonic acid modified active coke loaded nano gold cluster double-regulation composite material and preparation method and application thereof | |
| CN112813531A (en) | Titanium dioxide nanoflower modified polyacrylonitrile nanofiber desulfurizer and preparation method thereof | |
| CN112934201B (en) | Composite waste gas adsorption material and preparation method thereof | |
| CN108448123B (en) | Cerium-based catalyst for low-temperature water gas shift reaction and preparation method thereof | |
| CN112934183B (en) | Organic waste gas adsorbent and preparation method thereof | |
| CN86101504A (en) | High efficiency drier self-indicating | |
| CN111545173B (en) | EG/functionalized MIL-101 composite material and preparation method and application thereof | |
| CN118204065B (en) | Preparation method of zeolite molecular sieve for VOCs treatment | |
| CN114950550B (en) | Chromium-free environment-friendly catalyst material for civil air defense | |
| CN118767892A (en) | Preparation process of active carbon with high adsorption and high degradation performance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |