CN115106069A - 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
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- 239000013177 MIL-101 Substances 0.000 title claims abstract description 113
- 239000002131 composite material Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 150
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- 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 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920005604 random copolymer Polymers 0.000 claims abstract description 12
- 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 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 7
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- 229940078552 o-xylene Drugs 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 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 10
- 238000002156 mixing Methods 0.000 claims description 9
- 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 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 32
- 238000004887 air purification Methods 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 41
- 230000003068 static effect Effects 0.000 description 8
- 238000000746 purification Methods 0.000 description 5
- -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
- 230000000052 comparative effect Effects 0.000 description 3
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- 239000011651 chromium Substances 0.000 description 2
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- 125000004185 ester group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- 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
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- 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
- 125000000524 functional group Chemical group 0.000 description 1
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- 208000014951 hematologic disease Diseases 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
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- 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
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- 239000000047 product Substances 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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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]
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- 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
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- 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)
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- 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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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), a metal organic framework material MIL-101 is 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 material through chemical bond; the mass percentage of P (St-MMA-MAA) in the MIL-101/P (St-MMA-MAA) composite material is 3-10 wt%. The preparation method comprises the steps of carrying out hydrothermal reaction on a water mixed solution of sodium hydroxide, chromium nitrate nonahydrate, terephthalic acid and P (St-MMA-MAA), 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 because of their adverse effects on human health. Among them, benzene series have strong carcinogenic action, and can cause acute and chronic benzene poisoning after long-term exposure to benzene gas environment, which can cause cancer and a series of blood diseases. Currently, methods for purifying VOCs include adsorption methods, condensation purification methods, high-temperature combustion methods, and catalytic oxidation methods. The adsorption method has the obvious advantages of low energy consumption, environmental friendliness, high removal efficiency and the like.
The MIL-101 material has the advantages of high specific surface area, good pore size adjustability, modifiability and the like, has strong adsorption force on VOCs, but the MIL-101 has a large number of hydrophilic sites, and when water vapor exists in an adsorption environment, water molecules and benzene gas compete for adsorption on the surface of the MIL-101, so that the adsorption capacity of the 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; MIL-101 with octahedral shape and nanometer size is dispersed on P (St-MMA-MAA) to form a MIL-101/P (St-MMA-MAA) composite material; the 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), and the adsorption capacity of benzene gas is increased; meanwhile, P (St-MMA-MAA) has an ester group structure and excellent hydrophobicity, and the competitive adsorption capacity of the MIL-101/P (St-MMA-MAA) composite material to benzene gas in the presence of water vapor is greatly improved.
The MIL-101/P (St-MMA-MAA) composite material is composed of a metal organic framework material MIL-101 and a porous random copolymer material P (St-MMA-MAA), wherein the porous random copolymer is connected with the metal organic framework material through a chemical bond.
The mass percentage of P (St-MMA-MAA) in the MIL-101/P (St-MMA-MAA) composite material is 3-10 wt%.
Preferably, the mass percentage of P (St-MMA-MAA) in the MIL-101/P (St-MMA-MAA) composite material, which is the MIL-101 material, is 3-10 wt%;
the preparation method of the MIL-101/P (St-MMA-MAA) composite material for adsorbing benzene gas comprises the following steps: adding P (St-MMA-MAA) serving as a carrier into the MIL-101 precursor solution, uniformly mixing to obtain an MIL-101/P (St-MMA-MAA) precursor solution, and then preparing by a hydrothermal method.
More specifically, the method comprises the following steps:
a. uniformly dissolving styrene, methyl methacrylate and methacrylic acid 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-;
c. pouring the MIL-101/P (St-MMA-MAA) precursor solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the reaction kettle in an oven, and preserving the heat at the temperature of 160-180 ℃ for 18-24h to obtain an unpurified MIL-101/P (St-MMA-MAA) composite material;
d. adding the obtained unpurified MIL-101/P (St-MMA-MAA) composite material into N, N-dimethylformamide and hot ethanol for purification to obtain a purified MIL-101/P (St-MMA-MAA) composite material;
e. and drying the purified MIL-101/P (St-MMA-MAA) composite material to obtain the MIL-101/P (St-MMA-MAA) composite material.
The MIL-101/P (St-MMA-MAA) composite material for adsorbing benzene gas is applied 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 is made of Cr 3+ One end of the MIL-101/P (St-MMA-MAA) is bonded with P (St-MMA-MAA) through a coordination bond, and the other end of the MIL-101/P (St-MMA-MAA) is bonded with terephthalic acid through a coordination bond, so that the MIL-101/P composite material is bridged together, and the adsorption performance of benzene gases such as benzene, toluene and o-xylene of the MIL-101 material can be improved;
according to the invention, P (St-MMA-MAA) is introduced on the basis of MIL-101, 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. Tests prove that the invention has good adsorption capacity for benzene gas.
Drawings
FIG. 1 shows XRD patterns for MIL-101, P (St-MMA-MAA) and MIL-101/P (St-MMA-MAA) of example two, respectively.
FIG. 2 shows the benzene gas adsorption curves for MIL-101, MIL-101/P from example four (St-MMA-MAA), and MIL-101/P from example two (St-MMA-MAA), respectively.
FIG. 3 is an SEM photograph of MIL-101/P (St-MMA-MAA) of example two.
Detailed Description
The invention is described in further detail below with reference to examples:
the embodiment is a preferred embodiment based on the technical solution of the present invention, but is not limited thereto.
The first embodiment is as follows:
a. 10.43g of styrene, 3.00g of methyl methacrylate and 1.60g of methacrylic acid were homogeneously mixed in 50ml of toluene at room temperature; 0.1g of azobisisobutyronitrile was added and degassed under vacuum. Reacting at 70 deg.C for 24h, drying, and grinding to obtain P (St-MMA-MAA) powder;
b. mixing and ultrasonically treating 0.091g of (P (St-MMA-MAA) (the content of P (St-MMA-MAA) in an MIL-101/P (St-MMA-MAA) composite material for adsorbing benzene gas is 3 wt%), 2g of chromium nitrate nonahydrate, 0.2g of sodium hydroxide, 0.83g of terephthalic acid and 25ml of ionic water 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 for heat preservation at 170 ℃ for 18-24h to obtain an unpurified MIL-101/P (St-MMA-MAA) composite material;
d. adding the obtained unpurified MIL-101/P (St-MMA-MAA) composite material into N, N-dimethylformamide and hot ethanol for purification to obtain a purified MIL-101/P (St-MMA-MAA) composite material;
e. and (3) cleaning 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-based gas prepared in this example was measured for adsorption of benzene-based gas by a static dryer method at an ambient temperature of 25 ℃ and an initial benzene gas concentration of 2g/L for an adsorption time of 24 hours, and found to have an adsorption amount of 1338mg/g (that is, 1338mg of benzene gas was adsorbed per 1g of the MIL-101/P (St-MMA-MAA) composite material for adsorbing benzene-based gas, as follows).
Example two:
this embodiment is substantially the same as the first embodiment, except that: 0.152g of P (St-MMA-MAA) (5 wt% of P (St-MMA-MAA) in the MIL-101/P (St-MMA-MAA) composite material for adsorbing benzene-based gas), 2g of chromium nitrate nonahydrate, 0.2g of sodium hydroxide, 0.83g of terephthalic acid, 25ml of ionic water were mixed and sonicated, as follows:
a. the step is the same as the step of the first embodiment;
b. mixing and ultrasonically treating 0.303g of P (St-MMA-MAA) in an MIL-101/P (St-MMA-MAA) composite material for adsorbing benzene gas, wherein the content of P (St-MMA-MAA) in the composite material is 5 wt%, 2g of chromium nitrate nonahydrate, 0.2g of sodium hydroxide, 0.83g of terephthalic acid and 25ml of ionic water to obtain a precursor solution, namely an MIL-101/P (St-MMA-MAA) precursor solution;
c. the step is the same as the step of the first embodiment;
d. the step is the same as the step of the first embodiment;
e. the step is the same as the step of the first embodiment;
the MIL-101/P (St-MMA-MAA) composite material for adsorbing benzene gas prepared in the example was used for measuring the adsorption amount of benzene gas by a static dryer method under the conditions of an ambient temperature of 25 ℃, an initial benzene gas concentration of 2g/L and an adsorption time of 24 hours, and the adsorption amount was 1826 mg/g.
Example three:
this embodiment is substantially the same as the first embodiment, except that: 0.303g of P (St-MMA-MAA) (10 wt% of P (St-MMA-MAA) in the MIL-101/P (St-MMA-MAA) composite material for adsorbing benzene-based gas), 2g of chromium nitrate nonahydrate, 0.2g of sodium hydroxide, 0.83g of terephthalic acid, 25ml of ionic water were mixed and sonicated, specifically as follows:
a. the step is the same as the step of the first embodiment;
b. mixing and ultrasonically treating 0.303g of P (St-MMA-MAA) in 10 wt% of MIL-101/P (St-MMA-MAA) material for adsorbing benzene gas, 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. the step is the same as the step of the first embodiment;
d. the step is the same as the step of the first embodiment;
e. the step is the same as the step of the first embodiment;
the MIL-101/P (St-MMA-MAA) composite material for adsorbing benzene gas prepared in the example was used for measuring the adsorption amount of benzene gas by a static dryer method under the conditions of an ambient temperature of 25 ℃, an initial benzene gas concentration of 2g/L and an adsorption time of 24h, and the adsorption amount was 1258 mg/g.
Example four
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 were homogeneously mixed in 50ml of toluene at room temperature; 0.2g of azobisisobutyronitrile was added and degassed under vacuum. Reacted at 70 ℃ for 24h, dried and ground to obtain P (St-MMA-MAA) powder.
b. Mixing and ultrasonically treating 0.152g of (P (St-MMA-MAA) (5 wt% of P (St-MMA-MAA) in an MIL-101/P (St-MMA-MAA) composite material for adsorbing benzene gas), 2g of chromium nitrate nonahydrate, 0.2g of sodium hydroxide, 0.83g of terephthalic acid and 25ml of ionic water 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 for heat preservation at 170 ℃ for 18-24h to obtain an unpurified MIL-101/P (St-MMA-MAA) composite material;
d. adding the obtained unpurified MIL-101/P (St-MMA-MAA) composite material into N, N-dimethylformamide and hot ethanol for purification to obtain a purified MIL-101/P (St-MMA-MAA) composite material;
e. and (3) cleaning 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.
In the MIL-101/P (St-MMA-MAA) composite material for adsorbing benzene gas prepared in the pair of examples, the adsorption amount of benzene gas was measured by a static dryer method under the conditions of an ambient temperature of 25 ℃, an initial concentration of benzene gas of 2g/L, and an adsorption time of 24h, and the measured adsorption amount was 1663mg/g (i.e., 1663mg of benzene gas can be adsorbed by 1g of the MIL-101/P (St-MMA-MAA) composite material for adsorbing benzene gas, which is the same below).
Comparative example 1
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 ultrasonically treating to obtain a precursor solution A, wherein A is an 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 for heat preservation at 170 ℃ for 24 hours to obtain B;
c. adding the obtained product B into a certain amount of N, N-dimethylformamide and hot ethanol for purification;
d. and washing the purified product with ethanol, and drying to obtain the MIL-101 material.
The MIL-101 material prepared in the example measures the adsorption capacity of benzene gas by a static dryer method under the conditions that the ambient temperature is 25 ℃, the initial concentration of the benzene gas is 2g/L, and the adsorption time is 24h, and the measured adsorption capacity is 914 mg/g.
FIG. 1 shows XRD diffraction patterns of P (St-MMA-MAA), MIL-101 obtained in comparative example one, and MIL-101/P (St-MMA-MAA) composite material (MIL-101/P (St-MMA-MAA) obtained in example two, respectively. MIL-101/P (St-MMA-MAA) is consistent with the characteristic diffraction peak of MIL-101, and the MIL-101/P (St-MMA-MAA) composite material does not change the crystal form of MIL-101, and simultaneously completely retains the structure of MIL-101.
FIG. 2 is a graph showing data on static benzene adsorption for MIL-101 prepared in comparative example one, MIL-101/P (St-MMA-MAA) composite prepared in example four, and MIL-101/P (St-MMA-MAA) composite prepared in example two (MIL-101/P (St-MMA-MAA) for short). 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 to 1663mg/g, and the adsorption amount of the MIL-101/P (St-MMA-MAA) composite material prepared in example two was 1826 mg/g.
FIG. 3 is an SEM image of MIL-101/P (St-MMA-MAA) of example two with grain size of 50-100nm polyhedral, MIL-101 loaded on P (St-MMA-MAA).
The invention takes P (St-MMA-MAA) as a carrier, and adopts a hydrothermal method to synthesize and prepare the MIL-101/P (St-MMA-MAA) composite material with a multistage pore channel structure. The composite material takes P (St-MMA-MAA) as a matrix, MIL-101 with a microporous structure is introduced, and MIL-101/P (St-MMA-MAA) composite material molecules and a porous structure are constructed under the conditions of high temperature and high pressure; composite material made of Cr 3+ One end of the polymer is bonded with-COOH in P (St-MMA-MAA) through a coordination bond, and the other end of the polymer forms a coordination bond with terephthalic acid and is bridged together to form an MIL-101/P (St-MMA-MAA) composite material; the composite material keeps the micropore structure of MIL-101, the benzene ring structure of P (St-MMA-MAA) enhances the binding capacity of the P and benzene gas molecules, and the hydrophobic performance of the P is enhanced through an ester group functional group. The method has the characteristics of easy obtaining, high efficiency, low cost and low pollution when treating the benzene gas.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (7)
1. A MIL-101/P (St-MMA-MAA) composite material, 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 P through chemical bond connection, and the porous random copolymer material is connected with the metal organic framework material through chemical bonds;
the mass percentage of P (St-MMA-MAA) in the MIL-101/P (St-MMA-MAA) composite material is 3-10 wt%.
2. The method for preparing MIL-101/P (St-MMA-MAA) composite material according to claim 1, wherein: adding P (St-MMA-MAA) serving as a carrier into the MIL-101 precursor solution, uniformly mixing to obtain a composite material precursor solution, and preparing the MIL-101/P (St-MMA-MAA) composite material for adsorbing benzene gas by a hydrothermal method.
3. The method for preparing MIL-101/P (St-MMA-MAA) composite material according to claim 2, wherein: the hydrothermal reaction temperature 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 sequentially cleaning and drying with N, N-dimethylformamide and hot ethanol.
4. The method for preparing MIL-101/P (St-MMA-MAA) composite material according to claim 2, wherein: the preparation of the porous random copolymer material P (St-MMA-MAA) comprises the following steps: dissolving styrene, methyl methacrylate and methacrylic acid in toluene, adding azobisisobutyronitrile, and carrying out a heating reaction to obtain the porous random copolymer material P (St-MMA-MAA).
5. The method for preparing MIL-101/P (St-MMA-MAA) composite material according to claim 4, wherein: the proportion of styrene, methyl methacrylate and methacrylic acid is 1-10: 1-5: 1-5.
6. The method for preparing MIL-101/P (St-MMA-MAA) composite material according to claim 2, wherein: 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.
7. The method for preparing MIL-101/P (St-MMA-MAA) composite material according to claim 1, wherein: the benzene gas is one or more of benzene, toluene and o-xylene.
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