CN113145084A - MIL-101/PDVB composite material for adsorbing benzene gas and preparation method and application thereof - Google Patents
MIL-101/PDVB composite material for adsorbing benzene gas and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of indoor air purification materials, and particularly relates to an MIL-101/PDVB composite material for adsorbing benzene gas as well as a preparation method and an application thereof, wherein the preparation method comprises the following steps: mixing divinylbenzene, methacrylic acid, tetrahydrofuran, azodiisobutyronitrile and deionized water, stirring for 4 hours, putting into a polytetrafluoroethylene hydrothermal reaction kettle, preserving heat at 100 ℃ for 24 hours, cooling to volatilize a solvent, and then carrying out vacuum drying to obtain carboxyl modified PDVB; ultrasonically mixing sodium hydroxide, chromium nitrate nonahydrate, terephthalic acid, carboxyl modified PDVB and deionized water, putting the mixture into a polytetrafluoroethylene hydrothermal reaction kettle for reaction, preserving the heat at 150-170 ℃ for 18-24h, and then purifying and drying to obtain the MIL-101/PDVB composite material. The MIL-101/PDVB composite material provided by the invention has better adsorption performance on benzene, toluene and o-xylene.
Description
Technical Field
The invention belongs to the field of indoor air purification materials, and particularly relates to an MIL-101/PDVB composite material for adsorbing benzene gas and a preparation method and application thereof.
Background
Benzene, toluene and xylene are commonly referred to as triphenyl in industry, and benzene has the greatest harm to human body among the three substances. Benzene gas is a typical volatile organic compound, has strong carcinogenicity, and can cause cancer and a series of blood diseases. Benzene is a colorless, sweet transparent liquid at normal temperature and has a strong aromatic odor. Because benzene is highly volatile and readily diffuses when exposed to air, humans and animals inhale or come into contact with skin to a large amount of benzene entering the body, which can cause acute and chronic benzene poisoning. Common benzene gas treatment methods include an adsorption method, a condensation method, catalytic oxidation, a biological method and the like, wherein the adsorption method is one of the most economical and environment-friendly technologies, and the adsorption amount is particularly high at low concentration.
MIL-101 is a metal organic framework with chromium as a metal source, and is a tetrahedron formed by connecting chromium trimer and terephthalic acid, and then is bridged with the terephthalic acid to form a three-dimensional framework with a topological structure; MIL-101 is dominated by a microporous structure with a very small number of mesoporous structures. MIL-101 has a large number of unsaturated metal active sites (3mmol/g) and has a large adsorption capacity for benzene gas. However, MIL-101 has strong hydrophilicity, and is easily attacked by hydroxyl in water molecules mainly due to weak chromium-oxygen coordination, so that the structure is collapsed, and the adsorption capacity is reduced rapidly. Polydivinylbenzene is a high molecular polymer which is mainly of a mesoporous structure and has ultrahigh crosslinking property, and has excellent pore volume, ultrahigh hydrophobicity and lipophilicity; but its surface area is small and its pore size is too large, which is limited in handling small molecule contaminants.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides an MIL-101/PDVB composite material for adsorbing benzene gas and a preparation method and application thereof, wherein the composite material takes micron-sized carboxyl modified PDVB as a carrier; MIL-101 with octahedral shape and nanometer size is dispersed on the surface of carboxyl modified PDVB; the MIL-101/PDVB composite material keeps the mesoporous structure of carboxyl modified PDVB, so that the pore volume of the composite material is expanded, a good gas transmission channel is provided, and the adsorption quantity of the composite material to benzene gas is improved; the rich pore structure and swelling property of the carboxyl modified PDVB allow high-speed mass transfer, so that the adsorption rate of the composite material is enhanced, and the adsorption capacity of the composite material is improved; meanwhile, the benzene ring structure of the carboxyl modified PDVB enables the composite material to have excellent hydrophobic property, and the competitive adsorption capacity of MIL-101/PDVB to benzene gas is improved.
The invention is realized by the following technical scheme: a MIL-101/PDVB composite material for adsorbing benzene gas, wherein the structural formula of the composite material is as follows:
wherein P is a group derived from carboxyl-modified PDVB;
the structural formula of the carboxyl modified PDVB is as follows:
(the carboxyl modified PDVB is a three-dimensional hypercrosslinked structure, and the feeding range in the preparation process is m (methacrylic acid): m (divinylbenzene): 1:2-1: 8).
The mass percentage of PDVB in the MIL-101/PDVB composite material is 4% -7%.
Preferably, the mass percentage of the PDVB in the MIL-101/PDVB composite material is 5%.
The preparation method of the MIL-101/PDVB composite material for adsorbing the benzene gas comprises the following steps: the preparation method comprises the steps of adding carboxyl modified PDVB with micron-sized size (about 10-15 mu m) as a carrier into an MIL-101 precursor solution, uniformly mixing to obtain an MIL-101/PDVB precursor solution, and then preparing the precursor solution by a hydrothermal method.
More specifically, the method comprises the following steps:
a. mixing deionized water, methacrylic acid and/or acrylic acid, divinylbenzene and azodiisobutyronitrile according to the mass ratio of 0-2:0.2-1:1-2:0.05, dissolving in tetrahydrofuran, stirring at normal temperature for 4-8h, performing hydrothermal reaction to obtain carboxyl modified PDVB, and separating, drying and grinding to obtain the micron-sized carboxyl modified PDVB;
b. uniformly mixing chromium nitrate nonahydrate, sodium hydroxide, terephthalic acid and deionized water according to a molar ratio of 1:1:1: 278-;
c. pouring the MIL-101/PDVB precursor solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the kettle in a drying oven, and preserving heat for 18-24h at the temperature of 150-170 ℃ to obtain an unpurified MIL-101/PDVB composite material;
d. adding N, N-dimethylformamide and hot ethanol into the obtained unpurified MIL-101/PDVB composite material for purification to obtain a purified MIL-101/PDVB composite material;
e. and (3) cleaning the purified MIL-101/PDVB composite material by using distilled water and ethanol, and drying to obtain the MIL-101/PDVB composite material.
The application of the MIL-101/PDVB composite material for adsorbing benzene gas as a gas adsorbent is characterized in that: the benzene gas is one or more of benzene, toluene and o-xylene.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
the invention provides an MIL-101/PDVB composite material, which is made of Cr3+As a center, one side of the material is bonded with carboxyl modified PDVB through a coordination bond, and the other side of the material forms a coordination bond with terephthalic acid, so that the material is bridged together to form an MIL-101/PDVB composite material, and the selective adsorption of gases such as benzene, toluene, o-xylene and the like can be realized;
according to the invention, carboxyl modified PDVB is introduced on the basis of MIL-101, so that the prepared MIL-101/PDVB composite material has excellent pore volume and good gas transmission channel; meanwhile, the pore structure is enriched, and the composite material with the hierarchical pore structure is prepared;
the invention uses the carboxyl modified PDVB with ultrahigh hydrophobicity and lipophilicity as a carrier, (the purpose of the carboxyl modification is to combine the PDVB with Cr3+Coordination, the composite material is Cr3+Centered, the MIL-101 and the carboxyl modified PDVB are bridged together by bonding with the PDVB which is modified by carboxyl and has a benzene ring structure), the MIL-101 which has a porous structure, a high specific surface area and good thermal stability is loaded on the surface of the PDVB, and after adsorption saturation, the adsorbate is desorbed by thermal desorption or vacuum desorption, so that the recycling of the adsorbent can be realized, and secondary pollution is effectively avoided.
Drawings
FIG. 1 is FTIR photographs of MIL-101, carboxyl group-modified PDVB, and MIL-101/PDVB of example two, respectively.
FIG. 2 shows XRD diffraction patterns of MIL-101, carboxyl modified PDVB, and MIL-101/PDVB of example two, respectively.
FIG. 3 is a data plot of static benzene adsorption for MIL-101, carboxyl modified PDVB, and MIL-101/PDVB from example two, respectively.
Detailed Description
The invention is described in more detail below with reference to the following examples:
examples 1 to 4 are preferred examples based on the technical solution of the present invention, but are not limited thereto. For example, methacrylic acid or acrylic acid can be used for the preparation of carboxyl-modified PDVB, and methacrylic acid is taken as an example in the following examples. For example, the adsorption of benzene gas may be one or more of benzene, toluene and o-xylene, and benzene gas is exemplified in the following examples.
The first embodiment is as follows:
a. mixing 2ml of deionized water, 20ml of tetrahydrofuran, 1.6g of divinylbenzene, 0.4g of methacrylic acid and 0.05g of azobisisobutyronitrile at room temperature, stirring for 4-8h, pouring into a polytetrafluoroethylene hydrothermal reaction kettle, keeping the temperature at 100 ℃ for 24h, cooling along with a furnace until a solvent is volatilized, taking out, drying in a vacuum drying oven at 60 ℃ for 12h, and grinding to obtain carboxyl modified PDVB (hereinafter referred to as A), wherein the structural formula is as follows:
polydivinylbenzene (PDVB) is an adsorbent resin having characteristics of high specific surface area, large pore volume, controllable pore diameter, good chemical stability, etc., and thus is used as a gas adsorbent; and the benzene ring structure carried by the PDVB ensures that the composite material has excellent hydrophobic property, and improves the competitive adsorption capacity of the PDVB to benzene gas. According to the invention, the unique pore structure of the MIL-101 is combined, the PDVB is subjected to carboxyl modification, the carboxyl modified PDVB is taken as a carrier, the MIL-101 is loaded on the surface of the carboxyl modified PDVB to form an MIL-101/PDVB composite material, and the adsorption capacity to benzene, toluene or o-xylene and the like is enhanced.
b. Mixing and ultrasonically treating 0.118g A (the mass ratio of carboxyl modified PDVB in the MIL-101/PDVB composite material for adsorbing benzene gas (the MIL-101/PDVB composite material for adsorbing benzene gas in the invention can also be called as MIL-101/PDVB composite material or MIL-101/PDVB) is 4%), 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 B, namely an MIL-101/PDVB precursor solution;
c. pouring the precursor solution B into a polytetrafluoroethylene hydrothermal reaction kettle, and placing the kettle in an oven to keep the temperature at 150-170 ℃ for 18-24h to obtain an unpurified MIL-101/PDVB composite material;
d. adding N, N-dimethylformamide and hot ethanol into the obtained unpurified MIL-101/PDVB composite material for purification to obtain a purified MIL-101/PDVB composite material;
e. and (3) cleaning the purified MIL-101/PDVB composite material by using distilled water and ethanol, and drying to obtain the MIL-101/PDVB composite material for adsorbing benzene gas.
The MIL-101/PDVB composite material for adsorbing benzene gas prepared in the example measures the adsorption amount of benzene gas by using a static dryer method under the conditions of the ambient temperature of 25 ℃, the initial concentration of benzene gas of 2g/L and the adsorption time of 24h, and the adsorption amount is 1798mg/g (namely 1798mg of benzene gas can be adsorbed by every 1g of the MIL-101/PDVB composite material for adsorbing benzene gas, the same is applied below).
Example two:
this embodiment is substantially the same as the first embodiment, except that: "0.149 g of A (5% of carboxyl modified PDVB in the MIL-101/PDVB composite 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 are mixed and ultrasonically treated, and the concrete steps are as follows:
a. the step is the same as the step of the first embodiment;
b. mixing and ultrasonically treating 0.149gA (the proportion of carboxyl modified PDVB in the MIL-101/PDVB composite material for adsorbing benzene gas is 5%), 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 B, namely an MIL-101/PDVB 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/PDVB composite material for adsorbing benzene gas prepared in the example measures the adsorption capacity of benzene gas by using a static dryer method under the conditions of the ambient temperature of 25 ℃, the initial concentration of benzene gas of 2g/L and the adsorption time of 24h, and the measured adsorption capacity is 1916 mg/g.
Example three:
this embodiment is substantially the same as the first embodiment, except that: "0.181 gA (6% of carboxyl modified PDVB in the MIL-101/PDVB composite 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 are mixed and ultrasonically treated", and the concrete steps are as follows:
a. the step is the same as the step of the first embodiment;
b. mixing and ultrasonically treating 0.181gA (the ratio of carboxyl modified PDVB in MIL-101/PDVB for adsorbing benzene gas is 6%), 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 B, namely an MIL-101/PDVB 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/PDVB composite material for adsorbing benzene gas prepared in the example measures the adsorption capacity of benzene gas by using a static dryer method under the conditions of the ambient temperature of 25 ℃, the initial concentration of benzene gas of 2g/L and the adsorption time of 24h, and the measured adsorption capacity is 1713 mg/g.
Example four:
this embodiment is substantially the same as the first embodiment, except that: "0.213 gA (7% of carboxyl modified PDVB in the MIL-101/PDVB composite 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 are mixed and ultrasonically treated", and the concrete is as follows:
a. the step is the same as the step of the first embodiment;
b. mixing and ultrasonically treating 0.213gA (the ratio of carboxyl modified PDVB in the MIL-101/PDVB composite material for adsorbing benzene gas is 7%), 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 B, namely an MIL-101/PDVB 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/PDVB composite material for adsorbing benzene gas prepared in the example measures the adsorption quantity of the benzene gas by adopting 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 quantity is 1514 mg/g.
Comparative example 1
Mixing 2ml of deionized water, 20ml of tetrahydrofuran, 1.6g of divinylbenzene, 0.4g of methacrylic acid and 0.05g of azobisisobutyronitrile at room temperature, stirring for 4-8h, pouring into a polytetrafluoroethylene hydrothermal reaction kettle, keeping the temperature at 100 ℃ for 24h, cooling along with a furnace until the solvent is volatilized, taking out, drying in a vacuum drying oven at 60 ℃ for 12h, and grinding to obtain the carboxyl modified PDVB.
And measuring the adsorption quantity of the prepared carboxyl modified PDVB to the benzene gas by adopting a static dryer method under the conditions of the ambient temperature of 25 ℃, the initial concentration of the benzene gas of 2g/L and the adsorption time of 24h, wherein the measured adsorption quantity is 1108 mg/g.
Comparative example No. two
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. and (3) 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 distilled water and ethanol, and drying to obtain the MIL-101 material.
The MIL-101 material prepared in the example was used to measure the adsorption amount of benzene gas by a static dryer method at an ambient temperature of 25 deg.C, an initial benzene gas concentration of 2g/L, and an adsorption time of 24h, and the adsorption amount was 935 mg/g.
See FIG. 1 for FTIR photographs of carboxyl modified PDVB, MIL-101 and MIL-101/PDVB from example two, shown in the MIL-101/PDVB IR spectrum: carboxyl modified PDVB at 1720cm-1A distinct characteristic peak appears, which is the stretching vibration of C ═ O in the carboxyl group, indicating successful copolymerization of methacrylic acid with divinylbenzene. Characteristic peaks appear at the positions corresponding to the MIL-101 standard cards; MIL-101 Infrared Spectroscopy show: 1405 and 1629cm-1The absorption vibration of the O-C-O skeleton structure is taken as an organic skeleton of dicarboxylic acid; 1018 and 747cm-1Caused by the vibration of the benzene ring; 589cm-1The nearby absorption peak may be-COO groups are caused by in-plane, out-of-plane bending; MIL-101/PDVB IR spectrogram: there was a certain reduction in the intensity of the characteristic peak ascribed to the carboxyl group-modified PDVB, probably because MIL-101 was dispersed on the surface of the carboxyl group-modified PDVB, resulting in a certain reduction in the intensity of the characteristic peak ascribed to the carboxyl group-modified PDVB.
FIG. 2 shows XRD diffraction patterns of carboxyl-modified PDVB, MIL-101 and MIL-101/PDVB composite materials (MIL-101/PDVB for short) prepared in example II respectively, and it can be understood that carboxyl-modified PDVB has no obvious sharp diffraction peak, so that the carboxyl-modified PDVB can be presumed to be an amorphous material; the synthesized MIL-101 has distinct characteristic peaks at 2 θ ═ 2.9 °, 2 θ ═ 3.4 °, 2 θ ═ 5.2 °, 2 θ ═ 8.5 °, and 2 θ ═ 9.1 °. The MIL-101/PDVB is consistent with the characteristic diffraction peak of the MIL-101, and the MIL-101/PDVB composite material does not change the crystalline form of the MIL-101, and simultaneously completely maintains the structure of the MIL-101.
FIG. 3 is a graph showing the data of static benzene adsorption of carboxyl group-modified PDVB, MIL-101 and MIL-101/PDVB composite material (MIL-101/PDVB for short) prepared in example two. As can be seen from the figure, the static benzene adsorption capacity of the carboxyl modified PDVB is 1108mg/g, the static benzene adsorption capacity of the MIL-101 is 935mg/g, and the static benzene adsorption capacity of the MIL-101/PDVB composite material is improved and is 1916 mg/g.
The invention takes carboxyl modified PDVB with a mesoporous structure as a carrier, and adopts a one-step hydrothermal method to synthesize and prepare the MIL-101/PDVB composite material with a hierarchical pore structure. The composite material takes a mesoporous structure of carboxyl modified PDVB as a matrix, introduces MIL-101 with a microporous structure, and constructs MIL-101/PDVB composite material molecules and a pore structure through atom migration and lattice recombination under the conditions of high temperature and high pressure; composite material made of Cr3+One end of the polymer is bonded with carboxyl modified PDVB through a coordination bond, and the other end of the polymer is bonded with terephthalic acid through a coordination bond and bridged together to form the MIL-101/PDVB composite material; the composite material keeps the micropore structure of MIL-101, the benzene ring structure of the composite material is endowed with the carboxyl modified PDVB, the binding capacity of the composite material and benzene gas molecules is enhanced, and the selective adsorption of the composite material on the benzene molecules is realized. The method has the characteristics of easy obtaining, high efficiency, low cost and low pollution when treating the benzene gas.
Claims (5)
1. An MIL-101/PDVB composite material for adsorbing benzene gas, which is characterized in that: the structural formula of the composite material is as follows:
wherein P is a group derived from carboxyl-modified PDVB;
the structural formula of the carboxyl modified PDVB is as follows:
the mass percentage of PDVB in the MIL-101/PDVB composite material is 4% -7%.
2. The MIL-101/PDVB composite material for adsorbing benzene gas as claimed in claim 1, wherein: the mass percentage of PDVB in the MIL-101/PDVB composite material is 5%.
3. The method for preparing MIL-101/PDVB composite material for adsorbing benzene-based gas according to claim 1 or 2, wherein the method comprises: the preparation method comprises the steps of adding carboxyl modified PDVB with the particle size of 10-15 mu m as a carrier into an MIL-101 precursor solution, uniformly mixing to obtain an MIL-101/PDVB precursor solution, and then preparing the MIL-101/PDVB composite material for adsorbing benzene gas by a hydrothermal method.
4. The method for preparing the MIL-101/PDVB composite material for adsorbing the benzene gas according to claim 3, wherein the method comprises the following steps:
a. mixing deionized water, methacrylic acid and/or acrylic acid, divinylbenzene and azodiisobutyronitrile according to the mass ratio of 0-2:0.2-1:1-2:0.05, dissolving in tetrahydrofuran, stirring at normal temperature for 4-8h, performing hydrothermal reaction to obtain carboxyl modified PDVB, and separating, drying and grinding to obtain the carboxyl modified PDVB with the particle size of 10-15 mu m;
b. uniformly mixing chromium nitrate nonahydrate, sodium hydroxide, terephthalic acid and deionized water according to a molar ratio of 1:1:1: 278-;
c. pouring the MIL-101/PDVB precursor solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the kettle in a drying oven, and preserving heat for 18-24h at the temperature of 150-170 ℃ to obtain an unpurified MIL-101/PDVB composite material;
d. adding N, N-dimethylformamide and hot ethanol into the obtained unpurified MIL-101/PDVB composite material for purification to obtain a purified MIL-101/PDVB composite material;
e. and (3) cleaning the purified MIL-101/PDVB composite material by using distilled water and ethanol, and drying to obtain the MIL-101/PDVB composite material.
5. Use of the MIL-101/PDVB composite for adsorbing benzene-based gases as defined in claim 1 or 2 as a gas adsorbent, wherein: the benzene gas is one or more of benzene, toluene and o-xylene.
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| CN115106069A (en) * | 2022-07-20 | 2022-09-27 | 常州大学 | MIL-101/P (St-MMA-MAA) composite material and preparation method thereof |
| CN115286810A (en) * | 2022-08-15 | 2022-11-04 | 西北师范大学 | Preparation method of macromolecule induced hexagonal spindle-shaped bifunctional MOF |
| CN116081623A (en) * | 2023-04-11 | 2023-05-09 | 华侨大学 | Super-hydrophobic activated carbon material and preparation method and application thereof |
| CN116637602A (en) * | 2023-06-30 | 2023-08-25 | 常州大学 | MOF/COF composite material for adsorbing benzene pollutants and preparation method thereof |
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| CN116637602A (en) * | 2023-06-30 | 2023-08-25 | 常州大学 | MOF/COF composite material for adsorbing benzene pollutants and preparation method thereof |
| CN116637602B (en) * | 2023-06-30 | 2024-02-13 | 常州大学 | MOF/COF composite material for adsorbing benzene pollutants and preparation method thereof |
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