CN113209941A - Hydrophobic dual-ligand metal organic framework material, preparation method and application in VOCs adsorption - Google Patents
Hydrophobic dual-ligand metal organic framework material, preparation method and application in VOCs adsorption Download PDFInfo
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Abstract
The invention discloses a hydrophobic dual-ligand metal-organic framework material, a preparation method and application thereof in VOCs adsorption, wherein part of benzene rings in a metal-organic framework are replaced by naphthalene rings, and the positions connected with the naphthalene rings are located at two positions of 1-4 positions of the naphthalene rings. The metal organic framework material provided by the invention keeps stability in a humid environment and has the performance of efficiently adsorbing VOCs in the humid environment.
Description
Technical Field
The invention relates to a hydrophobic dual-ligand metal organic framework material, a preparation method and application thereof in VOCs adsorption.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
With the development of economy and industry, atmospheric pollution is a major environmental problem which must be faced globally, and particularly in developing countries, atmospheric pollution has become a major problem which endangers national health and limits economic development. A large amount of Volatile Organic Compounds (VOCs) are generated in the production process, and if the control is not standard, the environmental air quality is seriously influenced, and even the human health is harmed. The discharge of industrial source VOCs relates to a wide industrial range, and has the characteristics of high discharge intensity, high concentration, multiple pollutant types, long duration and the like. Therefore, pollution control of industrial VOCs has become a major research topic that must be addressed. Metal Organic Frameworks (MOFs) are a relatively new class of porous materials, assembled from inorganic metal nodes and organic ligands. In recent years, MOFs have received extensive attention in the fields of porous materials and adsorption due to their various attractive features such as high surface area and pore volume, easily tunable uniform pore size, chemically functionalized adsorption sites and the potential for post-synthesis modification.
Disclosure of Invention
The research of the inventor finds that the effect of adsorbing the VOCs by adopting the existing MOFs in the actual industrial environment is poor, and the further research shows that the VOCs are more than water vapor in coexistence in the industrial environment, and water molecules can possibly damage the crystal structure of the MOFs and competitive adsorption exists among the VOCs molecules. I.e. the practical use of MOFs in adsorptive separations to controlled storage and release applications, depends on their hydrophobicity and stability in humid or aqueous environments.
In order to solve the defects of the prior art, the invention aims to provide a hydrophobic dual-ligand metal-organic framework material, a preparation method and application in VOCs adsorption.
In order to achieve the purpose, the technical scheme of the invention is as follows:
on the one hand, the hydrophobic double-ligand metal organic framework material has the advantages that part of benzene rings in the metal organic framework are replaced by naphthalene rings, and the positions connected with the naphthalene rings are located in two positions of 1-4 positions of the naphthalene rings.
According to the invention, naphthalene rings are adopted to replace part of benzene rings in the MOFs, and the positions connected with the naphthalene rings are located at two positions of 1-4 positions of the naphthalene rings, so that the hydrophobic structure of the organic ligand is increased, the lipophilicity of the organic ligand is improved, the organic ligand is more beneficial to contact with VOCs, the adsorption performance of the organic ligand on the VOCs is improved, meanwhile, the hydrophobic structure is increased, the hydrophobicity of the MOFs is enhanced, and the stability of the MOFs in a humid environment is maintained. However, the space structure of the organic ligand also affects the pore size of the MOFs, and the pore size also affects the adsorption performance of the MOFs on VOCs, so that if the benzene ring is completely replaced by the naphthalene ring, the pores of the MOFs become smaller, and the adsorption performance of the MOFs on the VOCs is reduced, so that part of the benzene ring is replaced by the naphthalene ring, and the performance of adsorbing the VOCs in a humid environment is improved.
On the other hand, the preparation method of the hydrophobic dual-ligand metal-organic framework material is characterized in that part of the first organic ligand is replaced by the second organic ligand; the first organic ligand contains a benzene ring, the second organic ligand contains a naphthalene ring, and the positions connected with the naphthalene ring are located at two positions of 1-4 positions of the naphthalene ring.
According to the invention, the change of the MOFs structure is realized through the replacement of the organic ligand, so that the hydrophobic structure of the MOFs is increased, and the pore structure of the MOFs is adjusted, thereby improving the performance of the MOFs for adsorbing VOCs in a humid environment.
In a third aspect, the hydrophobic dual-ligand metal-organic framework material is applied to adsorption of VOCs. The hydrophobic dual-ligand metal-organic framework material provided by the invention has excellent performance of adsorbing VOCs in a humid environment, and part of the material has better VOCs adsorption performance than that of the raw material in a dry environment.
The invention has the beneficial effects that:
according to the invention, organic ligand terephthalic acid in MOFs is replaced by naphthalene dicarboxylic acid, so that the hydrophobic property of the MOFs is increased, and the adsorption effect of the MOFs on VOCs is improved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is an XRD of a UiO-66-NDC (X) hydrophobic metal organic framework material prepared by an example of the present invention.
FIG. 2 is a FT-TR spectrum of a UiO-66-NDC (X) hydrophobic metal organic framework material prepared according to an example of the present invention.
FIG. 3 is TG data for UiO-66-NDC (X) hydrophobic metal organic framework material prepared by the example of the present invention.
FIG. 4 shows BET data for UiO-66-NDC (X) hydrophobic metal organic framework material prepared according to an example of the present invention.
FIG. 5 shows an experimental apparatus for VOCs dynamic adsorption of UiO-66-NDC (X) hydrophobic metal organic framework material prepared by the embodiment of the present invention.
FIG. 6 shows the toluene dry adsorption breakthrough curves (a) and the adsorption capacities (b) of UiO-66-NDC (X) hydrophobic metal organic framework material prepared by the example of the present invention.
FIG. 7 shows the toluene wet adsorption breakthrough curves (a) and the adsorption capacities (b) of UiO-66-NDC (X) hydrophobic metal organic framework material prepared by the example of the present invention.
FIG. 8 is a toluene wet adsorption regenerability experiment for UiO-66-NDC (X) hydrophobic metal organic framework material prepared in an example of the present invention.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In view of the problem that MOFs are poor in hydrophobicity and stability in a humid or water environment, the invention provides a hydrophobic dual-ligand metal-organic framework material, a preparation method and application in VOCs adsorption.
The invention provides a typical embodiment of a hydrophobic dual-ligand metal-organic framework material, wherein a part of benzene rings in a metal-organic framework are replaced by naphthalene rings, and the positions connected with the naphthalene rings are located at two positions of 1-4 positions of the naphthalene rings.
According to the MOFs disclosed by the invention, naphthalene rings are adopted to replace part of benzene rings, and the positions connected with the naphthalene rings are located at two positions of 1-4 positions of the naphthalene rings, so that the hydrophobic structure of an organic ligand is increased, the lipophilicity of the organic ligand is improved, the organic ligand is more favorable for being in contact with VOCs, the adsorption performance of the organic ligand to the VOCs is improved, meanwhile, the hydrophobic structure is increased, the hydrophobicity of the MOFs is enhanced, and the stability of the MOFs in a humid environment is improved.
According to the invention, part of benzene rings are replaced by naphthalene rings, so that the condition that the pores of the MOFs are too small is prevented, and the diffusion performance of the VOCs in the MOFs is enhanced.
According to BET data, along with the replacement of naphthalene ring quantity, the micropore structure reduces and the mesopore structure increases, and the change increases the layered framework, is beneficial to the diffusion of toluene in pore channels and enhances the toluene adsorption capacity.
Naphthalene rings are introduced into MOFs, and the acting force of the naphthalene rings on toluene is greater than that of benzene rings on toluene, so that the toluene adsorption capacity is improved.
Several ways of the position of attachment of the naphthalene ring are shown below:
when the positions connected with the naphthalene rings are positioned at the 1 position and the 4 position of the naphthalene rings, the method is not only beneficial to maintaining the pore structure of MOFs and ensuring the performance of VOCs, but also beneficial to increasing the hydrophobic performance.
In some embodiments of this embodiment, the substituted molar percentage of naphthalene rings is 10 to 90%. E.g., 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, etc. When the substitution mole percentage content of the naphthalene ring is 15-35% (e.g. 15%, 20%, 25%, 30%, 35%), experiments prove that the condition has a better effect on adsorbing VOCs in a dry state, especially at 24-26%. When the substitution molar percentage of the naphthalene ring is 20-55% (e.g., 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%), experiments prove that the condition has a better effect of adsorbing VOCs in a wet environment, especially 45-55%.
Wherein the percent (%) substituted mole of naphthalene ring (mole of naphthalene ring in the hydrophobic double-ligand metal-organic framework material divided by mole of benzene ring in the original metal-organic framework) x 100%.
In some embodiments of this embodiment, the metal-organic framework is UiO-66. The invention adopts UiO-66 to carry out experiments, and has good effect.
In another embodiment of the invention, a preparation method of the hydrophobic dual-ligand metal-organic framework material is provided, wherein part of the first organic ligand is replaced by the second organic ligand; the first organic ligand contains a benzene ring, the second organic ligand contains a naphthalene ring, and the positions connected with the naphthalene ring are located at two positions of 1-4 positions of the naphthalene ring.
The preparation method of the hydrophobic dual-ligand metal organic framework material provided by the invention is the same as that of a conventional metal organic framework, and the difference is the selection and replacement of organic ligands. According to the invention, the change of the MOFs structure is realized through the replacement of the organic ligand, so that the hydrophobic structure of the MOFs is increased, and the pore structure of the MOFs is adjusted, thereby improving the performance of the MOFs for adsorbing VOCs in a humid environment.
Several ways of the position of attachment of the naphthalene ring are shown below:
when the positions connected with the naphthalene rings are positioned at the 1 position and the 4 position of the naphthalene rings, the method is not only beneficial to maintaining the pore structure of MOFs and ensuring the performance of VOCs, but also beneficial to increasing the hydrophobic performance.
In some examples of this embodiment, the molar amount of the second organic ligand is 10 to 90% of the total molar amount of the organic ligands. E.g., 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, etc. When the molar amount of the second organic ligand is 15 to 35% (e.g., 15%, 20%, 25%, 30%, 35%) of the total molar amount of the organic ligands, experiments prove that the condition is more effective for adsorbing VOCs in a dry state, especially at 24 to 26%. When the molar amount of the second organic ligand is 20-55% (e.g. 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%) of the total molar amount of the organic ligands, experiments prove that the condition has a better effect of adsorbing VOCs in a wet environment, especially 45-55%.
Wherein the total molar amount of the organic ligands is equal to the molar amount of the second organic ligand + the molar amount of the other part of the first organic ligands.
In some examples of this embodiment, the zirconium salt and the organic ligand are prepared using a solvothermal method; wherein the organic ligand is terephthalic acid (H)2BDC) and 1, 4-naphthalenedicarboxylic acid (H)2NDC)。
The zirconium salt of the present invention refers to a compound in which the cation is soluble in water and can ionize out zirconium ions, such as zirconium tetrachloride.
In one or more embodiments, the temperature of the solvothermal reaction is 115-125 ℃.
In one or more embodiments, the solvent of the solvothermal reaction is aqueous N, N-Dimethylformamide (DMF). The volume ratio of DMF to water is 1: 0.002-0.003.
In a third embodiment of the invention, an application of the hydrophobic dual-ligand metal-organic framework material in adsorption of VOCs is provided. The hydrophobic dual-ligand metal-organic framework material provided by the invention has excellent performance of adsorbing VOCs in a humid environment, and part of the material has better VOCs adsorption performance than that of the raw material in a dry environment.
Specifically, the adsorption of VOCs is the adsorption of VOCs in a humid environment.
The specific application method is that gas containing VOCs passes through the hydrophobic dual-ligand metal organic framework material. The hydrophobic dual-ligand metal-organic framework material needs to be heated and activated before being used as an adsorbent. The heating and activating temperature is 110-130 ℃.
In particular, the VOCs are benzene-based compounds (BTEX), such as toluene.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
The preparation method comprises the following steps:
1) 500mg of ZrCl40.3564mg of terephthalic acid, 115.8. mu.L of deionized water and 50mL of a solution of N, N-dimethylformamide were placed in a 100mL Erlenmeyer flask and stirred at 60 ℃ for 30 min.
2) Transferring the solution in the conical flask into a 100mL high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing the high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven, heating the high-pressure reaction kettle to ensure that the temperature of the oven is from room temperature to 120 ℃, and storing the high-pressure reaction kettle at the temperature for 24 hours; the rate of temperature rise was 5 ℃.
3) And closing the heating oven, reducing the temperature of the high-pressure reaction kettle in the oven to room temperature in a static state to obtain white powder, centrifuging, and repeatedly washing and centrifuging the collected solid product by using N, N-Dimethylformamide (DMF) for three times.
4) Putting the solid product obtained in the step 3) into an oven, heating, activating and drying for 10h at 120 ℃ to obtain the target product pure UiO-66 adsorbent, and recording the target product pure UiO-66 adsorbent as UiO-66.
Example 2
The preparation method comprises the following steps:
1) 500mg of ZrCl40.2673mg of terephthalic acid, 0.116mg of 1, 4-naphthalenedicarboxylic acid, 115.8. mu.L of deionized water and 50mL of a solution of N, N-dimethylformamide were placed in a 100mL conical flask and stirred at 60 ℃ for 30 minutes.
2) Transferring the solution in the conical flask into a high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing the high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven, heating the high-pressure reaction kettle to ensure that the temperature of the oven is from room temperature to 120 ℃, and storing the high-pressure reaction kettle for 24 hours at the temperature; the rate of temperature rise was 5 ℃.
3) And closing the heating oven, reducing the temperature of the high-pressure reaction kettle in the oven to room temperature in a static state to obtain white powder, centrifuging, and repeatedly washing and centrifuging the collected solid product by using N, N-Dimethylformamide (DMF) for three times.
4) Putting the solid product obtained in the step 3) into an oven, and heating, activating and drying at 120 ℃ for 10h to obtain a target product, namely UiO-66-NDC (25).
Example 3
The preparation method comprises the following steps:
1) 500mg of ZrCl40.18mg of terephthalic acid, 0.232mg of 1, 4-naphthalenedicarboxylic acid, 115.8. mu.L of deionized water and 50mL of a N, N-dimethylformamide solution were put into a 100 mL-volume Erlenmeyer flask and stirred at 60 ℃ for 30 minutes.
2) Transferring the solution in the conical flask into a high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing the high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven, heating the high-pressure reaction kettle to ensure that the temperature of the oven is from room temperature to 120 ℃, and storing the high-pressure reaction kettle for 24 hours at the temperature; the rate of temperature rise was 5 ℃.
3) And closing the heating oven, reducing the temperature of the high-pressure reaction kettle in the oven to room temperature in a static state to obtain white powder, centrifuging, and repeatedly washing and centrifuging the collected solid product by using N, N-Dimethylformamide (DMF) for three times.
4) Putting the solid product obtained in the step 3) into an oven, and heating, activating and drying at 120 ℃ for 10h to obtain a target product, namely UiO-66-NDC (50).
Example 4
The preparation method comprises the following steps:
1) 500mg of ZrCl40.464mg of 1, 4-naphthalenedicarboxylic acid, 115.8. mu.L of deionized water and 50mL of a N, N-dimethylformamide solution were added to a 100 mL-volume Erlenmeyer flask, and stirred at 60 ℃ for 30 minutes.
2) Transferring the solution in the conical flask into a high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing the high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven, heating the high-pressure reaction kettle to ensure that the temperature of the oven is from room temperature to 120 ℃, and storing the high-pressure reaction kettle for 24 hours at the temperature; the rate of temperature rise was 5 ℃.
3) And closing the heating oven, reducing the temperature of the high-pressure reaction kettle in the oven to room temperature in a static state to obtain white powder, centrifuging, and repeatedly washing and centrifuging the collected solid product by using N, N-Dimethylformamide (DMF) for three times.
4) Putting the solid product obtained in the step 3) into an oven, and heating, activating and drying at 120 ℃ for 10h to obtain a target product, namely UiO-66-NDC (100).
The materials obtained in examples 2 to 4 are collectively referred to as UiO-66-NDC (X).
The resulting material UiO-66-NDC (X) was characterized by XRD, as shown in FIG. 1. As can be seen from FIG. 1, the obtained UiO-66-NDC (X) material is highly consistent with the pure UiO-66 material, and the addition of the organic ligand naphthalenedicarboxylic acid does not change the original crystal structure of UiO-66.
The resulting material UiO-66-NDC (X) was characterized by FT-TR spectroscopy, as shown in FIG. 2. As can be seen from FIG. 2, it can be seen that as the H2NDC content of UiO-66 increases (from bottom to top in FIG. 6), H2An increase in NDC specific band and a decrease in H2BDC specific band. Successful introduction of the hydrophobic group naphthyl into the MOFs material structure was demonstrated.
The resulting material UiO-66-NDC (X) was characterized by BET, as shown in FIG. 3. As can be seen from fig. 3, the curve shows a steep rise at lower relative pressures, while another rise is observed at higher relative pressures, due to the microporosity present in these porous materials. The values of BET surface area and pore volume measured for UiO-66 and UiO-66-NDC (X) are given in Table 1. UiO-66 exhibits the greatest BET surface area and pore volume. A small hysteresis loop was observed for both UiO-66 of the dual ligand, demonstrating the presence of this mesopore for UiO-66-NDC (X). The existence of mesopores can generate a layered structure, which can remarkably improve the diffusion performance of MOFs and improve the adsorption capacity of the material.
TABLE 1 values for BET surface area and pore volume for UiO-66 and UiO-66-NDC (X).
The resulting material UiO-66-NDC (X) was characterized by TG, as shown in FIG. 4. As can be seen from fig. 4, the first weight loss occurs at temperatures up to 90 ℃, due to the removal of the solvent. The second phenomenon is observed in the range of 100-300 ℃, which is attributed to dehydroxylation of zirconium oxygen clusters. For the dual ligand UiO-66(Zr), a third weight loss was observed to occur at a slightly lower temperature than for pure UiO-66 (Zr). The decomposition temperature of the obtained sample is dependent on H2The increase in NDC content was reduced from 520 ℃ (UiO-66(Zr)) to 480 ℃ (UiO-66-NDC (100)), as better demonstrated by the DTG plot in FIG. 5.
Experimental example use of hydrophobic Metal organic framework Material UiO-66-NDC (X) in the adsorption of VOCs in the Dry (Wet) state:
VOCs adsorbs experimental apparatus as shown in FIG. 5, VOCs adsorbs experimental apparatus comprises gas cylinder, flowmeter, trace annotation pump, VOCs (water) steam generator, cushion flask, adsorption disc and hand-held type VOCs detector.
The synthesis air is used as carrier gas in the adsorption process, which is more consistent with practical industrial environment than nitrogen. Toluene (water) vapor is generated by a steam generator. The carrier gas flow is controlled by a mass flow controller. Before the experiment, the adsorbent was heated in an oven at 120 ℃ for 6 h. Toluene and water are respectively injected into the steam generator by the two micro-injection pumps to generate steam, the steam is brought into the buffer bottle by carrier gas to be fully mixed, then the steam is conveyed to the adsorption device and is connected with the VOCs detector, and finally, the processed data is exported.
The specific process is as follows: the VOCs (water) vapor generator was preheated to the specified 116 deg.C, and 0.5 g of each of the four synthesized UiO-66-NDC (X) materials was weighed into an adsorption tray. Preheating a VOCs (water) steam generator to a specified 116 ℃, introducing carrier gas, debugging and opening a handheld VOCs detector to perform VOCs dynamic adsorption experiment. And (5) adsorbing and saturating the material, transferring the adsorption disc to a heating oven, and heating, desorbing and regenerating.
The results are shown in fig. 6, 7 and 8. As can be seen from the above figures, the introduction of the non-polar functional group naphthyl into UiO-66 by the addition of H + NDC ligand improves the adsorption performance of VOCs molecules in high humidity environments. And the modified samples all showed higher adsorption performance than the original UiO-66 at different relative humidities. The optimum toluene adsorption capacity of UiO66-NDC (50) was 76mg/g, 69% higher than that of UiO-66, at a relative humidity of 50%. Finally, cyclic adsorption experiments have shown that UiO-66-NDC (50) can be effectively regenerated and reused for adsorption in five cyclic steps. These results indicate that the UiO-66NDC (X) material can be used as an effective adsorbent for the removal of VOCs in a practical industrial environment.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A hydrophobic dual-ligand metal-organic framework material is characterized in that a part of benzene rings in a metal-organic framework are replaced by naphthalene rings, and the positions connected with the naphthalene rings are located in two positions of 1-4 positions of the naphthalene rings.
2. The hydrophobic dual ligand metal-organic framework material of claim 1, wherein the linking position to the naphthalene ring is at the 1-position and the 4-position of the naphthalene ring.
3. The hydrophobic dual-ligand metal-organic framework material as claimed in claim 1, wherein the substitution mole percentage content of naphthalene ring is 10-90%;
preferably, the substitution mole percentage content of the naphthalene ring is 15-35%, and further preferably 24-26%;
preferably; the substitution mole percentage content of the naphthalene ring is 20-55%, and the preferable content is 45-55%.
4. The hydrophobic dual ligand metal-organic framework material of claim 1, wherein the metal-organic framework is UiO-66.
5. A preparation method of a hydrophobic dual-ligand metal organic framework material is characterized in that part of first organic ligands are replaced by second organic ligands; the first organic ligand contains a benzene ring, the second organic ligand contains a naphthalene ring, and the positions connected with the naphthalene ring are located at two positions of 1-4 positions of the naphthalene ring.
6. The method for preparing a hydrophobic dual ligand metal-organic framework material according to claim 5, wherein the linking positions with the naphthalene ring are located at the 1-position and the 4-position of the naphthalene ring.
7. The method of claim 5, wherein the molar amount of the second organic ligand is 10-90% of the total molar amount of the organic ligands;
preferably, the molar amount of the second organic ligand is 15 to 35 percent of the total molar amount of the organic ligands, and further preferably 24 to 26 percent;
preferably, the molar amount of the second organic ligand is 20 to 55 percent of the total molar amount of the organic ligands, and more preferably 45 to 55 percent.
8. The method for preparing a hydrophobic dual-ligand metal-organic framework material according to claim 5, wherein the hydrophobic dual-ligand metal-organic framework material is prepared by a solvothermal method by using a zirconium salt and an organic ligand; wherein the organic ligand is terephthalic acid and 1, 4-naphthalene dicarboxylic acid;
preferably, the temperature of the solvothermal reaction is 115-125 ℃;
preferably, the solvent of the solvothermal reaction is aqueous N, N-dimethylformamide; further preferably, the volume ratio of DMF to water is 1: 0.002-0.003.
9. Use of the hydrophobic dual-ligand metal-organic framework material according to any one of claims 1 to 4 or the hydrophobic dual-ligand metal-organic framework material obtained by the preparation method according to any one of claims 5 to 8 in adsorption of VOCs.
10. The use according to claim 9, wherein the adsorption of VOCs is adsorption of VOCs in a humid environment;
or before the hydrophobic dual-ligand metal-organic framework material is used as an adsorbent, heating and activating are needed; preferably, the temperature for heating and activating is 110-130 ℃;
or, the VOCs are benzene series compounds.
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| CN115555052A (en) * | 2022-11-23 | 2023-01-03 | 山东环投环境工程有限公司 | UiO-66@ titanium dioxide composite photocatalyst, and preparation method and application thereof |
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