CN115558120B - Metal organic framework material for trace BTEX adsorption and preparation method thereof - Google Patents

Metal organic framework material for trace BTEX adsorption and preparation method thereof Download PDF

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CN115558120B
CN115558120B CN202211190864.5A CN202211190864A CN115558120B CN 115558120 B CN115558120 B CN 115558120B CN 202211190864 A CN202211190864 A CN 202211190864A CN 115558120 B CN115558120 B CN 115558120B
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杨坤
胡来钢
邬文浩
杨曦
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Zhejiang University ZJU
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Abstract

The invention provides a metal organic framework material for trace BTEX adsorption and a preparation method thereof, and the metal organic framework material ZJU-620 (Al) related by the invention belongs to a hexagonal system and P31c space group. The metal organic framework material is mainly formed by rodlike aluminum metal clusters, 1,3, 5-trimethyl-2, 4, 6-tri (4-carboxyphenyl) benzene and formic acid through coordination and hydrogen bonding. Brunauer-Emmett-Teller specific surface area of ZJU-620 (Al) is 1347m 2 Per gram, micropore volume of 0.49cm 3 /g, pore size distribution inMainly focus onAnd can maintain structural stability in a solution having a pH of 3 to 12. Para-trace amounts of benzene based materials of this material, for example: benzene, toluene, ethylbenzene, ortho-xylene, meta-xylene, and para-xylene exhibit excellent enrichment ability.

Description

Metal organic framework material for trace BTEX adsorption and preparation method thereof
Technical Field
The invention relates to the research and development field of microporous metal-organic frame materials, in particular to a metal-organic frame material for trace BTEX adsorption and a preparation method thereof.
Background
The metal organic frameworks (Metal organic frameworks, MOFs) have the advantages of high specific surface area, adjustable pore size and the like, and show excellent adsorption performance on volatile organic pollutants (Volatile Organic Compounds, VOCs) in a high-pressure environment. However, MOFs materials require further improvement in the efficiency of separation of VOCs at low pressure. For example: xie et al report on P/P 0 Under the condition of=1 and 298K, the saturated adsorption quantity of ZIF-8 to benzene is 3.647mmol/g, and the adsorption quantity is P/P at low pressure 0 The adsorption amount of benzene at=0.01 is only 0.240mmol/g. (L.Xie, et al., metal-organic frameworks for the capture of trace aromatic volatile organic compounds, chem,2018,4,1911-1927.).Trace amounts of VOCs can cause carcinogenesis, teratogenicity, mutagenic hazards to humans, such as: benzene (benzone), toluene (tolene), ethylbenzene (ethylbenzone), ortho-xylene (ortho-xylene), meta-xylene (meta-xylene), para-xylene (para-xylene), i.e., BTEX.
The Polanyi theory states that the closer the pore size of the adsorbent is to the kinetic size of the adsorbent when the adsorbent is within the adsorption range of the adsorbent, the greater the adsorption affinity is produced, thus still having good adsorption to BTEX in trace amounts (k.yang, et al Adsorption of organic compounds by carbon nanomaterials in aqueous phase: polanyi theory and its application, chemical Reviews,2010,110,5989-6008.). Based on the Polanyi theory, the poor adsorption effect of most MOFs materials on trace BTEX is due to the fact that the pore sizes are not matched, and strong acting forces such as pi … pi interaction, hydrogen bonding and the like are difficult to form. The key to the authors' analysis to increase the trace adsorption of MOFs is to design a MOFs material with pore sizes close to the kinetic size of the BTEX molecules.
Disclosure of Invention
The invention provides a metal organic frame material for trace BTEX adsorption and a preparation method thereof, aiming at improving the technical problem that the existing metal organic frame material has low adsorption capacity and low efficiency on trace VOCs.
The invention adopts the following technical scheme: the invention firstly provides a preparation method of a metal organic framework material for trace BTEX adsorption, formic acid is selected as a regulator and a bridging agent, and 1,3, 5-trimethyl-2, 4, 6-tri (4-carboxyphenyl) benzene (H) 3 TMTA) as an organic ligand and aluminum nitrate nonahydrate as an aluminum source for the construction of metal organic framework materials. On one hand, formic acid can participate in the construction of aluminum clusters through coordination bonds, and on the other hand, the aldehyde hydrogen of formic acid can be connected with oxygen on other aluminum clusters through hydrogen bonding, so that the nodes of the metal clusters are increased. Furthermore, it is more emphasized that H 3 The methyl functional group on TMTA can shear the micropore size of MOFs, and the pore structure of MOFs is adjusted again.
The method specifically comprises the following steps: aluminum nitrate nonahydrate and 1,3, 5-trimethyl-2, 4, 6-tri (4-carboxyphenyl) benzene are dissolved in a solvent, formic acid is added, after ultrasonic treatment, heating is carried out to 120-130 ℃ for reaction for more than 72 hours, and then metal organic framework material ZJU-620 (Al) is obtained after post treatment.
Preferably, the reaction conditions are 130℃for 3 days.
Further, the molar ratio of the aluminum nitrate nonahydrate to the 1,3, 5-trimethyl-2, 4, 6-tris (4-carboxyphenyl) benzene is 1:1-2:1, and is optimally 1.5:1.
Further, the solvent is N, N-dimethylformamide.
Further, the total volume of the solvent and the formic acid to the total mass ratio of the aluminum nitrate nonahydrate and the 1,3, 5-trimethyl-2, 4, 6-tris (4-carboxyphenyl) benzene is 1:20-1:10 mL/mg.
Further, the volume ratio of the solvent to the formic acid is 3:1-4:1, and the optimal ratio is 3.25:1.
Further, the post-treatment is as follows: and after the reaction product is cooled to room temperature, centrifuging, washing insoluble matters obtained by centrifuging, and drying after washing to obtain the metal organic framework material ZJU-620 (Al).
Further, the washing is to sequentially use DMF and acetone for a plurality of rounds of washing.
The metal organic framework material ZJU-620 (Al) belongs to the space group of the hexagonal system P31 c. It is prepared from 1,3, 5-trimethyl-2, 4, 6-tris (4-carboxyphenyl) benzene (H 3 Anions after deprotonation of TMTA (TMTA) 3- ) Eight-coordinated Al bridged with formate 3+ The ions, the aldehyde hydrogen of formate and the oxygen of the other two rod-shaped aluminum clusters are bridged by hydrogen bonds, and the three-dimensional framework structure of the one-dimensional pore canal is formed.
The invention also provides application of the metal organic framework material ZJU-620 (Al) in VOCs adsorption storage, separation and sensing.
Compared with the prior art, the invention has the following beneficial effects:
(1) The ZJU-620 (Al) prepared by the invention has good thermal stability and chemical stability. The quality is not obviously lost at 320 ℃; in addition, ZJU-620 (Al) also has good chemical stability, and can keep stable structure after being soaked in acid-base solution with pH value of 3-12 for 24 hours.
(2) The ZJU-620 (Al) prepared by the invention has high specific surface area, rich micropore volume and proper pore size. The Brunauer-Emmett-Teller (BET) specific surface area was measured to be 1324m by low temperature nitrogen adsorption 2 Per gram, micropore volume of 0.49cm 3 And/g, all are micropores, and the pore diameters are distributed inMainly concentrate on->This size is close to the molecular kinetic size of BTEX and can produce a large adsorption potential.
(3) The ZJU-620 (Al) prepared by the invention has excellent adsorption effect on trace BTEX. At P/P 0 At a temperature of 298K, benzene adsorption was 3.80mmol/g, toluene adsorption was 3.30mmol/g, ethylbenzene adsorption was 2.72mmol/g, o-xylene adsorption was 2.51mmol/g, m-xylene adsorption was 2.59mmol/g, and p-xylene adsorption was 2.54mmol/g.
Drawings
FIG. 1 is a block diagram of a metal organic framework material ZJU-620 (Al) prepared in example 1 of the present invention;
FIG. 2 is a nitrogen adsorption and desorption isotherm plot at 77K for ZJU-620 (Al) prepared in example 1 of the present invention, including the product powder without any treatment, the powder after soaking in solutions of different pH;
FIG. 3 is an X-ray powder diffraction pattern of ZJU-620 (Al) prepared in example 1 of the present invention, including the powder of the product without any treatment, the powder after immersion in solutions of different pH and the X-ray powder diffraction pattern obtained by theoretical calculation;
FIG. 4 is a pore size distribution diagram of ZJU-620 (Al) prepared in example 1 of the present invention;
FIG. 5 is a thermogravimetric plot of ZJU-620 (Al) prepared in example 1 of the present invention;
FIG. 6 is a vapor absorption diagram of ZJU-620 (Al) prepared in example 1 of the present invention for benzene, toluene, ethylbenzene, ortho-xylene, meta-xylene, para-xylene at 298K;
FIG. 7 is a block diagram of BUT-18 (Al) prepared in comparative example 1 according to the present invention.
Detailed Description
The present invention will be described below with reference to examples, comparative examples and drawings, but the present invention is not limited to the examples.
Example 1 preparation of a homogeneous microporous Metal organic framework Material ZJU-620 (Al) Single Crystal
By reacting organic ligand H 3 TMTA (11 mg,0.023 mmol), aluminum nitrate nonahydrate (12.8 mg,0.034 mmol) and 1.3mL of N, N-Dimethylformamide (DMF) were added to a 50mL hydrothermal reaction vessel, 0.4mL of formic acid was added dropwise, and after sonication for 30 min. Heated to 130℃and reacted for 3 days. After the reaction vessel was cooled to room temperature, ZJU-620 (Al) was obtained by centrifugation, and washed sequentially 3 to 4 times with DMF and acetone. And (5) placing the washed product into a vacuum drying oven for drying. Finally, the specific surface area is 1347m 2 /g, pore size distribution inMainly concentrate on->
Example 2 preparation of a homogeneous microporous Metal organic framework Material ZJU-620 (Al) Single Crystal
By reacting organic ligand H 3 TMTA (16.3 mg,0.034 mmol), aluminum nitrate nonahydrate (12.8 mg,0.034 mmol) and 1.3mL of N, N-Dimethylformamide (DMF) were added to a 50mL hydrothermal reaction vessel, 0.4mL of formic acid was added dropwise, and after 30 minutes of sonication. Heated to 130℃and reacted for 3 days. After the reaction vessel was cooled to room temperature, ZJU-620 (Al) was obtained by centrifugation, and washed sequentially 3 to 4 times with DMF and acetone. And (5) placing the washed product into a vacuum drying oven for drying. Finally obtain the specific surface area of 1232m 2 /g, pore size distribution inMainly concentrate on->
Example 3 preparation of a homogeneous microporous Metal organic framework Material ZJU-620 (Al) Single Crystal
By reacting organic ligand H 3 TMTA (16.3 mg,0.034 mmol), aluminum nitrate nonahydrate (12.8 mg,0.034 mmol) and 1.3mL of N, N-Dimethylformamide (DMF) were added to a 50mL hydrothermal reaction vessel, 0.35mL of formic acid was added dropwise, and after 30 minutes of sonication. Heated to 130℃and reacted for 3 days. After the reaction vessel was cooled to room temperature, ZJU-620 (Al) was obtained by centrifugation, and washed sequentially 3 to 4 times with DMF and acetone. And (5) placing the washed product into a vacuum drying oven for drying. Finally obtain the specific surface area of 1141m 2 /g, pore size distribution inMainly concentrate on->
EXAMPLE 4 structural characterization of ZJU-620 (Al) without an object
The single crystal diffraction data of ZJU-620 (Al) are collected by using a Brucker D8 Venture single crystal X-ray diffractometer, and the collected data are analyzed and corrected by using a least square method to finally obtain the crystal structure of the ZJU-620 (Al), as shown in figure 1.
EXAMPLE 5 characterization of the chemical stability of the Metal organic framework Material ZJU-620 (Al) obtained in example 1
Chemical stability of the metal organic framework material ZJU-620 (Al) by immersing it in an aqueous solution with ph=3-12 for 24 hours, it can be seen that the structural stability can be maintained by comparing nitrogen adsorption and desorption isotherms before and after immersing with powder X-ray diffraction data, no collapse of the structure occurs, the nitrogen adsorption and desorption isotherms before and after immersing different pH solutions are shown in fig. 2, the powder after immersing different pH solutions and the X-ray powder diffraction obtained by theoretical calculation are shown in fig. 3, and the pore size distribution diagram of ZJU-620 (Al) is shown in fig. 4.
Example 6 characterization of the thermal stability of the Metal organic frame Material ZJU-620 (Al) obtained in example 1
The thermal stability of the metal organic framework material ZJU-620 (Al) was obtained by thermogravimetric analysis under nitrogen atmosphere, and the thermogravimetric curve is shown in FIG. 5.
Example 7 characterization of the organometallic framework materials ZJU-620 (Al) p-benzene, toluene, ethylbenzene, ortho-xylene, meta-xylene, para-xylene vapor adsorption obtained in example 1
The metal organic framework material ZJU-620 (Al) is prepared by performing steam adsorption on benzene, toluene, ethylbenzene, o-xylene and m-xylene at 298K through a BELSORP MAX2 steam adsorber, before performing steam adsorption, ZJU-620 (Al) is subjected to vacuum heating and activation in advance to remove impurities in pore channels, the steam adsorption isotherm is shown in figure 6, the adsorption effect of ZJU-620 (Al) on trace BTEX is better, and the adsorption quantity is still high under a low-pressure environment, wherein the emphasis is that the ZJU-620 (Al) is in P/P 0 The adsorption capacity of benzene can reach 3.80mmol/g at the pressure of 0.01.
Comparative example 1
Preparation of a Metal organic framework Material BUT-18 (Al), organic ligand H 3 TMTA (50 mg,0.1 mmol), aluminum nitrate nonahydrate (60 mg,0.16 mmol) and 15mL of N, N-Dimethylformamide (DMF) were added to a 50mL hydrothermal reaction vessel, followed by 2.5mL of acetic acid, sonicated for 30 minutes, and reacted at 200℃for 48 hours to give the product BUT-18 (Al), which was washed with DMF and acetone, and the washed product was activated in a vacuum oven at 80℃and the crystal structure was shown in FIG. 7.
Comparative example 2
By reacting organic ligand H 3 TMTA (11 mg,0.023 mmol), aluminum nitrate nonahydrate (12.8 mg,0.034 mmol) and 1.3mL of N, N-Dimethylformamide (DMF) were added to a 50mL hydrothermal reaction vessel, 1.4mL of formic acid was added dropwise, and the mixture was sonicated for 30 min. Heated to 130℃and reacted for 3 days. After the reaction kettle is cooled to room temperature, the reaction kettle is clear, and the ZJU-620 (Al) product is not obtained.
Comparative example 3
By reacting organic ligand H 3 TMTA (11 mg,0.023 mmol), aluminum nitrate nonahydrate (12.8 mg,0.034 mmol) and 1.3mL of N, N-Dimethylformamide (DMF) were added to a 50mL hydrothermal reaction vessel, 0.1mL of formic acid was added dropwise, and the mixture was sonicated for 30 min. Heated to 130℃and reacted for 3 days. After the reaction kettle is cooled to room temperature, a white turbid product is obtained through centrifugation, DMF is sequentially used, and acetone is sequentially washed for 3 to 4 times. And (5) placing the washed product into a vacuum drying oven for drying. The specific surface area is 682m 2 /g。
FIG. 1 is a crystal structure diagram of ZJU-620 (Al) of example 1, and FIG. 7 is a crystal structure diagram of BUT-18 (Al) of comparative example 1, although both are organic ligands H 3 TMTA and aluminum nitrate nonahydrate are synthesized as reaction reagents, but different acidic reagents are added in the synthesis process of the TMTA and aluminum nitrate nonahydrate, and the reaction temperature and the reaction time are different. From the schematic of the crystal structure of ZJU-620 (Al), formic acid participates in the structure of the ZJU-620 (Al) crystal, and two distinct aluminum clusters exist in ZJU-620 (Al) and BUT-18 (Al), which causes the ZJU-620 (Al) to form a completely new network structure. Analysis of the pore size distribution shows that the pore size distribution of ZJU-620 (Al) isMainly concentrate on->See fig. 4. In addition, ZJU-620 (Al) is immersed in the aqueous solution with pH value of 3-12, and the nitrogen adsorption and desorption isotherms before and after immersion and the powder X-ray diffraction patterns are not obviously changed, so that the ZJU-620 (Al) can still maintain the structural stability after being immersed in the solution with different pH values, namely, has good chemical stability, as shown in figures 2 and 3. In terms of thermal stability, the thermogravimetric curve measured under nitrogen atmosphere using thermogravimetric analysis shows that ZJU-620 (Al) only undergoes a significant mass loss at 320℃and has good thermal stability, as shown in FIG. 5. Vapor adsorption isotherms for ZJU-620 (Al) for benzene, toluene, ethylbenzene, ortho-xylene, meta-xylene, and para-xylene (BTEX), as seen in FIG. 6, are shown for ZJU-620 (Al) inExhibits a higher adsorption capacity for BTEX at low pressure, which can be attributed to the pore size distribution of ZJU-620 (Al) in +.>Mainly concentrate on->This is in accordance with the molecular kinetic dimensions of benzene, toluene, ethylbenzene, ortho-xylene, meta-xylene, para-xylene (/ -)> And +.>) Proximity. According to the Polanyi theory, when the adsorbate molecules are in the adsorption space range of the adsorbent, the closer the adsorbate molecules are to the surface of the adsorbent, the larger adsorption potential energy can be generated, and the higher adsorption capacity is achieved. Therefore, the metal organic framework material ZJU-620 (Al) not only has good chemical and thermal stability, but also has excellent adsorption capacity for trace BTEX.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of the invention should be assessed as that of the appended claims.

Claims (7)

1. A method for preparing a metal organic framework material for trace BTEX adsorption, which is characterized by comprising the following steps:
aluminum nitrate nonahydrate and 1,3, 5-trimethyl-2, 4, 6-tris (4-carboxyphenyl) benzene are dissolved in a solvent, followed by the addition of formic acid,after ultrasonic treatment, heating to 120-130 ℃ to react for more than 72 hours, and performing post-treatment to obtain a metal organic framework material ZJU-620 (Al) for trace BTEX adsorption; the molar ratio of the aluminum nitrate nonahydrate to the 1,3, 5-trimethyl-2, 4, 6-tri (4-carboxyphenyl) benzene is 1:1-2:1; the total volume ratio of the solvent and the formic acid to the total mass ratio of the aluminum nitrate nonahydrate and the 1,3, 5-trimethyl-2, 4, 6-tri (4-carboxyphenyl) benzene is 1:20-1:10 mL/mg; the volume ratio of the solvent to the formic acid is 3:1-4:1; the pore diameter of the metal organic framework material ZJU-620 (Al) for trace BTEX adsorption is distributed in
2. The method of claim 1, wherein the solvent is N, N-dimethylformamide.
3. The method according to claim 1, wherein the post-treatment is: and after the reaction product is cooled to room temperature, centrifuging, washing insoluble matters obtained by centrifuging, and drying after washing to obtain the metal organic framework material ZJU-620 (Al).
4. A process according to claim 3, wherein the washing is performed in several rounds using DMF and acetone in sequence.
5. A metal organic framework material for trace BTEX adsorption prepared by the method of any one of claims 1-4.
6. The metal-organic framework material of claim 5 wherein the metal-organic framework material is a porous material, the porous material is hexagonal and the P31c space group is formed by 1,3, 5-trimethyl-2, 4, 6-tris (4-carboxyphenyl) benzene (H 3 Anions after deprotonation of TMTA (TMTA) 3- ) Eight-coordinated Al bridged with formate 3+ Ions, and the aldehyde hydrogens of the formate and two other rodsThe oxygen of the aluminum cluster is bridged by hydrogen bonds and has a three-dimensional framework structure with one-dimensional pore channels.
7. Use of the metal organic framework material ZJU-620 (Al) according to claim 5 for trace BTEX adsorption.
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