CN117899838A - Multi-metal organic framework impregnated carbon material and preparation method and application thereof - Google Patents
Multi-metal organic framework impregnated carbon material and preparation method and application thereof Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 64
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 124
- 238000001179 sorption measurement Methods 0.000 claims abstract description 50
- 238000003756 stirring Methods 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000013094 zinc-based metal-organic framework Substances 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 150000003839 salts Chemical class 0.000 claims abstract description 23
- 239000003463 adsorbent Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000013110 organic ligand Substances 0.000 claims abstract description 7
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical group NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 42
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 40
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 40
- 238000001035 drying Methods 0.000 claims description 22
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 20
- 238000005303 weighing Methods 0.000 claims description 20
- 239000011592 zinc chloride Substances 0.000 claims description 20
- 235000005074 zinc chloride Nutrition 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- 229960001124 trientine Drugs 0.000 claims description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 abstract description 33
- 239000013084 copper-based metal-organic framework Substances 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 12
- 239000011148 porous material Substances 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
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- 231100000647 material safety data sheet Toxicity 0.000 description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 4
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- 238000002474 experimental method Methods 0.000 description 3
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to the technical field of gas adsorption materials, in particular to a multi-element metal organic framework impregnated carbon material, a preparation method and application thereof, wherein the preparation method of the impregnated carbon material comprises the steps of mixing metal salt I and metal salt II with an organic ligand for reaction to obtain mixed MOFs; taking a molar ratio of 2:1, adding the mixed MOFs and the organic adsorbent into water, and stirring and uniformly mixing to obtain an impregnating solution; the activated carbon is weighed and added into impregnating solution, stirred for 1-2 h at the rotating speed of 1000-1500 rpm, and dried at the temperature of 100-120 ℃ to obtain the impregnated carbon material, and the prepared impregnated carbon material has larger specific surface area and excellent gas adsorption performance and can be applied to SO 2 or NH 3 adsorption. According to the invention, the organic adsorbent, the Cu-MOFs and the Zn-MOFs are introduced into the mesoporous activated carbon framework, so that the metal salt is uniformly dispersed on the surface and in the pore canal of the activated carbon, a large number of micropores are formed, the porous activated carbon has rich oxygen-containing functional groups, more active sites are added, and the adsorption capacity of the composite adsorption material is greatly improved.
Description
Technical Field
The invention relates to the technical field of gas adsorption materials, in particular to a multi-metal organic framework impregnated carbon material and a preparation method and application thereof.
Background
Sulfur dioxide is a major air pollutant, mainly derived from the combustion of coal and gasoline, which can not only pose a hazard to human health, but also pose a serious threat to the manufacture, storage and operation of microelectronic devices. In addition, there is another pollutant ammonia in the air, which is commonly from various industries such as agriculture, chemical fertilizers, food and beverage, and rubber industry, and the toxic effect of this colorless irritant gas on the human body is related to its high water solubility, ammonia easily reacts with skin, eyes and respiratory system to form ammonium hydroxide, and in addition, ammonia causes particulate matter to pollute the air by forming salts and photochemical smog by oxidizing to nitric oxide.
At present, the existing gas purification mode generally adopts activated carbon, and the material has larger specific surface area, complex channel and pore network and adsorptivity, but has poor adsorption effect on low molecular weight and high polarity gases such as HCN, SO 2, NH 3 and the like without the unmodified activated carbon. In order to improve the adsorption capacity of the activated carbon, HNO 3 and an impregnated metal salt or metal complex are generally used for modification treatment, and HNO 3 is used as an oxidant, so that the number of acid groups (namely-COOH) and other oxygen-containing functional groups on the surface of the carbon can be increased, nano-scale metals or metal oxides can be uniformly distributed, and the adsorption performance can be improved. However, the activated carbon treated by HNO 3 can generate partial self-release gas, and release other polluted gases such as NO 2 and NO while treating SO 2 and NH 3, SO that the environment protection requirements of industries such as chips, panels and the like on gas adsorbents cannot be met, the adsorption performance of impregnated single metal salt is limited, the adsorption effect on multiple mixed gases is poor only for certain acid gases or alkaline gases, and multiple metals can possibly play a role in mutual inhibition. Therefore, developing a gas adsorbent that can adsorb multiple gases, has a high gas adsorption capacity, and does not produce self-outgas is a problem to be solved in some industries.
Disclosure of Invention
Therefore, the invention aims to provide a multi-element metal organic framework impregnated carbon material, a preparation method and application thereof, so as to at least solve the problems of low gas adsorption amount and self-gas release generated during adsorption and use of the existing gas adsorbent.
The invention solves the technical problems by the following technical means:
In a first aspect, the invention provides a method for preparing a multi-metal organic framework impregnated carbon material, comprising the following steps:
mixing metal salt I and metal salt II with an organic ligand to react to obtain mixed MOFs;
Adding the mixed MOFs and the organic adsorbent into water, and stirring and uniformly mixing to obtain an impregnating solution;
Weighing active carbon, adding the active carbon into the impregnating solution, stirring for 1-2 hours at the rotating speed of 1000-1500 rpm, and drying to obtain an impregnated carbon material;
The molar ratio of the mixed MOFs to the organic adsorbent is 2:1.
With reference to the first aspect, in some embodiments, the mixed MOFs comprise a molar ratio of (1 to 10): cu-MOFs and Zn-MOFs of (1-10).
With reference to the first aspect, in some embodiments, the first metal salt is any one of copper chloride, copper nitrate, and copper acetate, and the second metal salt is any one of zinc chloride, zinc nitrate, and zinc acetate.
With reference to the first aspect, in some embodiments, the organic ligand is trimesic acid or 2-methylimidazole.
With reference to the first aspect, in some embodiments, the organic adsorbent is triethylene tetramine or diethylene triamine.
In combination with the first aspect, in some embodiments, the activated carbon has a water capacity of 85%, a moisture content of 2%, an antiwear strength of 90%, and a protection time from benzene vapor of 50min.
With reference to the first aspect, in some embodiments, the temperature of the drying is 100 to 120 ℃.
In a second aspect, the invention provides a multi-metal organic framework impregnated carbon material prepared by the preparation method.
In a third aspect, the invention provides the use of the multi-metal organic framework impregnated carbon material described above for adsorbing SO 2 or NH 3.
The invention synthesizes the multi-element metal organic framework impregnated carbon material by a one-step method, and introduces the organic adsorbent, cu-MOFs and Zn-MOFs into the mesoporous activated carbon framework, so that metal salts are uniformly dispersed on the surface and in pore channels of the activated carbon, a large number of micropores are formed, the porous carbon has rich oxygen-containing functional groups, more active sites are added, and the adsorption capacity of the composite adsorption material is greatly improved.
In the invention, on one hand, the organic adsorbent and the mixed MOFs are used for impregnating the activated carbon, so that the MOFs are uniformly distributed on the surface and in the pore canal of the activated carbon by the organic adsorbent, a large number of micropores are formed, gas adsorption sites are increased, and the adsorption capacity of the activated carbon is improved; on the other hand, the multielement MOFs is impregnated, and Cu and Zn have the synergistic effect, so that the adsorption effect on the multielement mixed gas can be improved; on the other hand, the invention can replace HNO 3 strong acid to modify the active carbon, and does not generate other polluted gas.
Through experiments, under the conditions of 298.2K and 101.3kPa, the mass adsorption ratio of the activated carbon to NH 3 is about 0.53% mg.g -1, the mass adsorption ratio to SO 2 is about 0.66% mg.g -1, the mass adsorption ratio of Cu-MOFs/TETA/Zn-MOFs@AC to NH 3 is about 4.28% mg.g -1, and the mass adsorption ratio to SO 2 is about 3.38% mg.g -1; the mass adsorption ratio of Cu-MOFs/MSDS/Zn-MOFs@AC to NH 3 was about 3.35% mg.g -1 and the mass adsorption ratio to SO 2 was about 3.51% mg.g -1. According to the invention, by introducing two metal salt materials, modifying the surface of the material and adjusting the pore structure, the adsorption effect on toxic gases such as SO 2, NH 3 and the like is greatly improved.
Drawings
FIG. 1 is an XRD diffraction pattern of AC, cu-MOFs/TETA/Zn-MOFs@AC and Cu-MOFs/MSDS/Zn-MOFs@AC;
FIG. 2 is a graph of the initial adsorption SO 2 gas efficiencies of AC, cu-MOFs/TETA/Zn-MOFs@AC and Cu-MOFs/MSDS/Zn-MOFs@AC;
FIG. 3 is a graph of adsorption and desorption of N 2 for AC, cu-MOFs/TETA/Zn-MOFs@AC, and Cu-MOFs/MSDS/Zn-MOFs@AC.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The following examples were conducted under conventional conditions or conditions recommended by the manufacturer, without specifying the specific conditions. The raw materials, equipment or instruments used are conventional products commercially available without identifying the manufacturer.
In the present invention, TETA represents triethylenetetramine, MSDS represents diethylenetriamine, and AC represents activated carbon.
The existing active carbon treated by HNO 3 can generate partial self-release gas, and release other polluted gases such as NO 2, NO and the like while treating SO 2 and NH 3, SO that the environment-friendly requirement of industries such as chips, panels and the like on gas adsorbents cannot be met, the adsorption performance of impregnated single metal salt is limited, the adsorption effect on multiple mixed gases is poor only for certain acid gases or alkaline gases, and multiple metals can possibly play a role in mutual inhibition. Therefore, the invention provides a multi-metal organic framework impregnated carbon material, a preparation method and application thereof, and organic adsorbents, cu-MOFs and Zn-MOFs are introduced into a mesoporous activated carbon AC framework, so that the Cu-MOFs and the Zn-MOFs are uniformly dispersed on the surface and in pore channels of the activated carbon AC, a large number of micropores are formed, more active sites are increased, and the adsorption capacity of the composite adsorption material is greatly improved.
The preparation method of the multi-element metal organic framework impregnated carbon material comprises the following steps:
mixing metal salt I and metal salt II with an organic ligand to react to obtain mixed MOFs;
Taking a molar ratio of 2:1, adding the mixed MOFs and the organic adsorbent into water, and stirring and uniformly mixing to obtain an impregnating solution;
And (3) weighing active carbon, adding the active carbon into the impregnating solution, stirring for 1-2 hours at the rotating speed of 1000-1500 rpm, and drying at the temperature of 100-120 ℃ to obtain the impregnated carbon material.
Wherein, the mixed MOFs comprises the following components in mole ratio (1-10): the Cu-MOFs and the Zn-MOFs of (1-10), wherein the first metal salt is any one of copper chloride, copper nitrate and copper acetate, and the second metal salt is any one of zinc chloride, zinc nitrate and zinc acetate. The organic ligand is trimesic acid or 2-methylimidazole. The organic adsorbent is triethylene tetramine or diethylene triamine. The active carbon used in the invention has water content of 85%, water content of 2%, strength of 90%, and protection time for benzene steam of 50min, of course, the active carbon is not limited to coal pillar carbon, but can be coconut shell, apricot shell, walnut shell, wood pillar, bamboo charcoal, alumina-based ball and other materials with adsorptivity suitable for serving as catalyst carriers.
The invention is illustrated by the following examples:
example 1
The embodiment adopts a one-step method to synthesize the multi-element metal organic framework impregnated carbon material, and comprises the following specific steps:
1.344g of copper chloride, 4.2g of trimesic acid and 1.363g of zinc chloride are weighed out in sequence, added into 18mL of water and stirred until dissolved.
And (2) weighing 1.462g of TETA, adding the TETA into the solution in the step (1), and stirring until the TETA is dissolved to obtain an impregnating solution.
And (3) taking 5g of coconut shell activated carbon, adding the impregnating solution into the coconut shell activated carbon, vigorously stirring for 1h at a rotating speed of 1500rpm, and drying at 110 ℃ for 2h to obtain the impregnated carbon material.
Example 2
The preparation method of the multi-element metal organic framework impregnated carbon material in the embodiment is as follows:
1.344g of copper chloride, 4.2g of trimesic acid and 1.363g of zinc chloride are weighed out in sequence, added into 18mL of water and stirred until dissolved.
And (2) weighing 1.032g of MSDS, adding into the solution in the step (1), and stirring until the MSDS is dissolved to obtain an impregnating solution.
And (3) taking 5g of coconut shell activated carbon, adding the impregnating solution into the coconut shell activated carbon, vigorously stirring for 2 hours at a rotating speed of 1000rpm, and drying at 110 ℃ for 2 hours to obtain the impregnated carbon material.
Example 3
The preparation method of the multi-element metal organic framework impregnated carbon material in the embodiment is as follows:
2.688g of copper chloride, 6.3g of trimesic acid and 1.363g of zinc chloride are weighed in sequence, added into 18mL of water and stirred until dissolved.
And (2) weighing 1.462g of TETA, adding the TETA into the solution in the step (1), and stirring until the TETA is dissolved to obtain an impregnating solution.
And (3) taking 5g of coconut shell activated carbon, adding the impregnating solution into the coconut shell activated carbon, vigorously stirring for 1h at a rotating speed of 1500rpm, and drying at 120 ℃ for 1.5h to obtain the impregnated carbon material.
Example 4
The preparation method of the multi-element metal organic framework impregnated carbon material in the embodiment is as follows:
5.376g of copper chloride, 10.5g of trimesic acid and 1.363g of zinc chloride are weighed in sequence, added into 18mL of water and stirred until dissolved.
And (2) weighing 1.462g of TETA, adding the TETA into the solution in the step (1), and stirring until the TETA is dissolved to obtain an impregnating solution.
And (3) taking 5g of coconut shell activated carbon, adding the impregnating solution into the coconut shell activated carbon, vigorously stirring for 1.5h at a rotation speed of 1300rpm, and drying at 110 ℃ for 2h to obtain the impregnated carbon material.
Example 5
The preparation method of the multi-element metal organic framework impregnated carbon material in the embodiment is as follows:
8.064g of copper chloride, 14.7g of trimesic acid and 1.363g of zinc chloride are weighed in the step (1), sequentially added into 18mL of water, and stirred until dissolved.
And (2) weighing 1.462g of TETA, adding the TETA into the solution in the step (1), and stirring until the TETA is dissolved to obtain an impregnating solution.
And (3) taking 5g of coconut shell activated carbon, adding the impregnating solution into the coconut shell activated carbon, vigorously stirring for 1h at a rotating speed of 1500rpm, and drying at 100 ℃ for 3h to obtain the impregnated carbon material.
Example 6
The preparation method of the multi-element metal organic framework impregnated carbon material in the embodiment is as follows:
10.752g of copper chloride, 18.9g of trimesic acid and 1.363g of zinc chloride are weighed and sequentially added into 18mL of water, and stirred until dissolved.
And (2) weighing 1.462g of TETA, adding the TETA into the solution in the step (1), and stirring until the TETA is dissolved to obtain an impregnating solution.
And (3) taking 5g of coconut shell activated carbon, adding the impregnating solution into the coconut shell activated carbon, vigorously stirring for 1h at a rotating speed of 1500rpm, and drying at 110 ℃ for 2h to obtain the impregnated carbon material.
Example 7
The preparation method of the multi-element metal organic framework impregnated carbon material in the embodiment is as follows:
13.44g of copper chloride, 23.1g of trimesic acid and 1.363g of zinc chloride are weighed out in sequence, added into 18mL of water and stirred until dissolved.
And (2) weighing 1.462g of TETA, adding the TETA into the solution in the step (1), and stirring until the TETA is dissolved to obtain an impregnating solution.
And (3) taking 5g of coconut shell activated carbon, adding the impregnating solution into the coconut shell activated carbon, vigorously stirring for 1h at a rotating speed of 1500rpm, and drying at 110 ℃ for 2h to obtain the impregnated carbon material.
Example 8
The preparation method of the multi-element metal organic framework impregnated carbon material in the embodiment is as follows:
1.344g of copper chloride, 4.2g of trimesic acid and 1.363g of zinc chloride are weighed out in sequence, added into 18mL of water and stirred until dissolved.
And (2) weighing 2.924g of TETA, adding into the solution in the step (1), and stirring until the TETA is dissolved to obtain an impregnating solution.
And (3) taking 5g of coconut shell activated carbon, adding the impregnating solution into the coconut shell activated carbon, vigorously stirring for 1h at a rotating speed of 1500rpm, and drying at 110 ℃ for 2h to obtain the impregnated carbon material.
Example 9
The preparation method of the multi-element metal organic framework impregnated carbon material in the embodiment is as follows:
1.344g of copper chloride, 4.2g of trimesic acid and 1.363g of zinc chloride are weighed out in sequence, added into 18mL of water and stirred until dissolved.
And (2) weighing 5.848g of TETA, adding into the solution in the step (1), and stirring until the TETA is dissolved to obtain an impregnating solution.
And (3) taking 5g of coconut shell activated carbon, adding the impregnating solution into the coconut shell activated carbon, vigorously stirring for 1h at a rotating speed of 1500rpm, and drying at 110 ℃ for 2h to obtain the impregnated carbon material.
Example 10
The preparation method of the multi-element metal organic framework impregnated carbon material in the embodiment is as follows:
1.344g of copper chloride, 4.2g of trimesic acid and 1.363g of zinc chloride are weighed out in sequence, added into 18mL of water and stirred until dissolved.
And (2) weighing 8.722g of TETA, adding into the solution in the step (1), and stirring until the TETA is dissolved to obtain an impregnating solution.
And (3) taking 5g of coconut shell activated carbon, adding the impregnating solution into the coconut shell activated carbon, vigorously stirring for 1h at a rotating speed of 1500rpm, and drying at 110 ℃ for 2h to obtain the impregnated carbon material.
Example 11
The preparation method of the multi-element metal organic framework impregnated carbon material in the embodiment is as follows:
1.344g of copper chloride, 4.2g of trimesic acid and 1.363g of zinc chloride are weighed out in sequence, added into 18mL of water and stirred until dissolved.
And (2) weighing 11.696g of TETA, adding into the solution in the step (1), and stirring until the TETA is dissolved to obtain an impregnating solution.
And (3) taking 5g of coconut shell activated carbon, adding the impregnating solution into the coconut shell activated carbon, vigorously stirring for 1h at a rotating speed of 1500rpm, and drying at 110 ℃ for 2h to obtain the impregnated carbon material.
Example 12
The preparation method of the multi-element metal organic framework impregnated carbon material in the embodiment is as follows:
1.344g of copper chloride, 4.2g of trimesic acid and 1.363g of zinc chloride are weighed out in sequence, added into 18mL of water and stirred until dissolved.
And (2) weighing 14.62g of TETA, adding into the solution in the step (1), and stirring until the TETA is dissolved to obtain an impregnating solution.
And (3) taking 5g of coconut shell activated carbon, adding the impregnating solution into the coconut shell activated carbon, vigorously stirring for 1h at a rotating speed of 1500rpm, and drying at 110 ℃ for 2h to obtain the impregnated carbon material.
Example 13
The preparation method of the multi-element metal organic framework impregnated carbon material in the embodiment is as follows:
2.688g of copper chloride, 6.3g of trimesic acid and 1.363g of zinc chloride are weighed in sequence, added into 18mL of water and stirred until dissolved.
And (2) weighing 1.032g of MSDS, adding into the solution in the step (1), and stirring until the MSDS is dissolved to obtain an impregnating solution.
And (3) taking 5g of coconut shell activated carbon, adding the impregnating solution into the coconut shell activated carbon, vigorously stirring for 2 hours at a rotating speed of 1000rpm, and drying at 110 ℃ for 2 hours to obtain the impregnated carbon material.
Example 14
The preparation method of the multi-element metal organic framework impregnated carbon material in the embodiment is as follows:
5.376g of copper chloride, 10.5g of trimesic acid and 1.363g of zinc chloride are weighed in sequence, added into 18mL of water and stirred until dissolved.
And (2) weighing 1.032g of MSDS, adding into the solution in the step (1), and stirring until the MSDS is dissolved to obtain an impregnating solution.
And (3) taking 5g of coconut shell activated carbon, adding the impregnating solution into the coconut shell activated carbon, vigorously stirring for 2 hours at a rotating speed of 1000rpm, and drying at 110 ℃ for 2 hours to obtain the impregnated carbon material.
Example 15
The preparation method of the multi-element metal organic framework impregnated carbon material in the embodiment is as follows:
1.344g of copper chloride, 4.2g of trimesic acid and 1.363g of zinc chloride are weighed out in sequence, added into 18mL of water and stirred until dissolved.
And (2) weighing 2.064g of MSDS, adding the MSDS into the solution in the step (1), and stirring until the MSDS is dissolved to obtain an impregnating solution.
And (3) taking 5g of coconut shell activated carbon, adding the impregnating solution into the coconut shell activated carbon, vigorously stirring for 2 hours at a rotating speed of 1000rpm, and drying at 110 ℃ for 2 hours to obtain the impregnated carbon material.
Example 16
The preparation method of the multi-element metal organic framework impregnated carbon material in the embodiment is as follows:
1.344g of copper chloride, 4.2g of trimesic acid and 1.363g of zinc chloride are weighed out in sequence, added into 18mL of water and stirred until dissolved.
And (2) weighing 4.128g of MSDS, adding the MSDS into the solution in the step (1), and stirring until the MSDS is dissolved to obtain an impregnating solution.
And (3) taking 5g of coconut shell activated carbon, adding the impregnating solution into the coconut shell activated carbon, vigorously stirring for 2 hours at a rotating speed of 1000rpm, and drying at 110 ℃ for 2 hours to obtain the impregnated carbon material.
Example 17
The preparation method of the multi-element metal organic framework impregnated carbon material in the embodiment is as follows:
1.344g of copper chloride, 4.2g of trimesic acid and 1.363g of zinc chloride are weighed out in sequence, added into 18mL of water and stirred until dissolved.
And (2) weighing 1.032g of MSDS, adding into the solution in the step (1), and stirring until the MSDS is dissolved to obtain an impregnating solution.
And (3) taking 5g of coconut shell activated carbon, adding the impregnating solution into the coconut shell activated carbon, vigorously stirring for 2 hours at a rotating speed of 1000rpm, and drying at 110 ℃ for 2 hours to obtain the impregnated carbon material.
The specific surface area test and the gas adsorption test are respectively carried out by taking the activated carbon, the impregnated carbon materials prepared in the examples 1 and 2 as samples to be tested, and the specific surface area test and the gas adsorption test are specifically as follows:
(1) The sample to be tested is respectively tested and analyzed by an X-ray diffractometer, and the result is shown in figure 1.
As can be seen from the XRD results of FIG. 1, both Cu-MOFs/TETA/Zn-MOFs@AC and Cu-MOFs/MSDS/Zn-MOFs@AC can show a Cu-MOFs diffraction peak and a Zn-MOFs diffraction peak, which proves that both impregnated carbon materials successfully load Cu-MOFs and Zn-MOFs.
(2) N 2 adsorption-desorption experiments were performed using a physical adsorption apparatus at 77K, and the results are shown in FIG. 3, and the specific surface area was measured. The sample to be tested was heated at 100℃for 6h before the adsorption experiment.
The specific surface area of the obtained AC is 1164.7m 2/g, the specific surface area of the Cu-MOFs/TETA/Zn-MOFs@AC is 1136m 2/g, the specific surface area of the Cu-MOFs/MSDS/Zn-MOFs@AC is 1236.8m 2/g, and the effect of impregnating organic and metal salts with proper concentration on the specific surface area of the activated carbon material is less. .
(3) And (3) gas adsorption test, wherein an adsorption equilibrium isotherm of the coconut shell activated carbon and the Cu-MOFs/TETA/Zn-MOFs adsorbent on the toxic and harmful gas of SO 2、NH3 is measured by a static adsorption device, and the test conditions are 298.2K and 101.3kPa. Prior to adsorption measurements, the sample to be tested for the adsorbent must be evacuated at 423.2K until no mass loss is observed, and then a quantity of adsorbent (about 3 g) is carefully loaded into the adsorption cell to reduce the attrition of the adhesive and ensure accurate determination of free volume. The test results are shown in Table 1. FIG. 2 is a graph of the initial adsorption SO 2 gas efficiencies of AC, cu-MOFs/TETA/Zn-MOFs@AC and Cu-MOFs/MSDS/Zn-MOFs@AC.
TABLE 1
As can be seen from the data in Table 1, the mass adsorption ratio of AC to NH 3 is about 0.53% mg.g -1, the mass adsorption ratio to SO 2 is about 0.66% mg.g -1, the mass adsorption ratio of Cu-MOFs/TETA/Zn-MOFs@AC to NH 3 is about 4.28% mg.g -1, and the mass adsorption ratio to SO 2 is about 3.38% mg.g -1; the mass adsorption ratio of Cu-MOFs/MSDS/Zn-MOFs@AC to NH 3 was about 3.35% mg.g -1 and the mass adsorption ratio to SO 2 was about 3.51% mg.g -1. By introducing two metal salt materials, the surface of the material is modified, the pore structure is adjusted, and the adsorption effect on toxic gas is greatly improved.
Thus, the multi-metal organic framework impregnated carbon material of the invention can be used to adsorb SO 2 or NH 3.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention. The technology, shape, and construction parts of the present invention, which are not described in detail, are known in the art.
Claims (9)
1. The preparation method of the multi-element metal organic framework impregnated carbon material is characterized by comprising the following steps of:
mixing metal salt I and metal salt II with an organic ligand to react to obtain mixed MOFs;
Adding the mixed MOFs and the organic adsorbent into water, and stirring and uniformly mixing to obtain an impregnating solution;
Weighing active carbon, adding the active carbon into the impregnating solution, stirring for 1-2 hours at the rotating speed of 1000-1500 rpm, and drying to obtain an impregnated carbon material;
The molar ratio of the mixed MOFs to the organic adsorbent is 2:1.
2. The method for preparing a multi-metal organic framework impregnated carbon material according to claim 1, wherein the mixed MOFs comprise (1-10) in a molar ratio: cu-MOFs and Zn-MOFs of (1-10).
3. The method for preparing the multi-metal organic framework impregnated carbon material according to claim 2, wherein the first metal salt is any one of copper chloride, copper nitrate and copper acetate, and the second metal salt is any one of zinc chloride, zinc nitrate and zinc acetate.
4. The method for preparing a multi-metal organic framework impregnated carbon material according to claim 1, wherein the organic ligand is trimesic acid or 2-methylimidazole.
5. The method for preparing a multi-metal organic framework impregnated carbon material according to claim 1, wherein the organic adsorbent is triethylene tetramine or diethylenetriamine.
6. The method for preparing the multi-metal organic framework impregnated carbon material according to claim 1, wherein the activated carbon has a water content of 85%, a water content of 2%, an antiwear strength of 90% and a protection time against benzene vapor of 50min.
7. The method for preparing a multi-metal organic framework impregnated carbon material according to claim 1, wherein the temperature of drying is 100-120 ℃.
8. A multi-element metal organic framework impregnated carbon material, characterized in that the impregnated carbon material is prepared by the preparation method according to any one of claims 1-7.
9. Use of the multi-metal organic framework impregnated carbon material according to claim 8 for adsorption of SO 2 or NH 3.
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