CN111450884A - Hydroxyl-containing covalent triazine framework material and preparation method and application thereof - Google Patents
Hydroxyl-containing covalent triazine framework material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 52
- 239000013311 covalent triazine framework Substances 0.000 title claims abstract description 41
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 7
- CVNOWLNNPYYEOH-UHFFFAOYSA-N 4-cyanophenol Chemical compound OC1=CC=C(C#N)C=C1 CVNOWLNNPYYEOH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000227 grinding Methods 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 230000015556 catabolic process Effects 0.000 claims abstract description 13
- 238000006731 degradation reaction Methods 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 13
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims abstract description 13
- BHXFKXOIODIUJO-UHFFFAOYSA-N benzene-1,4-dicarbonitrile Chemical compound N#CC1=CC=C(C#N)C=C1 BHXFKXOIODIUJO-UHFFFAOYSA-N 0.000 claims abstract description 10
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 230000009467 reduction Effects 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 7
- 230000002153 concerted effect Effects 0.000 claims description 4
- 229910001385 heavy metal Inorganic materials 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 9
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000593 degrading effect Effects 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 238000011160 research Methods 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- 239000010453 quartz Substances 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 125000006575 electron-withdrawing group Chemical group 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 238000005485 electric heating Methods 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000011345 viscous material Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 231100000049 endocrine disruptor Toxicity 0.000 description 3
- 239000000598 endocrine disruptor Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000001350 scanning transmission electron microscopy Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
A hydroxyl-containing covalent triazine framework material is prepared by the following method: taking terephthalonitrile and p-hydroxybenzonitrile as precursors, grinding and uniformly mixing the precursors at the temperature of minus 10-5 ℃ and N2Under the protection condition, dropwise adding trifluoromethanesulfonic acid, stirring for 1.5-2.5 h, then heating to 85-110 ℃, keeping for 25-35 min to obtain a solid substance, grinding, washing and drying to obtain the hydroxyl-containing covalent triazine frame material; the preparation method of the material of the invention is mildSimple, green and environment-friendly, and low in cost; meanwhile, the catalyst contains hydroxyl and cyano as active sites for electron donating and withdrawing groups and improves the catalytic degradation capability; researches show that the covalent triazine framework material has high capability of catalyzing and degrading bisphenol A and reducing hexavalent chromium in a high-synergistic mode, and meanwhile, the catalyst can keep good chemical and mechanical stability in repeated use for many times, and has great application potential in the fields of pollutant degradation and reduction, environmental protection and the like.
Description
Technical Field
The invention belongs to the technical field of material preparation and environment, and relates to a hydroxyl-containing covalent triazine framework material, and a preparation method and application thereof.
Background
Due to the use of a large number of environmental Endocrine Disruptors (EDCs), the safety of water environment and ecosystem is seriously threatened day by day, and the method is widely concerned by people. For example, bisphenol a is a representative one of EDCs, is an important organic chemical raw material of many acid esters and resins, and is a hydrophobic and nonvolatile organic pollutant. In addition, hexavalent chromium (cr (vi)) has high toxicity, high carcinogenicity, and is easy to migrate in the environment, and reduction of cr (vi) to cr (iii) with low toxicity is a key step in heavy metal chromium pollution abatement.
The covalent triazine framework material has the physicochemical properties of stable structure, large specific surface area, heat resistance and good hydrophobic property. But due to the high symmetry of the structure, the speed of electron transmission and transfer is slowed down. Therefore, it is a research direction to find a strong adsorption degradation property with a high active site, and to introduce an electron-donating and electron-withdrawing group to promote electron separation and transmission rate.
Disclosure of Invention
The invention aims to provide a covalent triazine framework material containing hydroxyl and having electron donating and withdrawing groups as well as a preparation method and application thereof.
The technical scheme of the invention is as follows:
a hydroxyl-containing covalent triazine framework material is prepared by the following method:
taking terephthalonitrile and p-hydroxybenzonitrile as precursors, grinding and uniformly mixing the precursors, and carrying out N reaction at-10-5 ℃ (preferably 0 ℃)2Under the protection condition, dropwise adding trifluoromethanesulfonic acid, stirring for 1.5-2.5 h (preferably 2h), and then heating to 85-1Keeping the temperature at 10 ℃ (preferably 100 ℃) for 25-35 min (preferably 30min) to obtain a solid substance, grinding the solid substance, washing and drying to obtain the hydroxyl-containing covalent triazine framework material;
the content of the substances of the p-hydroxy benzonitrile in the precursor is 1-20%, preferably 5-15%, and particularly preferably 10%;
after dropwise adding trifluoromethanesulfonic acid, the concentration of the total amount of the terephthalonitrile and the p-hydroxybenzonitrile in the trifluoromethanesulfonic acid is 1.2-2.5 mol/L, preferably 1.5 mol/L;
and grinding the solid substance, washing the solid substance with ammonia water, ethanol and water in sequence to remove impurities, and drying the solid substance in a vacuum drying oven at 50-70 ℃ (preferably 60 ℃) for 24 hours to obtain the hydroxyl-containing covalent triazine framework material.
The covalent triazine framework material containing hydroxyl and electron-donating and electron-withdrawing groups prepared by the invention has rich active sites and high electron separation and transmission capability. The material has light to dark colors according to different hydroxyl contents, and the appearance of the material is mostly a layered stacked material.
The hydroxyl-containing covalent triazine framework material can be applied to the concerted catalytic degradation of phenols and heavy metals in wastewater, such as concerted degradation of bisphenol A and reduction of hexavalent chromium.
The invention has the beneficial effects that:
provides a covalent triazine framework material containing hydroxyl and electron-donating and electron-withdrawing groups simultaneously, so as to enrich active sites for degrading and reducing pollutants and improve the catalytic effect. The catalyst has the following advantages in implementation: the preparation method of the catalyst is mild and simple, green and environment-friendly, and low in cost; meanwhile, the catalyst contains hydroxyl and cyano as active sites for electron donating and withdrawing groups and improves the catalytic degradation capability. The research finds that the covalent triazine framework material has high capability of catalyzing and degrading bisphenol A and reducing hexavalent chromium synergistically. Meanwhile, the catalyst can keep good chemical and mechanical stability in repeated use for many times, and has great application potential in the fields of pollutant degradation and reduction, environmental protection and the like.
Drawings
FIG. 1 is a scanning electron microscope image of the covalent triazine framework obtained in example 1;
FIG. 2 is a scanning electron microscope image of the covalent triazine framework obtained in example 3;
FIG. 3 is a transmission electron microscope image of the covalent triazine framework obtained in example 1;
FIG. 4 is a transmission electron microscope image of the covalent triazine framework obtained in example 3.
Detailed Description
The invention is further illustrated by the following examples, without restricting its scope to these.
Example 1
In this example, a covalent triazine framework material without hydroxyl and cyano groups as electron donating and withdrawing groups was prepared, and as a control example, the specific steps were as follows:
(1) 500mg of terephthalonitrile was charged into a quartz tube containing a rotor.
(2) In N2Under the protection of inert gas, 2.5ml of trifluoromethanesulfonic acid is slowly dropped into a quartz tube in a water bath environment at 0 ℃, and stirring is continued for 2h to obtain a yellow viscous substance.
(3) Transferring the quartz tube into a 100 ℃ electric heating constant temperature blast drying oven, and keeping for 30min to obtain a yellow transparent solid substance.
(4) The resulting material was transferred to grinding and after sufficient grinding, washed with ammonia, ethanol and water in sequence three times each to remove impurities.
(5) And then baking the obtained product in an oven at 60 ℃ for 24 hours to obtain white powder, namely the covalent triazine framework material.
Example 2
In this example, the specific steps for preparing a covalent triazine framework material containing both hydroxyl and cyano as electron donating and withdrawing groups are as follows:
(1) 476.2mg of terephthalonitrile and 23.8mg of p-hydroxybenzonitrile were sequentially added to an agate mortar, sufficiently ground, uniformly mixed and charged into a quartz tube containing a rotor.
(2) In N2Under the protection of inert gas, slowly dripping 2.5ml of trifluoromethyl into a quartz tube in a water bath environment at 0 DEG CSulfonic acid, stirring for 2h to give a red viscous mass.
(3) Transferring the quartz tube into a 100 ℃ electric heating constant temperature blast drying oven, and keeping for 30min to obtain a red transparent solid substance.
(4) The resulting material was transferred to grinding and after sufficient grinding, washed with ammonia, ethanol and water in sequence three times each to remove impurities.
(5) And then baking the mixture in an oven at 60 ℃ for 24 hours to obtain light yellow powder, namely the covalent triazine framework material containing hydroxyl and cyano as electron donating and withdrawing groups.
Example 3
In this example, the specific steps for preparing a covalent triazine framework material containing both hydroxyl and cyano as electron donating and withdrawing groups are as follows:
(1) 452.4mg of terephthalonitrile and 47.6mg of p-hydroxybenzonitrile were sequentially added to an agate mortar, sufficiently ground, uniformly mixed and charged into a quartz tube containing a rotor.
(2) In N2Under the protection of inert gas, 2.5ml of trifluoromethanesulfonic acid is slowly dropped into a quartz tube in a water bath environment at 0 ℃, and stirring is continued for 2 hours to obtain a reddish brown viscous substance.
(3) Transferring the quartz tube into a 100 ℃ electric heating constant temperature blast drying oven, and keeping for 30min to obtain a reddish brown transparent solid substance.
(4) The resulting material was transferred to grinding and after sufficient grinding, washed with ammonia, ethanol and water in sequence three times each to remove impurities.
(5) And then baking the mixture in an oven at 60 ℃ for 24 hours to obtain yellow powder, namely the covalent triazine framework material containing hydroxyl and cyano as electron donating and withdrawing groups.
Example 4
In this example, the specific steps for preparing a covalent triazine framework material containing both hydroxyl and cyano as electron donating and withdrawing groups are as follows:
(1) 428.6mg of terephthalonitrile and 71.4mg of p-hydroxybenzonitrile were sequentially added to an agate mortar, sufficiently ground, uniformly mixed and then charged into a quartz tube containing a rotor.
(2) In N2Under the protection of the inert gas, the reaction kettle is,in a water bath environment at 0 ℃, 2.5ml of trifluoromethanesulfonic acid is slowly dropped into a quartz tube, and stirring is continued for 2h, so that a reddish brown viscous substance is obtained.
(3) Transferring the quartz tube into a 100 ℃ electric heating constant temperature blast drying oven, and keeping for 30min to obtain a reddish brown transparent solid substance.
(4) The resulting material was transferred to grinding and after sufficient grinding, washed with ammonia, ethanol and water in sequence three times each to remove impurities.
(5) And then baking the mixture in an oven at 60 ℃ for 24 hours to obtain orange powder, namely the covalent triazine framework material containing hydroxyl and cyano as electron donating and withdrawing groups.
Example 5
In this example, the specific steps for preparing a covalent triazine framework material containing both hydroxyl and cyano as electron donating and withdrawing groups are as follows:
(1) 404.8mg of terephthalonitrile and 95.2mg of p-hydroxybenzonitrile were sequentially added to an agate mortar, sufficiently ground, uniformly mixed and then charged into a quartz tube containing a rotor.
(2) In N2Under the protection of inert gas, 2.5ml of trifluoromethanesulfonic acid is slowly dropped into a quartz tube in a water bath environment at 0 ℃, and stirring is continued for 2 hours to obtain a reddish brown viscous substance.
(3) Transferring the quartz tube into a 100 ℃ electric heating constant temperature blast drying oven, and keeping for 30min to obtain a reddish brown transparent solid substance.
(4) The resulting material was transferred to grinding and after sufficient grinding, washed with ammonia, ethanol and water in sequence three times each to remove impurities.
(5) And then baking the mixture in an oven at 60 ℃ for 24 hours to obtain orange powder, namely the covalent triazine framework material containing hydroxyl and cyano as electron donating and withdrawing groups.
The covalent triazine framework materials obtained in examples 1 and 3 were topographically characterized by scanning electron microscopy and transmission electron microscopy, the results of which are shown in fig. 1, fig. 2, fig. 3 and fig. 4. It is shown that the surface of the material of example 3 had significant wrinkles and protrusions, as compared to example 1, due to the presence of hydroxyl and cyano groups around the polymer as a result of the introduction of p-hydroxybenzonitrile. Scanning the examples 1 and 3 by a transmission electron microscope shows that the material has a layered structure, and after the p-hydroxybenzonitrile is introduced, the edge of the material has dentate defects, which is beneficial to exposing electron-donating and electron-withdrawing groups.
The covalent triazine framework material obtained in the examples 1-5 is utilized to carry out a test of synergistically degrading bisphenol A and reducing the removal rate of hexavalent chromium under simulated sunlight, the degradation experiment is carried out in a 100ml beaker, the reaction temperature is controlled at 25 ℃, 0.2 g/L of catalyst is dispersed in 100m L Cr (VI)/BPA mixed solution, wherein the concentrations of Cr (VI) and BPA are 10 mg/L and 0.05 mmol/L respectively, the initial pH value of the solution is 6.7, 2ml is sampled every 15min, and the total reaction time is 180 min.
The test results are shown in table 1, with the introduction of different contents of p-hydroxybenzonitrile, the removal capacity of the catalyst for synergistically degrading bisphenol a and reducing hexavalent chromium and the removal capacity for separately degrading bisphenol a and reducing hexavalent chromium are both increased and then decreased, and when the amount of the substance of p-hydroxybenzonitrile accounts for 10% of the total precursor, the highest capacity is exhibited, 100% of bisphenol a can be degraded and 90.26% of hexavalent chromium can be simultaneously reduced.
Therefore, the introduction of the p-hydroxybenzonitrile successfully forms two electron donating groups and two electron withdrawing groups of hydroxyl and cyano, and enriches active sites so as to promote the electron separation and transmission speed and improve the degradation and reduction capability. However, excessive addition of p-hydroxybenzonitrile causes a decrease in the degree of polymerization of the polymer, decreasing the number of triazine rings having a strong light response, resulting in a decrease in the photoresponse of the catalyst, degradation and reduction ability. The covalent triazine framework material has strong degradation and reduction capability, and the catalytic effect of the covalent triazine framework material can be controlled by adjusting the amount of raw material p-hydroxybenzonitrile.
TABLE 1 Co-valent triazine framework materials formed with varying amounts of p-hydroxybenzonitrile synergistically degrade bisphenol A and reduce hexavalent chromium removal in simulated sunlight
The above-described embodiment is merely a preferred embodiment of the present invention, and is not intended to limit the present invention. For example, in the embodiment, the precursor is selected from p-hydroxybenzonitrile as the raw material for introducing hydroxyl and cyano, which does not mean that only p-hydroxybenzonitrile can play a role of enriching active sites, and as long as the precursor with electron donating and electron withdrawing groups is selected, the precursor and the electron donating and electron withdrawing groups can perform polymerization reaction to generate triazine ring with strong light response performance, so that the effect of the invention can be realized. In addition, the quantity proportion of the precursor can be properly adjusted, and the effect of the invention can be realized when the proportion of the triazine ring and the electron-donating and electron-withdrawing groups is optimal. Further, trifluoromethanesulfonic acid is used as a polymerization catalyst, but it is not intended that trifluoromethanesulfonic acid alone be selected, and the effects of the present invention can be achieved as long as it functions to polymerize to form a triazine ring.
Claims (7)
1. A hydroxyl-containing covalent triazine framework material, characterized in that it is prepared as follows:
taking terephthalonitrile and p-hydroxybenzonitrile as precursors, grinding and uniformly mixing the precursors at the temperature of minus 10-5 ℃ and N2Under the protection condition, dropwise adding trifluoromethanesulfonic acid, stirring for 1.5-2.5 h, then heating to 85-110 ℃, keeping for 25-35 min to obtain a solid substance, grinding, washing and drying to obtain the hydroxyl-containing covalent triazine framework material.
2. The hydroxyl-containing covalent triazine framework material of claim 1, wherein the para-hydroxybenzonitrile is present in the precursor in an amount of 1 to 20%.
3. The hydroxyl-containing covalent triazine framework material of claim 2, wherein the para-hydroxybenzonitrile is present in the precursor in an amount of 5 to 15%.
4. The hydroxyl-containing covalent triazine framework material of claim 1, wherein the total amount of terephthalonitrile and p-hydroxyphenylnitrile is 1.2 to 2.5 mol/L in the trifluoromethanesulfonic acid after the trifluoromethanesulfonic acid is added dropwise.
5. The hydroxyl-containing covalent triazine framework material of claim 1, wherein the solid matter is ground, washed with ammonia water, ethanol and water in sequence to remove impurities, and then dried in a vacuum drying oven at 50-70 ℃ for 24h to obtain the hydroxyl-containing covalent triazine framework material.
6. Use of the hydroxyl-containing covalent triazine framework material of claim 1 for the concerted catalytic degradation of phenols and heavy metals in waste water.
7. Use of the hydroxy-containing covalent triazine framework material of claim 6 for the concerted catalytic degradation of bisphenol a and reduction of hexavalent chromium in wastewater.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113441179A (en) * | 2021-06-25 | 2021-09-28 | 浙江工业大学 | Thiophene-modified covalent triazine framework material and preparation and application thereof |
| CN114196013A (en) * | 2021-11-26 | 2022-03-18 | 浙江工业大学 | Thienyl carbon-nitrogen conjugated polymer and preparation method and application thereof |
| CN114790286A (en) * | 2022-03-30 | 2022-07-26 | 绍兴文理学院 | Preparation method of covalent triazine framework polymer microspheres |
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| CN114196013A (en) * | 2021-11-26 | 2022-03-18 | 浙江工业大学 | Thienyl carbon-nitrogen conjugated polymer and preparation method and application thereof |
| CN114196013B (en) * | 2021-11-26 | 2023-12-05 | 浙江工业大学 | Thienyl carbon-nitrogen conjugated polymer and preparation method and application thereof |
| CN114790286A (en) * | 2022-03-30 | 2022-07-26 | 绍兴文理学院 | Preparation method of covalent triazine framework polymer microspheres |
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