CN115646522B - Preparation method of potassium ion doped carbon nitride silicon dioxide heterojunction, product and application thereof - Google Patents
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 77
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 36
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 33
- 229910001414 potassium ion Inorganic materials 0.000 title claims abstract description 24
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 30
- 230000001699 photocatalysis Effects 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 19
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000003647 oxidation Effects 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 28
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 15
- 239000001103 potassium chloride Substances 0.000 claims description 14
- 235000011164 potassium chloride Nutrition 0.000 claims description 14
- 239000011941 photocatalyst Substances 0.000 claims description 13
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- ZINRVIQBCHAZMM-UHFFFAOYSA-N 1-Amino-2,4-dibromoanthraquinone Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(Br)=CC(Br)=C2N ZINRVIQBCHAZMM-UHFFFAOYSA-N 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical group [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000005411 L01XE02 - Gefitinib Substances 0.000 claims description 3
- QXKHYNVANLEOEG-UHFFFAOYSA-N Methoxsalen Chemical compound C1=CC(=O)OC2=C1C=C1C=COC1=C2OC QXKHYNVANLEOEG-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- XGALLCVXEZPNRQ-UHFFFAOYSA-N gefitinib Chemical compound C=12C=C(OCCCN3CCOCC3)C(OC)=CC2=NC=NC=1NC1=CC=C(F)C(Cl)=C1 XGALLCVXEZPNRQ-UHFFFAOYSA-N 0.000 claims description 3
- 229960002584 gefitinib Drugs 0.000 claims description 3
- 229960004469 methoxsalen Drugs 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- BUNGCZLFHHXKBX-UHFFFAOYSA-N 8-methoxypsoralen Natural products C1=CC(=O)OC2=C1C=C1CCOC1=C2OC BUNGCZLFHHXKBX-UHFFFAOYSA-N 0.000 claims description 2
- ZIPLUEXSCPLCEI-UHFFFAOYSA-N cyanamide group Chemical group C(#N)[NH-] ZIPLUEXSCPLCEI-UHFFFAOYSA-N 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- SQBBOVROCFXYBN-UHFFFAOYSA-N methoxypsoralen Natural products C1=C2OC(=O)C(OC)=CC2=CC2=C1OC=C2 SQBBOVROCFXYBN-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract description 21
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 239000000758 substrate Substances 0.000 abstract description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 229910052700 potassium Inorganic materials 0.000 abstract description 2
- 239000011591 potassium Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 5
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 halogen salt Chemical class 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical group COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- PCWZKQSKUXXDDJ-UHFFFAOYSA-N Xanthotoxin Natural products COCc1c2OC(=O)C=Cc2cc3ccoc13 PCWZKQSKUXXDDJ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000007805 chemical reaction reactant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses a preparation method of a potassium ion doped carbon nitride silicon dioxide heterojunction, a product thereof and application thereof in a reaction for preparing halogenated aromatic compounds by photocatalytic oxidation, wherein the preparation method comprises the following steps: and uniformly mixing the carbon nitride precursor, the potassium source and the silica sol, adding ethanol to enable the mixture to be gel, and calcining the gel at a high temperature in air to obtain the potassium ion doped carbon nitride silicon dioxide heterojunction. When the product prepared by the invention is used for preparing halogenated aromatic compounds by photocatalytic oxidation, the product has good conversion rate and selectivity on aromatic compound substrates, and has excellent catalytic activity on various aromatic compounds, the application range is wide, and the catalytic performance is still stable after repeated cyclic use.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a preparation method of a potassium ion doped carbon nitride silicon dioxide heterojunction, a product thereof and application thereof in a reaction for preparing halogenated aromatic compounds by photocatalytic oxidation.
Background
Halogenated aromatic compounds are important chemical reagents and raw materials, can be used as reaction starting materials and intermediates in organic synthesis, are industrially prepared by Friedel-Crafts reactions, and are often toxic and harmful in liquid bromine and organic solvents used in the reactions. Therefore, the oxidative halogenation of the aromatic compound by taking inorganic halogen salt as a raw material through the photocatalytic reaction is an environment-friendly method. In the preparation method, oxygen is reduced into superoxide radical firstly, then the superoxide radical oxidizes halogen anions into liquid bromine molecules, and the liquid bromine molecules are differentiated into hypobromous acid under the acidic condition, so that the aromatic compound is subjected to dehydrohalogenation reaction.
However, the existing photocatalysis systems for preparing halogenated aromatic compounds by photocatalytic oxidation are few, and most of reported photocatalysts are complicated to prepare and low in reaction activity, so that the photocatalysts with simple synthesis, wide sources of preparation raw materials, stable chemical properties, high activity and good selectivity are still the problems to be solved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a preparation method of a potassium ion doped carbon nitride silicon dioxide heterojunction, and the prepared product can be used for preparing halogenated aromatic compounds by photocatalytic oxidation and has good conversion rate and selectivity on aromatic compound substrates. The catalyst has excellent catalytic activity on various aromatic compounds, and has wide application range, and the catalytic performance is still stable after repeated cyclic use.
The specific technical scheme is as follows:
a preparation method of a potassium ion doped carbon nitride silicon dioxide heterojunction comprises the following steps:
and uniformly mixing the carbon nitride precursor, the potassium salt and the silica sol, adding ethanol to enable the mixture to be gel, and calcining the gel at a high temperature in air to obtain the potassium ion doped carbon nitride silicon dioxide heterojunction.
The preparation method disclosed by the invention takes the carbon nitride precursor, the potassium ion source and the silicon dioxide sol as raw materials, and the preparation method can be prepared by calcining at high temperature in air atmosphere, and has the advantages of simple preparation process and low cost.
Further experiments show that if potassium ions are not doped or only potassium ions are doped with the carbon nitride precursor, the catalytic activity of the prepared product is greatly reduced in the reaction of preparing halogenated aromatic compounds by photocatalytic oxidation.
Preferably:
the carbon nitride precursor is selected from the group consisting of cyanamide.
The potassium salt is selected from one or more of potassium chloride, potassium bromide and potassium iodide; further preferred is potassium chloride. Experiments show that the adoption of potassium chloride as a potassium source can realize high-concentration potassium ion doping in the system disclosed by the invention.
Preferably:
the mass content of silicon dioxide in the silica sol is 30-50%; the mass ratio of the carbon nitride precursor to the silicon dioxide in the silica sol is 1:0.5 to 5;
the mass ratio of the carbon nitride precursor to the potassium chloride is 1:0.1 to 1.
Preferably, the high-temperature calcination is carried out at 500-600 ℃ for 1-5 hours; further preferably 550℃for 4h.
Further preferred is:
the mass ratio of the carbon nitride precursor to the silicon dioxide in the silica sol is 1: 0.625-2.5;
the mass ratio of the carbon nitride precursor to the potassium chloride is 1:0.25 to 0.75.
Still further preferred is:
the mass ratio of the carbon nitride precursor to the silicon dioxide in the silica sol is 1:1.25 to 2.5;
the mass ratio of the carbon nitride precursor to the potassium chloride is 1:0.5 to 0.75.
More preferably:
the mass ratio of the carbon nitride precursor to the silicon dioxide in the silica sol is 1:1.25;
the mass ratio of the carbon nitride precursor to the potassium chloride is 1:0.5.
with the continuous preference of the mass ratio of the raw materials in the preparation method, the prepared catalyst has higher catalytic activity in the reaction of preparing halogenated aromatic compounds by photocatalytic oxidation.
The invention also discloses a potassium ion doped carbon nitride silicon dioxide heterojunction prepared according to the reaction. The prepared composite catalyst has a typical heterojunction structure, wherein silicon dioxide with heavier mass is a spherical inner core, and carbon nitride with lighter mass grows on the periphery.
The invention also discloses a reaction for preparing halogenated aromatic compounds by photocatalytic oxidation, which adopts the potassium ion doped carbon nitride silicon dioxide heterojunction as a photocatalyst and specifically comprises the following steps:
mixing an aromatic compound, a photocatalyst, a halogen source and a solvent to obtain a raw material liquid, introducing oxygen, and then irradiating with a light source.
The aromatic compound is selected from one or more of anisole, 8-methoxy psoralen, gefitinib Luo Jijia ester and naproxen methyl ester;
the halogen source is selected from NaBr and/or KBr;
the solvent is selected from mixed solvents of dilute sulfuric acid and acetonitrile; preferably, the mixed solvent is composed of 0.1-1.0M sulfuric acid and acetonitrile, and the volume ratio of the two is 0.5-2; more preferably, the solvent mixture is composed of 0.5M sulfuric acid and acetonitrile in equal volumes.
The concentration of the aromatic compound in the raw material liquid is 10-100 mM; preferably 50mM.
Preferably, oxygen at a pressure of 1 to 2 atmospheres is introduced.
Preferably, irradiation is performed with a visible light source (wavelength >420nm,300W xenon lamp) for 1-8 hours.
Experiments show that the photocatalyst prepared by the invention has excellent catalytic activity, and can realize higher yield only by 2 hours.
Further preferably, the aromatic compound is selected from anisole and/or naproxen methyl ester, and experiments show that the yield is up to 90% or more after 2 hours of reaction by adopting the photocatalyst disclosed by the invention.
Still preferably, the aromatic compound is selected from anisole, and experiments show that the yield is up to 99% after 2 hours of reaction by using the photocatalyst disclosed by the invention.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a potassium ion doped carbon nitride silicon dioxide heterojunction, and the prepared potassium ion doped carbon nitride silicon dioxide heterojunction can be used as a photocatalyst in a reaction for preparing halogenated aromatic compounds by photocatalytic oxidation. The application of the photocatalyst realizes the substitution of halogen anions on para or ortho hydrogen atoms of electron donating groups on benzene rings of aromatic compounds, and the photocatalyst has the advantages of high catalytic activity, wide applicable substrate range and excellent catalytic stability.
Drawings
FIG. 1 is a TEM image of a potassium ion doped carbon nitride silicon dioxide heterojunction prepared in example 1;
FIG. 2 is a nuclear magnetic resonance spectrum of the photocatalytic product prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to the following examples and the accompanying drawings, in order to make the objects, technical solutions and effects of the present invention more clear and clarified. It should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
Uniformly mixing 1g of cyanamide, 1.25g of silicon dioxide-containing Ludox silica sol (the mass content of silicon dioxide in the silica sol is 40%, the same applies below) and 0.5g of potassium chloride, slowly adding ethanol to enable the mixed solution to be gel, placing the gel into a muffle furnace, calcining in an air atmosphere, heating to 550 ℃ from room temperature at a heating rate of 2.3 ℃/min, and preserving heat for 4 hours to obtain a target product, namely the potassium ion doped carbon nitride silicon dioxide heterojunction.
Fig. 1 is a TEM image of a potassium ion doped carbon nitride silicon dioxide heterojunction prepared in this example, and it can be confirmed by observing the image that the deep black region with a heavier mass is a silicon dioxide spherical core, and the carbon nitride with a lighter mass grows on the periphery of carbon dioxide to form a heterojunction structure.
Catalytic activity test:
20mg of the potassium ion doped carbon nitride silicon dioxide heterojunction prepared in the embodiment, 5mL of 0.5M sulfuric acid aqueous solution (containing 0.5M potassium bromide), 5mL of acetonitrile and 0.5mmol of anisole are placed in a 20mL quartz glass reaction bottle, oxygen with one atmosphere is introduced into the reaction bottle, and the reaction is carried out for 1h under the irradiation of a xenon lamp light source.
Example 2
The preparation process was substantially the same as in example 1, except that the mass of potassium chloride added was replaced with 0.25g.
A catalytic activity test was carried out using the catalyst prepared in this example under exactly the same conditions as in example 1.
Example 3
The preparation process was substantially the same as in example 1, except that the mass of potassium chloride added was replaced with 0.75g.
A catalytic activity test was carried out using the catalyst prepared in this example under exactly the same conditions as in example 1.
The results of the photocatalytic activities in examples 1 to 3 above are shown in Table 1 below, and by taking example 1 as an example, the nuclear magnetic resonance spectrum of the prepared photocatalytic product is shown in FIG. 2, and it can be confirmed by observing the graph that the photocatalytic product is p-bromoanisole.
TABLE 1
Example 4
The preparation process was essentially the same as in example 1, except that the added Ludox silica sol contained 0.625g of silica.
The catalyst prepared in this example was used for the catalytic activity test under the same conditions as in example 1 except that the reaction time was prolonged to 2 hours.
Example 5
The preparation process was essentially the same as in example 1, except that the Ludox silica sol to be added contained 2.5g of silica.
The catalyst prepared in this example was used for the catalytic activity test under the same conditions as in example 1 except that the reaction time was prolonged to 2 hours.
Example 6
A catalytic activity test was carried out using the catalyst prepared in example 1, and the test conditions were substantially the same as in example 1 except that the reaction time was replaced with 2 hours.
The results of the photocatalytic activities in example 1 and examples 4 to 6 are shown in Table 2 below.
TABLE 2
Examples 7 to 9
The catalyst prepared in example 1 was used except that the substrate anisole was replaced with 8-methoxypsoralene, gefitinib Luo Jijia ester and naproxen methyl ester, respectively, in the catalytic activity test, and the respective structural formulas are shown in Table 3, while the photocatalytic activity results in examples 7 to 9 are shown in Table 3 below.
TABLE 3 Table 3
Comparative example 1
The catalyst prepared in example 1 was used for the catalytic activity test under substantially the same conditions as in example 6, except that the reaction atmosphere was replaced with argon at one atmosphere by oxygen at one atmosphere.
Comparative example 2
1g of cyanamide is weighed, placed in a muffle furnace, calcined in an air atmosphere, heated to 550 ℃ from room temperature at a heating rate of 2.3 ℃/min, and kept for 4 hours to prepare the target product.
The catalyst prepared in this comparative example was used for the catalytic activity test under exactly the same conditions as in example 6.
Comparative example 3
Taking 1g of cyanamide and 0.5g of potassium chloride, uniformly mixing, slowly adding ethanol to enable the mixed solution to be gel, placing the gel into a muffle furnace, calcining in an air atmosphere, heating to 550 ℃ from room temperature at a heating rate of 2.3 ℃/min, and preserving heat for 4 hours to obtain the target product.
The catalyst prepared in this comparative example was used for the catalytic activity test under exactly the same conditions as in example 6.
Comparative example 4
Uniformly mixing 1g of cyanamide and 1.25g of silicon dioxide-containing Ludox silica sol, slowly adding ethanol to enable the mixed solution to be gel, placing the gel into a muffle furnace, calcining in an air atmosphere, heating to 550 ℃ from room temperature at a heating rate of 2.3 ℃/min, and preserving heat for 4 hours to obtain a target product.
The catalyst prepared in this comparative example was used for the catalytic activity test under exactly the same conditions as in example 6.
The results of the photocatalytic activities of example 6 and comparative examples 1 to 4 are shown in Table 4 below.
TABLE 4 Table 4
Stability performance test:
to further test the catalytic stability of the potassium ion doped carbon nitride silicon dioxide heterojunction prepared by the invention, the catalyst prepared in example 1 is taken as a test object, the yield of the photocatalytic product after different cycle times is tested, and the test conditions adopted in each test are exactly the same as those in example 6. The test results are listed in table 5 below.
TABLE 5
| Number of cycles | Reaction time (h) | Yield (%) |
| 1 | 2 | 99 |
| 2 | 2 | 99 |
| 3 | 2 | 98 |
| 4 | 2 | 99 |
| 5 | 2 | 98 |
Claims (5)
1. A method for preparing halogenated aromatic compounds by photocatalytic oxidation is characterized in that a potassium ion doped carbon nitride silicon dioxide heterojunction is used as a photocatalyst, and specifically comprises the following steps:
mixing an aromatic compound, a photocatalyst, a halogen source and a solvent to obtain a raw material liquid mixed with the catalyst, and introducing oxygen to irradiate the raw material liquid by the light source;
the preparation method of the potassium ion doped carbon nitride silicon dioxide heterojunction comprises the following steps:
uniformly mixing a carbon nitride precursor, potassium salt and silica sol, adding ethanol to enable the mixture to be gel, and calcining the gel at a high temperature in air to obtain the potassium ion doped carbon nitride silicon dioxide heterojunction;
the carbon nitride precursor is selected from cyanamide;
the potassium salt is selected from one or more of potassium chloride, potassium bromide and potassium iodide;
the mass ratio of the carbon nitride precursor to the silicon dioxide in the silica sol is 1: 1.25-2.5;
and the high-temperature calcination is carried out at 550-600 ℃ for 1-5 hours.
2. The method for preparing halogenated aromatic compounds by photocatalytic oxidation according to claim 1, wherein the mass content of silica in the silica sol is 30-50%.
3. The method for producing a halogenated aromatic compound by photocatalytic oxidation according to any one of claims 1 to 2, characterized in that said potassium salt is selected from potassium chloride;
the mass ratio of the carbon nitride precursor to the potassium salt is 1:0.5 to 0.75.
4. A method for preparing halogenated aromatic compound by photocatalytic oxidation according to claim 3, characterized in that:
the mass ratio of the carbon nitride precursor to the silicon dioxide in the silica sol is 1:1.25;
the mass ratio of the carbon nitride precursor to the potassium chloride is 1:0.5.
5. the method for producing a halogenated aromatic compound by photocatalytic oxidation according to claim 1, characterized in that:
the aromatic compound is selected from one or more of anisole, 8-methoxy psoralen, gefitinib Luo Jijia ester and naproxen methyl ester;
the halogen source is selected from NaBr and/or KBr;
the solvent is selected from mixed solvents of dilute sulfuric acid and acetonitrile;
the concentration of the aromatic compound in the raw material liquid is 10-100 mM.
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| CN103285894A (en) * | 2013-05-23 | 2013-09-11 | 河北科技大学 | Photocatalyst for halogenation reaction of organic matters and preparation method of photocatalyst |
| CN103301856A (en) * | 2013-05-23 | 2013-09-18 | 河北科技大学 | Application of nano noble metal/semiconductor composite photocatalyst to halogenation reaction of organic matters |
| CN106391086A (en) * | 2016-09-29 | 2017-02-15 | 中国地质大学（北京） | Preparation method of C3N4/SiO2 heterojunction photocatalyst |
| CN110560119A (en) * | 2019-08-14 | 2019-12-13 | 华东理工大学 | Preparation and application of potassium-doped inverse opal carbon nitride photocatalyst |
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| CN105498821B (en) * | 2015-12-17 | 2018-06-12 | 苏州大学 | It is a kind of for composite material of catalytic degradation nitrogen oxides and its preparation method and application |
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