CN111905797A - Hydroxyl copper fluoride/carbon nitride composite catalyst and preparation method and application thereof - Google Patents
Hydroxyl copper fluoride/carbon nitride composite catalyst and preparation method and application thereof Download PDFInfo
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- CN111905797A CN111905797A CN202010909706.5A CN202010909706A CN111905797A CN 111905797 A CN111905797 A CN 111905797A CN 202010909706 A CN202010909706 A CN 202010909706A CN 111905797 A CN111905797 A CN 111905797A
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- NJMQPXGAYDNODA-UHFFFAOYSA-L copper;fluoride;hydroxide Chemical compound [OH-].[F-].[Cu+2] NJMQPXGAYDNODA-UHFFFAOYSA-L 0.000 title claims description 41
- 238000002360 preparation method Methods 0.000 title abstract description 13
- SUNFRGUABVCWQB-UHFFFAOYSA-N copper;hypofluorous acid Chemical compound [Cu].FO SUNFRGUABVCWQB-UHFFFAOYSA-N 0.000 claims abstract description 31
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 16
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 8
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000000356 contaminant Substances 0.000 claims abstract 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 17
- 229940043267 rhodamine b Drugs 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 11
- -1 cyanamide compound Chemical class 0.000 claims description 10
- 239000002957 persistent organic pollutant Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000010335 hydrothermal treatment Methods 0.000 claims description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 claims description 4
- 229960004989 tetracycline hydrochloride Drugs 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 229960003742 phenol Drugs 0.000 claims 1
- 239000010949 copper Substances 0.000 abstract description 26
- 239000000463 material Substances 0.000 abstract description 18
- 230000015556 catabolic process Effects 0.000 abstract description 12
- 238000006731 degradation reaction Methods 0.000 abstract description 12
- 229910052802 copper Inorganic materials 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 abstract description 2
- 238000004043 dyeing Methods 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 238000007639 printing Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 230000000593 degrading effect Effects 0.000 description 10
- 238000005215 recombination Methods 0.000 description 6
- 230000006798 recombination Effects 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 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 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000013032 photocatalytic reaction Methods 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000012028 Fenton's reagent Substances 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000012360 testing method 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
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001912 cyanamides Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 238000005303 weighing Methods 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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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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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
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Abstract
The invention relates to a copper hydroxyfluoride/carbon nitride composite catalyst, which is prepared by mixing copper hydroxyfluoride and carbon nitride, wherein copper hydroxyfluoride (Cu) is obtained by taking copper nitrate, hexamethylenetetramine and fluoride as raw materials and adopting a hydrothermal method2(OH)3F) Then mechanically grinding the mixture and carbon nitride to obtain a target product. The composite catalyst has simple preparation process and low cost, widens the application of a copper-based material in the field of catalysis by synthesizing novel polyhydroxy copper fluoride, has excellent catalytic performance and ultrahigh stability under the irradiation of visible light by the synergistic action of photocatalysis and a novel Fenton-like system, and can be used for printing and dyeing wastewater and antibioticsRemoval and degradation of phenolic organic contaminants.
Description
Technical Field
The invention belongs to the technical field of catalyst synthesis, and particularly relates to a catalystHydroxyl copper fluoride/carbon nitride (Cu)2(OH)3F/g-C3N4) A composite catalyst material, a preparation method thereof and application thereof in degrading organic pollutants by photocatalysis and Fenton technology of the same type.
Background
With the rapid development of industrialization, the environmental pollution problem is becoming more serious, and water is being used as a life source, and the solution of water pollution problem is more urgent, in recent years, high-concentration and structurally stable organic wastewater is produced in large quantities, so how to effectively remove the high-concentration and difficult-to-degrade organic wastewater has become an important research field.
The photocatalyst is widely noticed as an advantage of low cost, high efficiency, cleanness, safety, no toxicity, no secondary pollution, etc., but because photo-generated electrons and holes belong to opposite charges, they can undergo in-vivo recombination or in-vitro recombination, and consume energy by releasing light or heat, thereby hindering the degradation of environmental pollutants on the surface of the catalyst. Therefore, in practical use, recombination of photogenerated electrons and holes is suppressed, and photogeneration e is fully utilized-And h+The oxidation and reduction energy is the problem that the photocatalytic oxidation technology needs to overcome mainly by improving the quantum yield of the photocatalytic reaction, prolonging the photogenerated exciton recombination time or accelerating the exciton transmission speed on the interface.
In recent years, copper-based materials have been known to have multiple oxidation states
The copper-based material is used as the Fenton-like reagent, so that the defects of the traditional Fenton reagent in the reagent application, such as narrow pH operation range, difficult recovery of the catalyst, secondary pollution and the like, can be overcome. As a copper-based material which is less researched, the polyhydroxy copper halide has various varieties and a simple preparation method, and if the polyhydroxy copper halide is used in the field of catalysis, the application field of the copper-based material can be widened while the excellent properties of the polyhydroxy copper halide are fully exerted.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and is simple to useA hydroxyl copper fluoride/carbon nitride (Cu) is synthesized and provided by a single method2(OH)3F/g-C3N4) The composite catalyst material inhibits the photo-generated electron-hole recombination of the photocatalyst through the synergistic effect of two advanced oxidation technologies, and accelerates the Fenton-like reaction rate, so that the composite catalyst material has an excellent effect of degrading organic pollutants through photocatalysis.
The invention also provides the hydroxyl copper fluoride/carbon nitride (Cu)2(OH)3F/g-C3N4) A preparation method of the composite catalyst material and application thereof in photocatalytic degradation of water pollutants such as dye.
In order to achieve the purpose, the invention adopts the following technical scheme:
the composite catalyst consists of hydroxyl copper fluoride and carbon nitride, and the weight of the hydroxyl copper fluoride accounts for 20-60% of that of the carbon nitride.
In the hydroxyl copper fluoride/carbon nitride composite catalyst, cyanamide compounds can be calcined at 550 ℃ for 3-4h to obtain carbon nitride. The cyanamide compound is melamine or dicyandiamide and the like.
In the above copper hydroxyfluoride/carbon nitride composite catalyst, the copper hydroxyfluoride can be obtained by the following steps: dissolving copper nitrate and hexamethylenetetramine in deionized water, adjusting the pH value to be neutral by using ammonia water, adding fluoride, uniformly stirring, carrying out hydrothermal treatment in a reaction kettle at 85-135 ℃ for 2-8h under a closed condition, naturally cooling to room temperature, washing and drying to obtain a light blue powdery sample, namely the copper hydroxyfluoride.
The fluoride is one or a mixture of more than two of sodium fluoride, potassium fluoride and calcium fluoride.
The invention provides a preparation method of the hydroxyl copper fluoride/carbon nitride composite catalyst, which comprises the following steps:
1) dissolving copper nitrate and hexamethylenetetramine in deionized water, adjusting the pH value to be neutral by using ammonia water, and then adding fluoride and stirring uniformly; the mass ratio of the copper nitrate to the hexamethylenetetramine to the fluoride is 1.4-1.5:0.8-0.9: 1.2-1.3;
2) carrying out hydrothermal treatment on the product obtained in the step 1) in a reaction kettle at 85-135 ℃ for 2-8h (preferably at 95 ℃ for 2 h) under a closed condition, naturally cooling to room temperature, washing and drying to obtain a light blue powdery sample, namely the hydroxyl copper fluoride;
3) calcining cyanamide compound at 550 ℃ for 3-4h to obtain carbon nitride;
4) and (3) mixing the hydroxyl copper fluoride obtained in the step 2) and the carbon nitride obtained in the step 3) in proportion, and mechanically grinding uniformly to obtain the hydroxyl copper fluoride/carbon nitride composite catalyst.
The invention also provides application of the hydroxyl copper fluoride/carbon nitride composite catalyst in photocatalytic degradation of different organic pollutants.
Further, the invention provides application of the hydroxyl copper fluoride/carbon nitride composite catalyst in photocatalytic degradation of rhodamine B, tetracycline hydrochloride and bisphenol A.
According to the invention, Fenton-like reagent hydroxyl copper fluoride is synthesized by a hydrothermal method, and carbon nitride is obtained by a calcining method; the two catalysts were then composited by mechanical attrition. In the prepared hydroxyl copper fluoride/carbon nitride composite catalyst, the hydroxyl copper fluoride is attached to the surface of carbon nitride; the carbon nitride structure is blocky, and the hydroxyl copper fluoride structure is flaky; the composite catalyst material has good photocatalytic degradation performance and can be used for degrading various organic pollutants.
Cu2(OH)3F as a Fenton-like reagent can accelerate and replace Fe2+To H2O2Acting as a catalyst, Cu2(OH)3F/g-C3N4The Fenton-photocatalysis two advanced oxidation technologies of the composite material are combined, so that the speed-determining step of the Fenton reaction can be accelerated, and the g-C can be inhibited3N4The photogenerated electrons and the holes are compounded, so that the rhodamine B as the organic wastewater pollutant is rapidly degraded.
Compared with the prior art, the invention has the following beneficial effects:
1) the hydroxyl copper fluoride/carbon nitride composite catalyst is obtained by simple hydrothermal, calcination and mechanical grinding, and has the advantages of simple operation process, short preparation time and low cost. In addition, compared with other reagents, the catalyst material disclosed by the invention has the advantages of extremely fast speed and good cyclicity in degrading organic pollutants, can effectively solve the problem that carbon nitride photogenerated carriers are easy to compound, widens the pH operation range of the traditional Fenton reagent, and improves the stability of the material.
2) The hydroxyl copper fluoride/carbon nitride composite catalyst is used for removing and degrading organic pollutants under the irradiation of visible light, and the application range of a single material is expanded due to the synergistic effect of the composite catalyst while the respective defects are made up. The test result shows that: the hydroxyl copper fluoride/carbon nitride composite catalyst has extremely excellent photocatalytic performance under simulated sunlight, can achieve the purpose of quickly degrading pollutants, and has great potential in the aspect of treating industrial wastewater.
Drawings
FIG. 1 shows g-C in the present invention3N4SEM images of the material;
FIG. 2 shows Cu in the present invention2(OH)3SEM image of material F;
FIG. 3 shows copper hydroxyfluoride/carbon nitride (Cu) in example 1 of the present invention2(OH)3F/g-C3N4) SEM image of the composite catalyst;
FIG. 4 shows copper hydroxyfluoride/carbon nitride (Cu) in example 1 of the present invention2(OH)3F/g-C3N4) XRD pattern of the composite catalyst;
FIG. 5 shows copper hydroxyfluoride/carbon nitride (Cu) in example 1 of the present invention2(OH)3F/g-C3N4) XPS plot of composite catalyst;
FIG. 6 shows examples 1 to 3 of the present invention in which copper hydroxyfluoride/carbon nitride (Cu) is used2(OH)3F/g-C3N4) A performance diagram of degrading rhodamine B of the composite catalyst;
FIG. 7 shows copper hydroxyfluoride/carbon nitride (Cu) in example 1 of the present invention2(OH)3F/g-C3N4) A performance diagram of the composite catalyst for degrading different organic pollutants;
FIG. 8 shows the present inventionEXAMPLES example 1 Hydroxycopper fluoride/carbon nitride (Cu)2(OH)3F/g-C3N4) And (4) a circulation experiment result chart of the composite catalyst.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.
Example 1 preparation of a 40% Hydroxycopper fluoride/carbon nitride composite catalyst
A preparation method of the hydroxyl copper fluoride/carbon nitride composite catalyst comprises the following steps:
1) dissolving 1.44g of copper nitrate and 0.82g of hexamethylenetetramine in a polytetrafluoroethylene lining filled with 60ml of deionized water, stirring for 10min, adjusting the pH value to be neutral by using ammonia water, then adding 1.28g of sodium fluoride, and continuously stirring for 10 min;
2) putting the product obtained in the step 1) into a reaction kettle for sealing, then transferring the product into a forced air drying oven for hydrothermal treatment at 95 ℃ for 2h, naturally cooling to room temperature, washing for 3 times by deionized water, and drying at 60 ℃ for 4h to obtain a light blue powdery sample, namely the hydroxyl copper fluoride Cu2(OH)3F, SEM picture of FIG. 2;
3) the melamine is put into a muffle furnace to be calcined for 4 hours at 550 ℃ to obtain the carbon nitride g-C3N4The SEM picture is shown in figure 1;
4) 0.52g of hydroxyl copper fluoride and 1.3g of carbon nitride are mixed and mechanically ground uniformly to obtain 40 percent of hydroxyl copper fluoride/carbon nitride (Cu)2(OH)3F/g-C3N4) And (3) compounding a catalyst.
FIG. 1 shows g-C in the present invention3N4SEM images of the material; the carbon nitride obtained by calcining melamine can be seen in the figure as a blocky structure, with a dense overall structure and a large block.
FIG. 2 shows Cu in the present invention2(OH)3SEM image of material F; in the figure, it can be seen that the hydroxyl copper fluoride obtained by hydrothermal treatment has a layered structure, uniform size and good crystallinity.
FIG. 3 is an SEM image of 40% copper hydroxyfluoride/carbon nitride of example 1, showing that the layered copper hydroxyfluoride is attached to the bulk carbon nitride surface. FIG. 4 is a comparative XRD diagram of 40% copper hydroxyfluoride/carbon nitride in example 1, and the combined diagram shows the peaks corresponding to copper hydroxyfluoride and carbon nitride, which indicates that copper hydroxyfluoride and carbon nitride are well combined. FIG. 5 is an XPS plot of 40% copper hydroxyfluoride/carbon nitride of example 1, showing that the composite contains Cu, O, F, C, N, H elements, among which H is not detectable.
Example 2 preparation of 20% Hydroxycopper fluoride/carbon nitride composite catalyst
A preparation method of the hydroxyl copper fluoride/carbon nitride composite catalyst comprises the following steps:
1) -3) the procedure is as in example 1;
4) 0.26g of hydroxyl copper fluoride and 1.3g of carbon nitride are mixed and mechanically ground uniformly to obtain 20 percent of hydroxyl copper fluoride/carbon nitride (Cu)2(OH)3F/g-C3N4) And (3) compounding a catalyst.
Example 3 preparation of 60% Hydroxycopper fluoride/carbon nitride composite catalyst
1) -3) the procedure is as in example 1;
4) 0.78g of hydroxyl copper fluoride and 1.3g of carbon nitride are mixed and mechanically ground uniformly to obtain 60 percent of hydroxyl copper fluoride/carbon nitride (Cu)2(OH)3F/g-C3N4) And (3) compounding a catalyst.
Catalyst degradation test:
10mg of the 40%, 20% and 60% copper hydroxyfluoride/carbon nitride composite catalyst prepared in examples 1 to 3 was weighed, added to 50ml of 20mg/L rhodamine B solution, placed in the dark, stirred and adsorbed in the dark for 40 minutes to reach equilibrium, and then 0.2ml of H was added2O2Carrying out photocatalytic reaction under a xenon lamp (lambda is more than or equal to 400 nm), sampling every 5min, and measuring the absorbance of rhodamine B in supernatant after filtering. The degradation method of tetracycline hydrochloride and bisphenol A is the same as above.
FIG. 6 shows 40% copper hydroxyfluoride/carbon nitride (40% Cu) obtained in example 12(OH)3F/CN) sample degrading yeast for degrading rhodamine B through photocatalysisLine, visible in the figure: the photocatalytic performance of the material is far higher than that of single carbon nitride, and the degradation rate of rhodamine B can reach more than 98% after the reaction is carried out for 30 min. This indicates that H is allowed to form after the carbon nitride is complexed with the copper hydroxyfluoride2O2Can rapidly generate hydroxyl free radical with strong oxidizing property and simultaneously generate hydroxyl free radical in Cu+And Cu2+In the conversion, the recombination of photo-generated electrons and holes of the carbon nitride is inhibited, the synergistic effect of photocatalysis and Fenton effect is accelerated, and the organic pollutants can be rapidly degraded.
FIG. 6 shows the 20%, 60% copper hydroxyfluoride/carbon nitride (20% Cu) results of examples 2 and 3 simultaneously2(OH)3F/CN、60%Cu2(OH)3F/CN) sample photocatalytic degradation rhodamine B degradation curve. It can be seen in the figure that: after the reaction is carried out for 40min and 50min respectively, the degradation rate of the sample on rhodamine B can reach 97 percent and 94 percent respectively, and the photocatalytic performance is far higher than that of a single carbon nitride sample.
FIG. 7 shows that after 40min of reaction under the same conditions, the degradation efficiency of 40% copper hydroxyfluoride/carbon nitride on rhodamine B is 99%, the degradation efficiency on tetracycline hydrochloride is 76%, and the degradation rate on bisphenol A is 68%, which indicates that the obtained compound has good degradation effects on different pollutants.
Catalyst cycling experiments:
weighing 10mg of 40% hydroxyl copper fluoride/carbon nitride composite catalyst in the embodiment 1 of the invention, adding the 40% hydroxyl copper fluoride/carbon nitride composite catalyst into 50ml of rhodamine B solution with the concentration of 20mg/L, placing the rhodamine B solution in the dark, stirring the rhodamine B solution in the dark for dark adsorption for 40 minutes to reach balance, and adding 0.2ml of H2O2Carrying out photocatalytic reaction under a xenon lamp (lambda is more than or equal to 400 nm), and after the catalyst is degraded, measuring the absorbance of rhodamine B in the supernatant through filtration. The catalyst obtained by filtration was washed and dried, and then added again to 50ml of 20mg/L rhodamine B solution to carry out photocatalytic reaction under the same conditions, and the same operation was repeated 5 times, and the results are shown in FIG. 8.
As can be seen in fig. 8: after five times of circulation, the rhodamine decoloring rate of the 40% hydroxyl copper fluoride/carbon nitride composite catalyst is not reduced and can still reach 99%.
To sum up, the following steps are carried out: the hydroxyl copper fluoride/carbon nitride composite catalyst has good catalytic degradation and catalytic stability, and has wide application prospect in the actual organic printing and dyeing wastewater treatment.
Claims (6)
1. The copper hydroxyfluoride/carbon nitride composite catalyst is characterized by being prepared by mixing copper hydroxyfluoride and carbon nitride, wherein the copper hydroxyfluoride accounts for 20-60% of the weight of the carbon nitride.
2. The copper hydroxyfluoride/carbon nitride composite catalyst according to claim 1, wherein carbon nitride is obtained by calcining a cyanamide compound at 550 ℃ for 3 to 4 hours.
3. The copper hydroxyfluoride/carbon nitride composite catalyst according to claim 1, wherein the copper hydroxyfluoride is obtained by: dissolving copper nitrate and hexamethylenetetramine in deionized water, adjusting the pH value to be neutral by using ammonia water, adding fluoride, uniformly stirring, carrying out hydrothermal treatment in a reaction kettle at 85-135 ℃ for 2-8h under a closed condition, naturally cooling to room temperature, washing and drying to obtain a light blue powdery sample, namely the copper hydroxyfluoride.
4. A method for preparing the copper hydroxyfluoride/carbon nitride composite catalyst according to any one of claims 1 to 3, comprising the steps of:
1) dissolving copper nitrate and hexamethylenetetramine in deionized water, adjusting the pH value to be neutral by using ammonia water, and then adding fluoride and stirring uniformly; the mass ratio of the copper nitrate to the hexamethylenetetramine to the sodium fluoride is 1.4-1.5:0.8-0.9: 1.2-1.3;
2) carrying out hydrothermal treatment on the product obtained in the step 1) in a reaction kettle at 85-135 ℃ for 2-8h under a closed condition, naturally cooling to room temperature, washing and drying to obtain a light blue powdery sample, namely the hydroxyl copper fluoride;
3) calcining cyanamide compound at the temperature of 450-550 ℃ for 3-4h to obtain carbon nitride;
4) and (3) mixing the hydroxyl copper fluoride obtained in the step 2) and the carbon nitride obtained in the step 3) in proportion, and mechanically grinding uniformly to obtain the hydroxyl copper fluoride/carbon nitride composite catalyst.
5. Use of the copper hydroxyfluoride/carbon nitride composite catalyst of any one of claims 1 to 3 for photocatalytic degradation of organic pollutants
6. The use of claim 5, wherein the organic contaminant is one or a mixture of more than two of rhodamine B, tetracycline hydrochloride and phenol.
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