CN110624594A - Magnetic Fe3O4/ZnO/g-C3N4Composite photocatalyst and preparation method thereof - Google Patents
Magnetic Fe3O4/ZnO/g-C3N4Composite photocatalyst and preparation method thereof Download PDFInfo
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- CN110624594A CN110624594A CN201910960738.5A CN201910960738A CN110624594A CN 110624594 A CN110624594 A CN 110624594A CN 201910960738 A CN201910960738 A CN 201910960738A CN 110624594 A CN110624594 A CN 110624594A
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000002105 nanoparticle Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 12
- 239000002135 nanosheet Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 238000007885 magnetic separation Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002077 nanosphere Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 12
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 6
- 239000000969 carrier Substances 0.000 abstract description 4
- 238000009388 chemical precipitation Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000006798 recombination Effects 0.000 abstract description 2
- 238000005215 recombination Methods 0.000 abstract description 2
- 230000000593 degrading effect Effects 0.000 abstract 1
- 230000031700 light absorption Effects 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- 239000003403 water pollutant Substances 0.000 abstract 1
- 239000011787 zinc oxide Substances 0.000 description 51
- 229910001868 water Inorganic materials 0.000 description 10
- 239000011701 zinc Substances 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 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 description 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical group C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 229910007541 Zn O Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
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- 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
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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
- B01J35/33—Electric or magnetic 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
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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
- C02F1/30—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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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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
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2101/36—Organic compounds containing halogen
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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
-
- 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
The invention discloses magnetic Fe3O4/ZnO/g‑C3N4A preparation method of a composite photocatalyst belongs to the technical field of photocatalysis. Aiming at the existing Fe3O4/ZnO/g‑C3N4The composite material has poor performance due to the appearance, the grain diameter and the size, and the method synthesizes the magnetic Fe by a chemical precipitation method3O4/ZnO/g‑C3N4A composite photocatalyst is provided. Magnetic Fe obtained3O4/ZnO/g‑C3N4The composite nanometer grain photocatalyst is prepared with ZnO/g-C3N4The formation of the heterojunction effectively inhibits the recombination of photon-generated carriers, expands the range of the material for light absorption and improves the utilization rate of visible light. The photocatalyst has better photocatalytic activity under visible light, and the activity of the photocatalyst is hardly reduced after the sample is repeatedly used for 5 times after being magnetically recovered, so that the use cost is reduced, and the secondary pollution caused by the photocatalyst in degrading water pollutants is avoided. The method has the characteristics of cheap raw materials, simple synthetic method, large-scale preparation and the like.
Description
Technical Field
The invention belongs to the technical field of photocatalysis and environmental protection, and particularly relates to magnetic Fe3O4/ZnO/g-C3N4A preparation method of a composite nanoparticle photocatalyst.
Background
In recent years, many industrial (such as textile, printing and dyeing, etc.) organic waste water seriously affect ecological environment and human health. By applying the semiconductor photocatalysis technology, harmful substances in the organic wastewater can be effectively converted into CO under the irradiation of sunlight or ultraviolet light source2And water and other harmless matters, so as to treat waste water. Therefore, the semiconductor photocatalysis technology is applied to purifying the waste water, and people attract more and more attention.
ZnO is a semiconductor material with wide application. ZnO is also an important semiconductor photocatalyst, and the forbidden band width at room temperature is 3.37 eV. ZnO under ultraviolet irradiation generates high-activity cavity which can decompose organic pollutant into products (such as CO) without secondary pollution2、H2O), thereby achieving the purpose of decontamination. However, ZnO is only photon excited in the uv region, which limits practical applications of ZnO. g-C compared with zinc oxide3N4Has a narrow forbidden bandwidth (2.2e V), responds to the visible light region, and has the characteristics of low raw material cost, good thermal stability, easy preparation and the like. ZnO is mixed with g-C3N4Is compounded due to g-C3N4The carrier is matched with a ZnO energy band, so that the separation efficiency of carriers is improved, and the degradation efficiency of organic pollutants can be effectively improved. And the light response range is enlarged, and the utilization rate of sunlight is improved.
The photocatalyst used for treating organic wastewater is mainly a powder product. Powdered photocatalystThe reagent is difficult to separate from the solution after use and recycle, and the disadvantages limit the practical application of the reagent to a certain extent. Thus, g-C3N4ZnO and magnetic g-C3N4And the compounded photocatalyst can be quickly recovered under the action of an external magnetic field, so that the secondary pollution of the photocatalyst to a water body in practical application is prevented. At present, Fe is prepared3O4/ZnO/g-C3N4The compounding method mainly adopts the pyrolysis method to prepare g-C3N4And then preparing Fe by using methods such as ultrasonic dispersion, hydrothermal method, reflux method, solid phase method and the like3O4/ZnO/g-C3N4A composite material. The preparation methods have the defects of high cost, difficult control of the shape and size and the like, and more importantly, are difficult to prepare on a large scale. Practice has shown that the microscopic morphological structure of the photocatalyst plays a crucial role in its performance. Therefore, the method for preparing Fe with simple process, suitability for large-scale production and controllable shape is developed3O4/ZnO/g-C3N4The method has important significance in the application of the photocatalysis field.
Disclosure of Invention
Aiming at the defects of the prior preparation technology, the invention provides magnetic Fe3O4/ZnO/g-C3N4A preparation method of a composite nanoparticle photocatalyst. The chemical reagent used in the method is cheap, the synthesis condition is mild, and the preparation process is simple; by chemical precipitation in Fe3O4And ZnO nano-particles exist, magnetic Fe is synthesized in one step3O4/ZnO/g-C3N4A composite photocatalyst; magnetic Fe prepared3O4/ZnO/g-C3N4The compound has the advantages of no impurity, high purity, convenient use, and easy recovery and reuse.
The invention provides magnetic Fe3O4/ZnO/g-C3N4The preparation method of the composite nano-particle photocatalyst comprises the following specific steps:
1) 10g of CO (NH) are weighed2)2Placing in a crucible, and heatingHeating to 550 ℃ in a tubular electric furnace at a heating rate of 5 ℃/min, preserving heat for 2 hours, and cooling to prepare g-C3N4Nanosheets.
2) 3mmol of Zn (NO) are weighed3)2·6H2O is dissolved in 30mL of deionized water, and 6mmol of NH is weighed4HCO3Dissolving in 60mL of deionized water, and adding NH4HCO3Adding Zn (NO) to the solution3)2·6H2Magnetically stirring in O solution for 15min, centrifugally washing, drying, and calcining in tubular electric furnace at 400 deg.c for 2 hr. And preparing the ZnO nano-sheet.
4) Weighing 10mmol FeCl3·6H2O and 5mmol FeCl2·4H2O was dissolved in 150mL of deionized water and stirred at 55 ℃ for 40 min. 100mL of NH was added3·H2O is dropped into the solution. After stirring for 1 hour, a reddish brown suspension was obtained. Magnetic separation, washing and drying to prepare Fe3O4Nanospheres.
5) 0.5g of Fe was weighed out separately3O4And 0.5g of ZnO and 0.03 to 0.09g (preferably 0.07g) of-C3N4Of Fe3O4And ZnO is added into the mixture, wherein the concentration of the added ZnO is 0.6-1.8 mg/mL and 50mL g-C3N4A methanol solution; and stirring after mixing, and collecting a stirred sample. The sample was dried in vacuo. Preparation of Fe3O4/ZnO/g-C3N4Composite nanoparticles.
The invention has the beneficial effects that:
1. the invention adopts a chemical precipitation method to produce Fe3O4And ZnO nano-particles exist, magnetic Fe is synthesized in one step3O4/ZnO/g-C3N4A composite nanoparticle photocatalyst. The preparation process is simple, the size is uniform, and the used reagent is low in cost.
2. Magnetic Fe3O4/ZnO/g-C3N4The heterojunction of the composite nanoparticle not only inhibits the recombination of photon-generated carriers, but also expands the photoresponse range of the photocatalyst and greatly improves the utilization rate of visible light.
3. Magnetic Fe obtained by the invention3O4/ZnO/g-C3N4The composite nanoparticle photocatalyst has high activity under visible light, has the advantages of convenience in use, convenience in recovery, reusability and the like when organic dye is degraded by photocatalysis, and the degradation efficiency of rhodamine-B in 120min can reach more than 97.3%.
Drawings
FIG. 1 shows X-ray diffraction (XRD) patterns of products obtained in examples 1 to 4 of the present invention.
FIG. 2 is an X-ray diffraction (XRD) spectrum of the product obtained in examples 1-4 of the present invention.
FIG. 3 is a spectrum of infrared spectroscopy (FT-IR) of the product obtained in examples 1 to 4 of the present invention.
FIG. 4 is a Transmission Electron Microscope (TEM) photograph of the product obtained in example 1 of the present invention.
FIG. 5 is a graph showing the variation of RhB concentration with reaction time of the products obtained in examples 1 to 4 of the present invention.
Detailed Description
Example 1
1) 10g of CO (NH) are weighed2)2Placing the mixture in a crucible, heating the mixture to 550 ℃ in a tubular electric furnace at the heating rate of 5 ℃/min, preserving the heat for 2 hours, and cooling to prepare the g-C3N4Nanosheets.
2) 3mmol of Zn (NO) are weighed3)2·6H2O is dissolved in 30mL of deionized water, and 6mmol of NH is weighed4HCO3Dissolving in 60mL of deionized water, and adding NH4HCO3Adding Zn (NO) to the solution3)2·6H2Magnetically stirring in O solution for 15min, centrifugally washing, drying, and calcining in tubular electric furnace at 400 deg.c for 2 hr. And preparing the ZnO nano-sheet.
4) Weighing 10mmol FeCl3·6H2O and 5mmol FeCl2·4H2O was dissolved in 150mL of deionized water and stirred at 55 ℃ for 40 min. 100mL of NH was added3·H2O is dropped into the solution. After stirring for 1 hour, a reddish brown suspension was obtained. Magnetic separation, washing and drying to prepare Fe3O4Nanospheres.
5) 0.5g of Fe was weighed out separately3O4And ZnO and 0.07g g-C3N4Of Fe3O4And ZnO addition 50mLg-C3N4In methanol solution. And stirring after mixing, and collecting a stirred sample. The sample was dried in vacuo. Preparation of Fe3O4/ZnO/g-C3N4Composite nanoparticles.
Example 2
1) 10g of CO (NH) are weighed2)2Placing the mixture in a crucible, heating the mixture to 550 ℃ in a tubular electric furnace at the heating rate of 5 ℃/min, preserving the heat for 2 hours, and cooling to prepare the g-C3N4Nanosheets.
2) 3mmol of Zn (NO) are weighed3)2·6H2O is dissolved in 30mL of deionized water, and 6mmol of NH is weighed4HCO3Dissolving in 60mL of deionized water, and adding NH4HCO3Adding Zn (NO) to the solution3)2·6H2Magnetically stirring in O solution for 15min, centrifugally washing, drying, and calcining in tubular electric furnace at 400 deg.c for 2 hr. And preparing the ZnO nano-sheet.
4) Weighing 10mmol FeCl3·6H2O and 5mmol FeCl2·4H2O was dissolved in 150mL of deionized water and stirred at 55 ℃ for 40 min. 100mL of NH was added3·H2O is dropped into the solution. After stirring for 1 hour, a reddish brown suspension was obtained. Magnetic separation, washing and drying to prepare Fe3O4Nanospheres.
5) 0.5g of Fe was weighed out separately3O4And ZnO and 0.03g g-C3N4Of Fe3O4And ZnO 50mL of g-C3N4In methanol solution. And stirring after mixing, and collecting a stirred sample. The sample was dried in vacuo. Preparation of Fe3O4/ZnO/g-C3N4Composite nanoparticles.
Example 3
1) 10g of CO (NH) are weighed2)2Placing in a crucible, heating in a tubular electric furnace at a heating rate of 5 deg.C/minKeeping the temperature for 2 hours at 550 ℃, and preparing the g-C after cooling3N4Nanosheets.
2) 3mmol of Zn (NO) are weighed3)2·6H2O is dissolved in 30mL of deionized water, and 6mmol of NH is weighed4HCO3Dissolving in 60mL of deionized water, and adding NH4HCO3Adding Zn (NO) to the solution3)2·6H2Magnetically stirring in O solution for 15min, centrifugally washing, drying, and calcining in tubular electric furnace at 400 deg.c for 2 hr. And preparing the ZnO nano-sheet.
4) Weighing 10mmol FeCl3·6H2O and 5mmol FeCl2·4H2O was dissolved in 150mL of deionized water and stirred at 55 ℃ for 40 min. 100mL of NH was added3·H2O is dropped into the solution. After stirring for 1 hour, a reddish brown suspension was obtained. Magnetic separation, washing and drying to prepare Fe3O4Nanospheres.
5) 0.5g of Fe was weighed out separately3O4And ZnO and 0.05g g-C3N4Of Fe3O4And ZnO 50mL of g-C3N4In methanol solution. And stirring after mixing, and collecting a stirred sample. The sample was dried in vacuo. Preparation of Fe3O4/ZnO/g-C3N4Composite nanoparticles.
Example 4
1) 10g of CO (NH) are weighed2)2Placing the mixture in a crucible, heating the mixture to 550 ℃ in a tubular electric furnace at the heating rate of 5 ℃/min, preserving the heat for 2 hours, and cooling to prepare the g-C3N4Nanosheets.
2) 3mmol of Zn (NO) are weighed3)2·6H2O is dissolved in 30mL of deionized water, and 6mmol of NH is weighed4HCO3Dissolving in 60mL of deionized water, and adding NH4HCO3Adding Zn (NO) to the solution3)2·6H2Magnetically stirring in O solution for 15min, centrifugally washing, drying, and calcining in tubular electric furnace at 400 deg.c for 2 hr. And preparing the ZnO nano-sheet.
4) Weighing 10mmol FeCl3·6H2O and 5mmol FeCl2·4H2O was dissolved in 150mL of deionized water and stirred at 55 ℃ for 40 min. 100mL of NH was added3·H2O is dropped into the solution. After stirring for 1 hour, a reddish brown suspension was obtained. Magnetic separation, washing and drying to prepare Fe3O4Nanospheres.
5) 0.5g of Fe was weighed out separately3O4And ZnO and 0.09g g-C3N4Of Fe3O4And ZnO 50mL of g-C3N4In methanol solution. And stirring after mixing, and collecting a stirred sample. The sample was dried in vacuo. Preparation of Fe3O4/ZnO/g-C3N4Composite nanoparticles.
As shown in fig. 1 and 2: examples 1-4 ZnO and Fe products3O4The XRD pattern of the sample coincides with the diffraction peak positions of the standard cards (JCPDS 36-1451) and (JCPDS 65-3107). g-C3N4The peak position of the diffraction peak of (2) also coincides with the characteristic peak thereof. Fe obtained in examples 1 to 43O4/ZnO/g-C3N4No other diffraction peaks are found in the XRD spectrogram of the composite nanoparticle, which indicates that Fe3O4And g-C3N4The introduction of (a) does not change the crystalline form of ZnO. Without significant g-C3N4The diffraction peak may be due to better dispersibility or low crystallinity.
To further confirm g-C3N4The products obtained in examples 1 to 4 were subjected to IR spectroscopy in the presence of the composite material. As shown in fig. 3: is located at 3435cm-1Is caused by O-H stretching. This may be due to water adsorption on the sample surface. At 1232cm-1、1326cm-1、1406cm-1、1575cm-1And 1645cm-1Absorption peak of (b) corresponds to g-C3N4Stretching mode of the C-N heterocyclic ring of (1). At 810cm-1Has an absorption peak of g-C3N4Typical bending vibrations of s-triazine units. Located at 500cm-1And 599cm-1This is due to the vibration of Zn-O and Fe-O. Description of the preparationThe sample was Fe3O4/ZnO/g-C3N4A composite material.
To further verify Fe3O4/ZnO/g-C3N4The structure of the composite photocatalyst is characterized by a Transmission Electron Microscope (TEM) for the product obtained in the embodiment 1 of the invention. As shown in fig. 4: flake g-C3N4Composed of square-shaped ZnO and spherical Fe3O4ZnO and Fe in support, composite material3O4The radius sizes of the particles are respectively 18-20nm and 10-15 nm. This structure shows ZnO/g-C3N4The heterojunction is formed, so that the separation efficiency of the carriers is improved, and the degradation efficiency of organic pollutants can be effectively improved. Fe3O4The nano particles are uniformly distributed in the composite material, and play a crucial role in quickly recovering the magnetic force of the photocatalyst.
FIG. 5 is a graph showing the RhB concentration of the product obtained in examples 1 to 4 of the present invention as a function of the reaction time. As shown in the figure: concentration of rhodamine-B solution: 5 mg/L; when the reaction time of a xenon lamp (the wavelength lambda is more than or equal to 400nm) with a visible light source of 250W is 120min, the concentration of rhodamine-B is only 3.7 percent of that of the initial rhodamine-B.
Claims (4)
1. Magnetic Fe3O4/ZnO/g-C3N4The composite photocatalyst is characterized in that the flake g-C in the composite photocatalyst3N4Composed of square-shaped ZnO and spherical Fe3O4ZnO and Fe in support, composite material3O4The radius sizes of the particles are respectively 18-20nm and 10-15 nm; fe3O4、ZnO、g-C3N4And the mass ratio of the three components is 1:1 (0.06-0.18).
2. Magnetic Fe according to claim 13O4/ZnO/g-C3N4A composite photocatalyst, characterized by Fe3O4、ZnO、g-C3N4And the mass ratio of the three is 1:1: 0.14.
3. Magnetic Fe according to claim 13O4/ZnO/g-C3N4The preparation method of the composite photocatalyst comprises the following specific steps:
1) 10g of CO (NH) are weighed2)2Placing the mixture in a crucible, heating the mixture to 550 ℃ in a tubular electric furnace at the heating rate of 5 ℃/min, preserving the heat for 2 hours, and cooling to prepare the g-C3N4Nanosheets;
2) 3mmol of Zn (NO) are weighed3)2·6H2O is dissolved in 30ml of deionized water, and 6mmol of NH is weighed4HCO3Dissolving in 60ml of deionized water, and adding NH4HCO3Adding Zn (NO) to the solution3)2·6H2Magnetically stirring in O solution for 15min, centrifuging, washing, drying, and calcining in a tubular electric furnace at 400 deg.C for 2 hr; preparing ZnO nanosheets;
4) weighing 10mmol FeCl3·6H2O and 5mmol FeCl2·4H2Dissolving O in 150ml deionized water, and stirring at 55 deg.C for 40 min; 100ml of NH were added3·H2Dripping O into the solution; stirring for 1 hour to obtain a reddish brown suspension; magnetic separation, washing and drying to prepare Fe3O4Nanospheres;
5) 0.5g of Fe was weighed out separately3O40.5g of ZnO and (0.03-0.09 g) g of-C3N4Of Fe3O4And ZnO is added into 50mL of g-C with the concentration of 0.6mg/mL to 1.8mg/mL respectively3N4A methanol solution; stirring after mixing, and collecting a stirred sample; the sample was dried in vacuum; preparation of Fe3O4/ZnO/g-C3N4Composite nanoparticles.
4. Magnetic Fe according to claim 33O4/ZnO/g-C3N4The preparation method of the composite photocatalyst is characterized in that 0.5g of Fe is weighed in the step 5)3O40.5g of ZnO and 0.07g g-C3N4。
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