CN111659440A - photo-Fenton catalyst, preparation method thereof and application thereof in water treatment - Google Patents
photo-Fenton catalyst, preparation method thereof and application thereof in water treatment Download PDFInfo
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Abstract
The invention discloses a photo-Fenton catalyst, a preparation method thereof and application thereof in water treatment, and belongs to the technical field of water treatment. The invention provides a method for preparing g-C3N4/Fe2O3A method of preparing the composite catalyst and a photo-Fenton water treatment method using the catalyst. The invention firstly prepares g-C3N4Nanosheet, then ferric nitrate and ammonium bicarbonate are used as raw materials, and g-C3N4The nanosheet is subjected to composite modification to obtain g-C3N4/Fe2O3And (c) a complex. g-C prepared by the method of the invention3N4/Fe2O3photo-Fenton catalyst, Fe2O3Quantum dots are loaded to g-C by means of fixed-point deposition3N4The surface of the nano-sheet brings more catalytic active sites and larger reaction contact area, and when the nano-sheet is used for degrading antibiotic pollutants in water, the nano-sheet has excellent catalytic performance, high degradation efficiency on the antibiotic pollutants, low operation cost, no secondary pollution and wide application prospect.
Description
Technical Field
The invention relates to a photo-Fenton catalyst, a preparation method thereof and application thereof in water treatment, belonging to the technical field of water treatment.
Background
In recent years, the problem of environmental pollution caused by antibiotics has become more severe, and the antibiotic residues are frequently detected in water bodies. The accumulation of antibiotics in water can induce the generation of drug-resistant strains, which leads to the change of microbial flora, thereby harming human health and ecological safety. The photo-Fenton oxidation technology mainly utilizes photo-excitation to accelerate Fe2+Regeneration and activation of H2O2、H2Small molecules such as O and dissolved oxygen, and active oxygen free radicals (OH and O) are accelerated2 -Etc.) to oxidatively degrade organic contaminants. The technology has the advantages of simple operation, mild reaction conditions, high reaction rate, high mineralization efficiency and the like, and shows wide application prospect in the field of antibiotic wastewater treatment. The photo-fenton oxidation technology is classified into a homogeneous phase and a heterogeneous phase according to the phase state of a reaction system. Compared with a homogeneous system, the heterogeneous photo-Fenton system has the advantages of capability of avoiding the generation of iron-containing sludge, easiness in recycling and reusing of the catalyst and the like, and is highly valued by researchers.
Hematite (Fe)2O3) Has the advantages of environmental protection, stable structure, low cost, no toxicity, abundant existence in nature and the like. The researchers found that Fe provides higher specific surface area and more catalytic active sites2O3Nanoparticles are a widely used photo-fenton catalyst. However, these Fe2O3The use of nanoparticles as photo-fenton catalysts for the degradation of organic contaminants still presents some problems:
(1) the nano particle catalyst has higher surface energy, so that agglomeration is easy to occur, surface active sites are reduced, and the degradation efficiency of organic matters is reduced.
(2) Due to Fe3+To Fe2+The conversion rate of (a) is low, and the catalytic efficiency of the nanoparticles as photo-fenton catalysts is also to be further improved.
Disclosure of Invention
[ problem ] to
With Fe2O3When the nano particles are used as the photo-Fenton catalyst, the nano particle catalyst is easy to agglomerate due to high surface energy, so that the surface active sites are reduced, and the degradation efficiency of organic matters is reduced. In addition, due to Fe3+To Fe2+Low conversion of (3), Fe2O3The catalytic efficiency of the nanoparticles as photo-fenton catalysts is also to be further improved.
[ solution ]
In order to solve the above problems, the present invention provides a process for preparing g-C3N4/Fe2O3Method for preparing composite catalyst, and light-Fenton water treatment by using the catalyst, g-C prepared by the method of the invention3N4/Fe2O3photo-Fenton catalyst, Fe2O3Quantum dots are loaded to g-C by means of fixed-point deposition3N4The surface of the nano-sheet brings more catalytic active sites and larger reaction contact area, and when the nano-sheet is used for degrading antibiotic pollutants in water, the nano-sheet has excellent catalytic performance, high efficiency of degrading the antibiotic pollutants and low cost.
The invention provides a method for preparing a photo-Fenton catalyst g-C3N4/Fe2O3The method of (a), the method comprising the steps of:
(1) taking a carbon nitride precursor for two-stage calcination to obtain g-C3N4Nanosheets;
(2) g to C3N4Adding the nanosheet into a solvent, ultrasonically dispersing, sequentially adding ferric nitrate and ammonium bicarbonate into the dispersion liquid, stirring, separating, washing and drying to obtain the productDrying the product at 1.0-5.0 deg.C for min-1Heating to 300-400 ℃ for 2-4 h to obtain g-C3N4/Fe2O3And (c) a complex.
In an embodiment of the present invention, in step (1), the carbon nitride precursor is any one or more of urea, melamine, thiourea, and dicyanodiamine.
In one embodiment of the present invention, the mass of the carbon nitride precursor in the step (1) is 30 to 60 g.
In one embodiment of the present invention, the two-stage calcination process in step (1) is as follows: first stage calcination: covering the carbon nitride precursor for calcining at the temperature of 1.0-5.0 ℃ for min-1Heating to 550 ℃ at the speed of the temperature, and keeping the temperature for 2-4 h; and (3) second-stage calcination: re-calcining the product obtained in the first stage of calcination, wherein the calcination process is carried out without covering a cover and the temperature is 1.0-5.0 ℃ for min-1Heating to 500 ℃ at the speed of (1), and keeping the temperature for 2-4 h to obtain g-C3N4Nanosheets.
In one embodiment of the present invention, the solvent in step (2) is an ethanol solution.
In one embodiment of the present invention, g to C in the solvent of step (2)3N4The concentration of (b) is 1.0-10.0 g/L.
In one embodiment of the present invention, the concentration of ferric nitrate in the dispersion liquid in the step (2) is 1.0 to 10.0 mol/L.
In one embodiment of the invention, the concentration of ammonium bicarbonate in the dispersion liquid in the step (2) is 3.0-30.0 mol/L.
In one embodiment of the invention, the dried product in step (2) is at 2 ℃ min-1Heating to 300 ℃ for 2h to give g-C3N4/Fe2O3And (c) a complex.
The invention provides a photo-Fenton catalyst g-C prepared by the preparation method3N4/Fe2O3。
The present invention provides the photo-Fenton catalyst g-C3N4/Fe2O3The application in degrading organic pollutant in water.
The present invention provides the photo-Fenton catalyst g-C3N4/Fe2O3A method for degrading organic contaminants in water, the method comprising:
(1) subjecting photo-Fenton catalyst g-C3N4/Fe2O3Adding into water solution of organic pollutant, controlling reaction temperature at 5-40 deg.C, and stirring continuously to reach adsorption balance;
(2) adding hydrogen peroxide into an adsorption equilibrium system, starting a xenon lamp to excite visible light with lambda being more than 420nm, taking out reaction liquid at intervals, filtering out a catalyst, measuring the concentration of organic pollutants in filtrate by using a colorimetric method, and determining the degradation efficiency of the organic pollutants according to the change of the concentration.
In one embodiment of the present invention, g to C in step (1)3N4/Fe2O3The mass ratio of the addition amount to the aqueous solution of the organic pollutants is 2: 10000-4: 10000.
In one embodiment of the present invention, the concentration of the aqueous solution of the organic pollutant in step (1) is 10 to 40 mg/L.
In one embodiment of the present invention, the amount of the hydrogen peroxide added in the step (2) is 20 to 70 mmol/L.
[ advantageous effects ]:
(1) the invention obtains g-C3N4/Fe2O3photo-Fenton catalyst, Fe2O3Quantum dots are loaded to g-C by means of fixed-point deposition3N4The surface of the nano-sheet is greatly increased in g-C3N4The dispersion of the surface of the nano-sheet effectively solves the problem of nano-particle agglomeration;
(2) the invention obtains g-C3N4/Fe2O3photo-Fenton catalyst, Fe2O3Quantum dots dispersedly deposited on g-C3N4The surface of the nanosheet brings more catalytic active sites and larger reaction contact area, and is beneficial to improving the degradation of pollutants;
(3) the invention obtains g-C3N4/Fe2O3photo-Fenton catalyst, g-C3N4Nanosheet and Fe2O3The quantum dots form effective heterojunction at the interface, so that the separation and transmission of photo-generated charges are improved, and Fe is accelerated3+To Fe2+The catalytic performance is further improved by the conversion of the catalyst;
(4) the invention obtains g-C3N4/Fe2O3photo-Fenton catalyst, g-C3N4/Fe2O3The catalyst can show high-efficiency catalytic activity on various organic pollutants such as tetracycline, methyl orange, rhodamine B, phenol and the like;
(5) the invention obtains g-C3N4/Fe2O3photo-Fenton catalyst, Fe2O3Quantum dots dispersedly deposited on g-C3N4Nanosheet surface, in contrast to other nanotopography of Fe2O3(nanoparticles, nanorods, nanosheets, and echinoid nanostructures) modified g-C3N4The nano-sheet compound has higher tetracycline catalytic degradation activity;
(6) the invention obtains g-C3N4/Fe2O3photo-Fenton catalyst, g-C3N4/Fe2O3The synthesis method is simple, and the production cost of the catalyst is greatly reduced.
Drawings
FIG. 1 shows photo-Fenton catalysts g-C prepared in example 13N4/Fe2O3A TEM image of (a).
FIG. 2 shows photo-Fenton catalysts g-C prepared in example 13N4/Fe2O3Wherein (a), (b), (C) and (d) are high resolution XPS spectra of C1s, N1s, Fe2p and O1s, respectively.
FIG. 3 is g-C prepared as in example 1 in example 43N4/Fe2O3The change curve of tetracycline concentration with time is degraded by the catalyst in the photo-Fenton process.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.
[ example 1 ]
(1) Adding 30g urea into crucible, adding crucible cover, and heating at 2.5 deg.C for min-1Heating to 550 deg.C for 4h, adding the obtained product into the crucible again, without crucible cover, and heating at 2 deg.C for 2 min-1Heating to 500 ℃ for 2h to give g-C3N4Nanosheets;
(2) g-C obtained in step (1)3N4Adding the nano-sheets into ethanol solution with the concentration of 2.0g L-1Ultrasonic treatment until the dispersion is uniform, and sequentially adding ferric nitrate and ammonium bicarbonate into the dispersion liquid to make the concentrations respectively be 1.0 and 3.0mol L-1Stirring for 10h, filtering, separating, washing with deionized water, drying, and heating at 2 deg.C for 2 min-1Heating to 350 ℃ for 2h to obtain g-C3N4/Fe2O3And (c) a complex.
Characterization test:
1. photo-Fenton catalysts g-C prepared for this example3N4/Fe2O3Transmission electron microscopy, FIG. 1 shows photo-Fenton catalysts g-C prepared in this example3N4/Fe2O3Can be seen from the graph: fe2O3Quantum dots are uniformly deposited on g-C3N4Surface of, wherein Fe2O3The particle size of (a) is between 3 and 5 nm.
2. photo-Fenton catalysts g-C prepared for this example3N4/Fe2O3FIG. 2 shows photo-Fenton catalysts g-C prepared in this example by measuring X-ray photoelectron spectroscopy3N4/Fe2O3The XPS spectrum of (A) can be seen from the figure: fe2O3Successfully loaded in g-C3N4A surface.
[ example 2 ]
(1) Adding 30g urea into crucible, adding crucible cover, and heating at 1.0 deg.C for min-1Heating to 550 deg.C for 2h, adding the obtained product into the crucible again, without crucible cover, and heating at 1.0 deg.C for 1.0 min-1Heating to 500 ℃ for 2h to give g-C3N4Nanosheets;
(2) g-C obtained in step (1)3N4Adding the nano-sheets into ethanol solution with the concentration of 4.0g L-1Ultrasonic dispersing, adding ferric nitrate and ammonium bicarbonate into the dispersion liquid in sequence, wherein the concentration is 1.0 mol L and 3.0mol L respectively-1Stirring for 10h, filtering, separating, washing with deionized water, drying, and heating at 1.0 deg.C for min-1Heating to 300 ℃ for 2h to give g-C3N4/Fe2O3And (c) a complex.
[ example 3 ]
(1) Adding 60g urea into crucible, adding crucible cover, and heating at 5.0 deg.C for min-1Heating to 550 deg.C for 4h, adding the obtained product into the crucible again, without crucible cover, and heating at 5.0 deg.C for a further min-1Heating to 500 ℃ for 4h to give g-C3N4Nanosheets;
(2) g-C obtained in the step (1)3N4Adding the nano-sheets into ethanol solution with the concentration of 10.0g L-1Ultrasonic dispersing, adding ferric nitrate and ammonium bicarbonate into the dispersion liquid in sequence, wherein the concentration is respectively 10.0mol L and 30.0mol L-1Stirring for 10h, filtering, separating, washing with deionized water, drying, and cooling at 5.0 deg.C for min-1Heating to 400 ℃ for 4h to give g-C3N4/Fe2O3And (c) a complex.
[ example 4 ] catalytic degradation of Tetracycline
g-C prepared as in example 13N4/Fe2O3Catalyzing and degrading tetracycline:
(1) examples according to a mass ratio of 2:100001 g-C3N4/Fe2O3Adding into a solution with a concentration of 20mg L-1In the tetracycline aqueous solution, controlling the reaction temperature to be 25 ℃, and continuously stirring to achieve adsorption balance;
(2) adding 50mmol L into the adsorption equilibrium system-1Hydrogen peroxide and starting a 300W xenon lamp to excite lambda>And (3) visible light of 420nm, taking out the reaction liquid at intervals, filtering out the catalyst, measuring the concentration of tetracycline in the filtrate by a colorimetric method, and determining the degradation efficiency of the tetracycline according to the change of the concentration, wherein the degradation efficiency is marked as # 1. FIG. 3 is g-C prepared in example 13N4/Fe2O3The change curve of tetracycline concentration with time is degraded by the catalyst in the photo-Fenton process.
g-C prepared as in example 23N4/Fe2O3Catalyzing and degrading tetracycline:
(1) g-C obtained in example 2 was mixed at a mass ratio of 2:100003N4/Fe2O3Adding into a solution with a concentration of 20mg L-1In the tetracycline aqueous solution, controlling the reaction temperature to be 25 ℃, and continuously stirring to achieve adsorption balance;
(2) adding 50mmol L into the adsorption equilibrium system-1Hydrogen peroxide and starting a 300W xenon lamp to excite lambda>And (4) visible light of 420nm, taking out the reaction liquid at intervals, filtering out the catalyst, measuring the concentration of tetracycline in the filtrate by a colorimetric method, and determining the degradation efficiency of the tetracycline according to the change of the concentration, wherein the degradation efficiency is marked as # 2.
g-C prepared as in example 33N4/Fe2O3Catalyzing and degrading tetracycline:
(1) g-C obtained in example 3 was mixed at a mass ratio of 2:100003N4/Fe2O3Adding into a solution with a concentration of 20mg L-1In the tetracycline aqueous solution, controlling the reaction temperature to be 25 ℃, and continuously stirring to achieve adsorption balance;
(2) adding 50mmol L into the adsorption equilibrium system-1Hydrogen peroxide and starting a 300W xenon lamp to excite lambda>Visible light of 420nm, taking out reaction liquid at intervals, filtering out catalystAnd determining the tetracycline degradation efficiency by colorimetry according to the concentration change, and marking as 3 #.
The degradation efficiencies (1#, 2#, 3#) of TC were obtained by three examples, and the measurement results are shown in table 1 below.
TABLE 1 analysis results of TC degradation efficiency of catalysts of examples 1 to 3 in a reaction time of 60min
| 1# | 2# | 3# |
| 87％ | 81％ | 78％ |
As can be seen from the above table, in g-C3N4/Fe2O3The method for removing tetracycline antibiotics in the water body by the photo-Fenton water treatment method of the catalyst has the advantages of excellent degradation performance, simple operation and lower operation cost according to experimental and analytical results.
[ example 5 ] catalytic degradation of methyl orange
(1) g-C obtained in example 1 was mixed at a mass ratio of 4:100003N4/Fe2O3Adding into a solution with a concentration of 20mg L-1In the methyl orange water solution, controlling the reaction temperature to be 25 ℃, and continuously stirring to achieve adsorption balance;
(2) 70mmol L was added to the adsorption equilibrium system-1Hydrogen peroxide and starting a 300W xenon lamp to excite lambda>Visible light of 420nm, taking out reaction liquid at intervals, filtering out catalyst, and colorimetric methodAnd (3) measuring the concentration of methyl orange in the filtrate, determining the degradation efficiency of the methyl orange according to the change of the concentration, and finding that the degradation efficiency of the methyl orange reaches 93 percent within 60min of reaction time.
[ example 6 ] catalytic degradation of rhodamine B
(1) g-C obtained in example 1 was mixed at a mass ratio of 4:100003N4/Fe2O3Adding into a solution with a concentration of 20mg L-1In the rhodamine B water solution, controlling the reaction temperature to be 25 ℃, and continuously stirring to achieve adsorption balance;
(2) 70mmol L was added to the adsorption equilibrium system-1Hydrogen peroxide and starting a 300W xenon lamp to excite lambda>And (3) visible light of 420nm is taken out at intervals, the catalyst is filtered out, the concentration of rhodamine B in the filtrate is measured by a colorimetric method, the degradation efficiency of the rhodamine B is determined according to the concentration change, and the result shows that the degradation efficiency of the rhodamine B reaches 99% within 20min of reaction time.
[ example 7 ] catalytic degradation of phenol
(1) g-C obtained in example 1 was mixed at a mass ratio of 4:100003N4/Fe2O3Adding into a solution with a concentration of 20mg L-1In the phenol aqueous solution, controlling the reaction temperature to be 25 ℃, and continuously stirring to achieve adsorption balance;
(2) 70mmol L was added to the adsorption equilibrium system-1Hydrogen peroxide and starting a 300W xenon lamp to excite lambda>And (3) visible light of 420nm, taking out the reaction liquid at intervals, filtering out the catalyst, measuring the concentration of phenol in the filtrate by a liquid phase method, determining the degradation efficiency of the phenol according to the change of the concentration, and finding that the degradation efficiency of the phenol reaches 90% within 60min of reaction time.
[ COMPARATIVE EXAMPLE 1 ] with Fe2O3g-C in nanoparticle form3N4/Fe2O3Catalytic degradation of tetracycline
(1) Adding 30g urea into crucible, adding crucible cover, and heating at 2.5 deg.C for min-1Heating to 550 deg.C for 4h, adding the obtained product into the crucible again, without crucible cover, and heating at 2 deg.C for 2 min-1Heating to 500 ℃ for 2h to give g-C3N4Nanosheets;
(2) dissolving 0.675g ferric chloride in 37.5mL of a mixed solution of ammonia and water at a volume ratio of 1:2, transferring the resulting brown precipitate to a 50mL polytetrafluoroethylene-lined stainless steel autoclave, heating to 180 ℃ for 8h, washing with water and ethanol, and drying the resulting product to obtain Fe2O3Nanoparticles having a size between 90-110 nm;
(3) g-C obtained in step (1)3N4The nano-sheets are dispersed in ethanol solution with the concentration of 2.0g L-1Ultrasonically dispersing, and adding Fe obtained in the step (2) into the dispersion liquid2O3Nanoparticles at a concentration of 0.08g L-1Stirring for 6h, transferring the obtained dispersion to a stainless steel autoclave lined with polytetrafluoroethylene, heating to 150 deg.C for 4h, separating the product, washing with ethanol and drying to obtain Fe2O3g-C in nanoparticle form3N4/Fe2O3A complex;
(4) g-C obtained in the step (3) is mixed according to the mass ratio of 2:100003N4/Fe2O3Adding into a solution with a concentration of 20mg L-1In the tetracycline aqueous solution, controlling the reaction temperature to be 25 ℃, and continuously stirring to achieve adsorption balance;
(5) adding 50mmol L into the adsorption equilibrium system-1Hydrogen peroxide and starting a 300W xenon lamp to excite lambda>And (3) visible light of 420nm, taking out the reaction liquid at intervals, filtering out the catalyst, measuring the concentration of tetracycline in the filtrate by a colorimetric method, and determining the degradation efficiency of the tetracycline according to the change of the concentration, wherein the result shows that the degradation efficiency of the tetracycline is 47% within 60min of reaction time.
[ COMPARATIVE EXAMPLE 2 ] containing Fe2O3Nanorod-like g-C3N4/Fe2O3Catalytic degradation of tetracycline
(1) Adding 30g urea into crucible, adding crucible cover, and heating at 2.5 deg.C for min-1Is heated to 550 ℃ for 4 hours, and the product obtained is added again to the crucible withoutAdding crucible cover, and heating at 2 deg.C for min-1Heating to 500 ℃ for 2h to give g-C3N4Nanosheets;
(2) dissolving 0.7g of ferrous sulfate in 21mL, adding 6.0mL of hydrogen peroxide, stirring, transferring the resulting yellow suspension to a 50mL stainless steel autoclave lined with polytetrafluoroethylene, heating to 200 ℃ for 6h, separating, washing with water and ethanol, and drying the product to obtain Fe2O3A nanorod;
(3) g-C obtained in step (1)3N4The nano-sheets are dispersed in ethanol solution with the concentration of 2.0g L-1Ultrasonically dispersing, and adding Fe obtained in the step (2) into the dispersion liquid2O3Nanorod with concentration of 0.08g L-1Stirring for 6h, transferring the obtained dispersion to a 100mL stainless steel autoclave lined with Teflon, heating to 150 deg.C for 4h, separating the product, washing with ethanol and drying to obtain Fe-containing powder2O3Nanorod-like g-C3N4/Fe2O3A complex;
(4) g-C obtained in the step (3) is mixed according to the mass ratio of 2:100003N4/Fe2O3Adding into a solution with a concentration of 20mg L-1In the tetracycline aqueous solution, controlling the reaction temperature to be 25 ℃, and continuously stirring to achieve adsorption balance;
(5) adding 50mmol L into the adsorption equilibrium system-1Hydrogen peroxide and starting a 300W xenon lamp to excite lambda>And (3) visible light of 420nm, taking out the reaction liquid at intervals, filtering out the catalyst, measuring the concentration of tetracycline in the filtrate by a colorimetric method, and determining the degradation efficiency of the tetracycline according to the change of the concentration, wherein the result shows that the degradation efficiency of the tetracycline is 35% within 60min of reaction time.
[ COMPARATIVE EXAMPLE 3 ] with Fe2O3g-C of nanosheet morphology3N4/Fe2O3Catalytic degradation of tetracycline
(1) Adding 30g urea into crucible, adding crucible cover, and heating at 2.5 deg.C for min-1Heating to 550 ℃ for 4 hours, adding the obtained product into the crucible again,without adding crucible cover, and heating at 2 deg.C for min-1Heating to 500 ℃ for 2h to give g-C3N4Nanosheets;
(2) adding 0.68g ferric chloride into a mixed solution of 1.75mL water and 25mL ethanol, adding 2.0g sodium acetate, stirring to disperse uniformly, transferring the obtained dispersion into a 50mL stainless steel autoclave with a polytetrafluoroethylene lining, heating to 180 ℃ for 12h, separating, washing with water and drying the product to obtain Fe2O3Nanosheets.
(3) g-C obtained in step (1)3N4The nano-sheets are dispersed in ethanol solution with the concentration of 2.0g L-1Ultrasonically dispersing, and adding Fe obtained in the step (2) into the dispersion liquid2O3Nanosheets, concentration 0.08g L-1Stirring for 6h, transferring the obtained dispersion to a 100mL stainless steel autoclave lined with Teflon, heating to 150 deg.C for 4h, separating the product, washing with ethanol and drying to obtain Fe-containing powder2O3g-C of nanosheet morphology3N4/Fe2O3A complex;
(4) g-C obtained in the step (3) is mixed according to the mass ratio of 2:100003N4/Fe2O3Adding into a solution with a concentration of 20mg L-1In the tetracycline aqueous solution, controlling the reaction temperature to be 25 ℃, and continuously stirring to achieve adsorption balance;
(5) adding 50mmol L into the adsorption equilibrium system-1Hydrogen peroxide and starting a 300W xenon lamp to excite lambda>And (3) visible light of 420nm, taking out the reaction liquid at intervals, filtering out the catalyst, measuring the concentration of tetracycline in the filtrate by a colorimetric method, and determining the degradation efficiency of the tetracycline according to the change of the concentration, wherein the result shows that the degradation efficiency of the tetracycline is 57% within 60min of reaction time.
Comparative example 4 having Fe2O3g-C of sea urchin-like nanostructures3N4/Fe2O3Catalytic degradation of tetracycline
(1) Adding 30g urea into crucible, adding crucible cover, and heating at 2.5 deg.C for min-1Heating to 550 ℃ for 4h, and mixing the obtained solutionAdding the product into the crucible again without adding crucible cover, and heating at 2 deg.C for min-1Heating to 500 ℃ for 2h to give g-C3N4Nanosheets;
(2) adding 0.015mol of ferric chloride and 0.76mmol of ammonium sulfate into 30mL of water, stirring until the ferric chloride and the ammonium sulfate are dissolved, transferring the obtained solution into a 50mL stainless steel autoclave with a polytetrafluoroethylene lining, heating to 120 ℃ for 12h, separating, washing with water and ethanol, drying the product, heating the dried product in air to 600 ℃ at the speed of 2 ℃ min < -1 >, and keeping the temperature for 2h to obtain Fe2O3Sea urchin-like nanostructures.
(3) g-C obtained in step (1)3N4The nano-sheets are dispersed in ethanol solution with the concentration of 2.0g L-1Ultrasonically dispersing, and adding Fe obtained in the step (2) into the dispersion liquid2O3Sea urchin-like nanostructure with concentration of 0.08g L-1Stirring for 6h, transferring the obtained dispersion to a 100mL stainless steel autoclave lined with Teflon, heating to 150 deg.C for 4h, separating the product, washing with ethanol and drying to obtain Fe-containing powder2O3g-C of sea urchin-like nanostructures3N4/Fe2O3A complex;
(4) g-C obtained in the step (3) is mixed according to the mass ratio of 2:100003N4/Fe2O3Adding into a solution with a concentration of 20mg L-1In the tetracycline aqueous solution, controlling the reaction temperature to be 25 ℃, and continuously stirring to achieve adsorption balance;
(5) adding 50mmol L into the adsorption equilibrium system-1Hydrogen peroxide and starting a 300W xenon lamp to excite lambda>And (3) visible light of 420nm, taking out the reaction liquid at intervals, filtering out the catalyst, measuring the concentration of tetracycline in the filtrate by a colorimetric method, and determining the degradation efficiency of the tetracycline according to the change of the concentration, wherein the result shows that the degradation efficiency of the tetracycline is 37% within 60min of reaction time.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. Preparation of photo-Fenton catalyst g-C3N4/Fe2O3Characterized in that it comprises the following steps:
(1) taking a carbon nitride precursor for two-stage calcination to obtain g-C3N4Nanosheets;
(2) g to C3N4Adding the nanosheets into a solvent, ultrasonically dispersing, sequentially adding ferric nitrate and ammonium bicarbonate into a dispersion liquid, stirring, separating, washing and drying the obtained product, and then drying the dried product at the temperature of 1.0-5.0 ℃ for min-1Heating to 300-400 ℃ at the speed of (1), and keeping the temperature for 2-4 h to obtain g-C3N4/Fe2O3。
2. The method according to claim 1, wherein the carbon nitride precursor in step (1) is any one or more of urea, melamine, thiourea and dicyanodiamine.
3. The process according to claim 1, characterized in that the two-stage calcination in step (1) is carried out as follows: first stage calcination: covering the carbon nitride precursor for calcining at the temperature of 1.0-5.0 ℃ for min-1Heating to 550 ℃ at the speed of the temperature, and keeping the temperature for 2-4 h; and (3) second-stage calcination: re-calcining the product obtained in the first stage of calcination, wherein the calcination process is carried out without covering a cover and the temperature is 1.0-5.0 ℃ for min-1Heating to 500 ℃ at the speed of (1), and keeping the temperature for 2-4 h to obtain g-C3N4Nanosheets.
4. The method according to claim 1, wherein the solvent in step (2) is an ethanol solution.
5. The method according to claim 1, wherein g-C is contained in the solvent in the step (2)3N4The concentration of (b) is 1.0-10.0 g/L.
6. The method according to claim 1, wherein the concentration of ferric nitrate in the dispersion liquid in the step (2) is 1.0-10.0 mol/L, and the concentration of ammonium bicarbonate is 3.0-30.0 mol/L.
7. photo-Fenton catalyst g-C prepared by the method according to any one of claims 1 to 63N4/Fe2O3。
8. The photo-Fenton catalyst of claim 7 g-C3N4/Fe2O3The application in degrading organic pollutant in water.
9. The application according to claim 8, characterized in that the method of application is as follows:
(1) subjecting photo-Fenton catalyst g-C3N4/Fe2O3Adding the mixture into an aqueous solution of organic pollutants, controlling the reaction temperature to be 5-40 ℃, and continuously stirring to achieve adsorption balance;
(2) adding hydrogen peroxide into an adsorption equilibrium system, starting a xenon lamp to excite visible light with lambda being more than 420nm, taking out reaction liquid at intervals, filtering out a catalyst, measuring the concentration of organic pollutants in filtrate by using a colorimetric method, and determining the degradation efficiency of the organic pollutants according to the change of the concentration.
10. The use according to claim 9, wherein the hydrogen peroxide is added in the step (2) in an amount of 20 to 70mmol L-1。
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