CN112090425A - Magnetic carbon-supported TiO2Photocatalyst and preparation method thereof - Google Patents
Magnetic carbon-supported TiO2Photocatalyst and preparation method thereof Download PDFInfo
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- CN112090425A CN112090425A CN202011016456.9A CN202011016456A CN112090425A CN 112090425 A CN112090425 A CN 112090425A CN 202011016456 A CN202011016456 A CN 202011016456A CN 112090425 A CN112090425 A CN 112090425A
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- 238000002360 preparation method Methods 0.000 title claims description 29
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 88
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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Abstract
The invention provides a magnetic carbon-supported TiO2Photocatalyst of Fe3O4Coated with said Fe3O4Carbon material on surface, and TiO supported on surface of the carbon material2. The invention takes the carbon material as the carrier, is beneficial to TiO2Thereby improving the catalytic performance of the photocatalyst; with Fe3O4As magnetic core, Fe is mixed with carbon material3O4And TiO2The photocatalyst is tightly combined together, so that the photocatalyst has stronger magnetism, and the recycling of the photocatalyst is facilitated. The results of the examples show that the magnetic carbon supported TiO provided by the invention2The photocatalyst catalyzes and degrades methylene blue under the irradiation of ultraviolet light, and the degradation rate can reach 99.61%; meanwhile, the magnetic carbon-supported T provided by the inventioniO2The recovery rate of the photocatalyst can reach 98.57%, and the photocatalyst still has good catalytic effect after being recycled for 8 times.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to magnetic carbon-supported TiO2A photocatalyst and a preparation method thereof.
Background
With the increasing severity of environmental and energy issues, more and more researchers are working on the photocatalytic catalytic oxidative degradation of harmful and toxic pollutants in semiconductors. TiO 22As a basic N-type semiconductor material, the material has special crystal structure and surface structure, has the advantages of low price, strong photocatalytic activity, stable chemical property, wide application range, low dissolution rate, no toxicity and the like, is an important raw material of the photocatalyst, but TiO is used as a raw material2There are also some limitations for use in photocatalysts.
First, TiO2The forbidden band width of the catalyst is large, and the electron hole recombination probability is high in the photoreaction process, so that the photocatalytic efficiency is low, and the photocatalytic performance of the catalyst is weak; second, TiO2TiO with smaller particle size, stronger catalytic performance, but smaller particle size2The lighter the weight, the more difficult the recovery, the low repeated utilization rate, and the incomplete recovery easily causes secondary pollution. Therefore, the photocatalyst with strong photocatalytic performance and easy recovery is designed to be TiO2Is used for the photocatalyst and needs to solve one of the problems.
Disclosure of Invention
The invention aims to provide magnetismCarbon supported TiO2Photocatalyst and preparation method thereof, and magnetic carbon-supported TiO provided by the invention2The photocatalyst has higher photocatalytic performance and recycling rate.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a magnetic carbon-supported TiO2Photocatalyst of Fe3O4Coated with said Fe3O4Carbon material on surface, and TiO supported on surface of the carbon material2。
Preferably, the Fe3O4The particle size of the carbon material is 15-45 nm, and the thickness of the carbon material is 1-20 nm.
Preferably, the TiO is2The particle size of (A) is 83-121 nm; magnetic carbon supported TiO2Mass of photocatalyst, said TiO2The loading rate of (A) is more than 79%.
The invention provides the technical scheme of the magnetic carbon-supported TiO2The preparation method of the photocatalyst comprises the following steps:
preparing carbon-coated Fe by a hydrothermal method3O4；
Coating the carbon with Fe3O4And TiO2Mixing the sol and obtaining the magnetic carbon-carried TiO by ultrasonic2A photocatalyst.
Preferably, the hydrothermal method is in particular:
a. mixing ferric chloride, polyvinylpyrrolidone and water to obtain a mixed solution;
b. mixing the mixed solution obtained in the step a with hydrazine hydrate and sodium hydroxide, and carrying out oxidation-reduction reaction to obtain Fe3O4；
c. The Fe obtained in the step b is3O4Mixing with carbon source and water, and heating to obtain carbon-coated Fe3O4。
Preferably, the ratio of the amount of ferric chloride in the step a to the amount of hydrazine hydrate in the step b is (1-3): 1; the mass ratio of ferric chloride in the step a to sodium hydroxide in the step b is 1 (4-8).
Preferably, the carbon source in step c comprises starch, glucose or sucrose.
Preferably, the carbon source is mixed with Fe in step c3O4The ratio of the amounts of the substances (9-36) to (1).
Preferably, the heating temperature in the step c is 180-200 ℃, and the heating time is 6-24 hours.
Preferably, the carbon-coated Fe3O4Mass of and TiO2The volume ratio of the sol is 1 (40-50).
The invention provides a magnetic carbon-supported TiO2Photocatalyst of Fe3O4Coated with said Fe3O4Carbon material on surface, and TiO supported on surface of the carbon material2. The carbon material is used as a carrier, has good dispersibility in water, and is beneficial to TiO2Thereby improving the catalytic performance of the photocatalyst; with Fe3O4As magnetic core, Fe is mixed with carbon material3O4And TiO2The photocatalyst is tightly combined together, so that the photocatalyst has stronger magnetism, and the recycling of the photocatalyst is facilitated. The results of the examples show that the magnetic carbon supported TiO provided by the invention2The photocatalyst catalyzes and degrades methylene blue under the irradiation of ultraviolet light, the catalytic reaction can be completed within 10min, and the degradation rate can reach 99.61%; meanwhile, the magnetic carbon-supported TiO provided by the invention2The recovery rate of the photocatalyst can reach 98.57%, and the photocatalyst still has good catalytic effect after being recycled for 8 times.
The invention provides magnetic carbon-supported TiO2The preparation method of the photocatalyst has the advantages of simple operation and mild reaction conditions, and is suitable for large-scale production.
Drawings
FIG. 1 shows Fe prepared in example 1 of the present invention3O4SEM picture of (1);
FIG. 2 shows TiO prepared in example 1 of the present invention2SEM picture of (1);
FIG. 3 shows carbon-coated Fe prepared in example 1 of the present invention3O4SEM picture of (1);
FIG. 4 shows the present inventionMagnetic carbon-supported TiO prepared in example 12SEM image of photocatalyst;
FIG. 5 shows Fe prepared in example 1 of the present invention3O4EDS energy spectrum of (a);
FIG. 6 shows TiO prepared in example 1 of the present invention2EDS energy spectrum of (a);
FIG. 7 shows carbon-coated Fe prepared in example 1 of the present invention3O4EDS energy spectrum of (a);
FIG. 8 shows the magnetic carbon-supported TiO prepared in example 1 of the present invention2EDS energy spectrum of photocatalyst;
FIG. 9 shows carbon-coated Fe prepared in example 1 of the present invention3O4A TEM image of (B);
FIG. 10 shows the magnetic carbon-supported TiO prepared in example 1 of the invention2TEM images of the photocatalyst;
FIG. 11 shows Fe prepared in example 1 of the present invention3O4Carbon-coated Fe3O4And magnetic carbon-supported TiO2Pore size distribution of the photocatalyst;
FIG. 12 shows Fe prepared in example 1 of the present invention3O4Carbon-coated Fe3O4And magnetic carbon-supported TiO2Hysteresis loop diagram of photocatalyst;
FIG. 13 shows Fe prepared in example 1 of the present invention3O4Carbon-coated Fe3O4And magnetic carbon-supported TiO2Adsorption-desorption isotherm diagram of the photocatalyst;
FIG. 14 shows the magnetic carbon-supported TiO prepared in example 1 of the invention2A recovery rate and recycling curve chart of the photocatalyst;
FIG. 15 shows the magnetic carbon-supported TiO prepared in example 1 of the invention2The distribution of the photocatalyst in water;
FIG. 16 shows the magnetic carbon-supported TiO prepared in example 1 of the invention2The distribution condition of the photocatalyst under an external magnetic field;
FIG. 17 shows the magnetic carbon-supported TiO prepared in example 1 of the invention2And (3) distribution of the photocatalyst under an external magnetic field.
Detailed Description
The invention provides a magnetic carbon-supported TiO2Photocatalyst of Fe3O4Coated with said Fe3O4Carbon material on surface, and TiO supported on surface of the carbon material2。
The invention provides magnetic carbon-supported TiO2The photocatalyst comprises Fe3O4. In the invention, Fe3O4As magnetic core, Fe is mixed with carbon material3O4Magnetic core and TiO2The photocatalyst is tightly combined together, so that the photocatalyst has stronger magnetism, and the recycling of the photocatalyst is facilitated. In the present invention, the Fe3O4The particle size of (A) is preferably 15 to 45nm, more preferably 15 to 21 nm.
The invention provides magnetic carbon-supported TiO2The photocatalyst comprises the coating of the Fe3O4A carbon material on the surface. The carbon material is used as a carrier, has good dispersibility in water, and is beneficial to TiO2Thereby improving the catalytic performance of the photocatalyst. Meanwhile, the carbon material is used as an inert isolating layer, and Fe is used as an inert isolating layer3O4And TiO2Are tightly combined together to effectively realize TiO2Increases the service life of the catalyst and improves the Fe3O4With TiO2The defects of magnetic core corrosion and loss occur after direct contact. And, the stability of the carbon material ensures Fe3O4Stability of the magnetic core, in turn facilitating magnetic carbon-supported TiO2And (4) recovering the photocatalyst. In the present invention, the thickness of the carbon material is preferably 1 to 20nm, and more preferably 1 to 15 nm.
The invention provides magnetic carbon-supported TiO2The photocatalyst comprises TiO loaded on the surface of the carbon material2. In the present invention, TiO2As a main photocatalytic material, the material has the advantages of low price, strong photocatalytic activity and the like, and the carbon material and Fe are used3O4After combination, the magnetic carbon-supported TiO with higher photocatalytic performance and recycling rate is obtained2A photocatalyst. In the present invention, the TiO is2Has excellent particle diameterThe particle size is preferably 83 to 121nm, more preferably 98 to 121 nm. In the present invention, TiO is carried by magnetic carbon2Mass of photocatalyst, said TiO2The loading of (b) is preferably > 79%, more preferably > 86%.
The invention provides magnetic carbon-supported TiO2The photocatalyst takes carbon material as a carrier and is beneficial to TiO2Thereby improving the catalytic performance of the photocatalyst; with Fe3O4As magnetic core, Fe is mixed with carbon material3O4And TiO2The photocatalyst is tightly combined together, so that the photocatalyst has stronger magnetism, and the recycling of the photocatalyst is facilitated.
The invention provides the technical scheme of the magnetic carbon-supported TiO2The preparation method of the photocatalyst comprises the following steps:
preparing carbon-coated Fe by a hydrothermal method3O4；
Coating the carbon with Fe3O4And TiO2Mixing the sol and obtaining the magnetic carbon-carried TiO by ultrasonic2A photocatalyst.
The invention prepares the carbon-coated Fe by a hydrothermal method3O4. In the invention, hydrothermal method is adopted to prepare carbon-coated Fe3O4In which Fe is present3O4Almost no magnetic hysteresis, superparamagnetism, and Fe-to-carbon material3O4The coating effect is good, the coating rate is high, and the magnetic carbon-supported TiO with high photocatalytic performance and high recycling rate is favorably obtained2A photocatalyst.
In the present invention, the hydrothermal method is particularly preferably:
a. mixing ferric chloride, polyvinylpyrrolidone and water to obtain a mixed solution;
b. mixing the mixed solution obtained in the step a with hydrazine hydrate and sodium hydroxide, and carrying out oxidation-reduction reaction to obtain Fe3O4；
c. The Fe obtained in the step b is3O4Mixing with carbon source and water, and heating to obtain carbon-coated Fe3O4。
In the present invention, it is preferable to mix ferric chloride, polyvinylpyrrolidone and water to obtain a mixed solution. The operation of mixing the ferric chloride, the polyvinylpyrrolidone and the water is not particularly limited in the present invention, and a technical scheme for preparing a mixed solution, which is well known to those skilled in the art, may be adopted. In the invention, the mixing of the ferric chloride, the polyvinylpyrrolidone and the water is preferably carried out under the condition of stirring, and the stirring speed is preferably 100-400 r/min, and more preferably 200-300 r/min; the stirring time is preferably 20-50 min, and more preferably 30-40 min.
In the present invention, the mass ratio of the ferric chloride to the polyvinylpyrrolidone is preferably (1-2): 1, and more preferably (1.5-2): 1. In the present invention, the volume ratio of the total mass of the ferric chloride and the polyvinylpyrrolidone to the water is preferably (1.2 to 1.4) g:50mL, and more preferably (1.25 to 1.3) g:50 mL. In the invention, the polyvinylpyrrolidone is used as the surfactant, which is beneficial to increasing the solubility of the ferric chloride and further accelerating the dissolution of the ferric chloride.
After obtaining the mixed solution, the invention preferably mixes the mixed solution with hydrazine hydrate and sodium hydroxide, and obtains Fe through oxidation-reduction reaction3O4. The operation of mixing the mixed solution with hydrazine hydrate and sodium hydroxide is not particularly limited in the present invention, and a technical scheme for preparing a mixture, which is well known to those skilled in the art, may be adopted. In the invention, preferably, the mixed solution is mixed with hydrazine hydrate and then mixed with sodium hydroxide. In the present invention, the hydrazine hydrate is preferably added in the form of an aqueous solution of hydrazine hydrate. In the invention, the concentration of the hydrazine hydrate aqueous solution is preferably 70-85%, and more preferably 80-85%. In the present invention, the sodium hydroxide is preferably prepared into a sodium hydroxide solution and then mixed with the mixed solution. In the invention, the concentration of the sodium hydroxide solution is preferably 1-3 mol.L-1More preferably 2 mol. L-1. The method for preparing the sodium hydroxide solution is not particularly limited in the present invention, and a method for preparing a solution known to those skilled in the art may be used. In a specific embodiment of the present invention, the amount of the hydrazine hydrate aqueous solution is preferably 12.5mL, and the amount of the sodium hydroxide solution is preferably 15 mL.
In the invention, the mass ratio of the ferric chloride to the hydrazine hydrate is preferably (1-3) to 1, more preferably (1-2) to 1; the mass ratio of the ferric chloride to the sodium hydroxide is preferably 1 (4-8), and more preferably 1 (6-8).
In the present invention, the reaction process of the redox reaction is as follows:
N2H4·H2O+4FeCl3＝N2↑+4FeCl2+4HCl+H2O
8OH-+Fe2++2Fe3+＝Fe3O4↓+4H2O
in the invention, the temperature of the oxidation-reduction reaction is preferably 160-180 ℃, and more preferably 180 ℃; the time of the oxidation-reduction reaction is preferably 4-6 h, and more preferably 6 h.
After the redox reaction is finished, the invention preferably carries out centrifugation and washing on the products of the redox reaction in sequence to obtain Fe3O4. The operation of the centrifugation and washing in the present invention is not particularly limited, and a centrifugation and washing method known to those skilled in the art may be used. In the invention, the rotation speed of the centrifugation is preferably 1200-1600 r/min, and more preferably 1300-1500 r/min; the time for centrifugation is preferably 10-20 min, and more preferably 10-15 min. In the present invention, the washing detergent is preferably distilled water and absolute ethanol; the washing is preferably: washing with distilled water and absolute ethyl alcohol alternately for 3-5 times.
To obtain Fe3O4Then, the present invention preferably uses the Fe3O4Mixing with carbon source and water, and heating to obtain carbon-coated Fe3O4. In the present invention for said Fe3O4The operation of mixing with the carbon source and water is not particularly limited, and a method for preparing a mixture, which is well known to those skilled in the art, may be employed. In the present invention, the carbon source preferably includes starch, glucose or sucrose, more preferably glucose or sucrose, and most preferably glucose. In the present invention, the Fe3O4And a source of carbonThe volume ratio of the total mass to the water is preferably (1.5-2.0) g: (400-500) mL.
In the present invention, the carbon source is mixed with Fe3O4The ratio of the amounts of the substances (A) to (B) is preferably (9-36): 1, more preferably (9-18): 1, and most preferably 9: 1. The invention combines the carbon source with Fe3O4The amount ratio of the substances is controlled within the range, which is beneficial to obtaining the magnetic carbon-supported TiO with high photocatalysis performance and recycling rate2A photocatalyst.
In the invention, the heating temperature is preferably 180-200 ℃, and more preferably 180 ℃; the heating time is preferably 6-24 hours, and more preferably 12-24 hours. The invention completes the reaction of the carbon material to Fe by heating3O4The carbon material is well coated on the Fe3O4The surface and the carbon coating rate are high.
After the heating is finished, the invention preferably carries out centrifugation, washing and drying on the heated product in sequence to obtain the carbon-coated Fe3O4. The operation of the centrifugation, washing and drying is not particularly limited in the present invention, and the technical scheme of the centrifugation, washing and drying known to those skilled in the art can be adopted. In the invention, the rotation speed of the centrifugation is preferably 1200-1600 r/min, and more preferably 1300-1500 r/min; the time for centrifugation is preferably 10-20 min, and more preferably 10-15 min. In the present invention, the washing detergent is preferably distilled water and ethanol; the washing is preferably: washing with distilled water and ethanol for 3-5 times respectively. In the invention, the drying temperature is preferably 60-80 ℃, and more preferably 60 ℃; the drying time is preferably 40-80 min, and more preferably 60-70 min.
To obtain carbon-coated Fe3O4Then, the invention coats the carbon with Fe3O4And TiO2Mixing the sol and obtaining the magnetic carbon-carried TiO by ultrasonic2A photocatalyst.
The invention is directed to the TiO2The method for preparing the sol is not particularly limited, and TiO can be prepared by a method well known to those skilled in the art2The technical scheme of the sol is as follows. In the present invention, the TiO is2The method of preparation of the sol is preferably a hydrolysis method.
In the present invention, the hydrolysis method is particularly preferably: the tetra-n-butyl titanate and isopropanol are hydrolyzed to obtain TiO2And (3) sol. In the present invention, the volume ratio of tetra-n-butyl titanate to isopropyl alcohol is preferably 3: 1.
In the present invention, the hydrolysis reaction of tetra-n-butyl titanate with isopropanol is preferably carried out in secondary distilled water. In the invention, the hydrolysis reaction is preferably carried out under the condition of stirring, and the stirring speed is preferably 400-600 r/min, and more preferably 400-500 r/min; the stirring time is preferably sufficient to completely hydrolyze the tetrabutyl titanate. In a specific embodiment of the present invention, the pH of the redistilled water is preferably adjusted to 2.5, and the reagent for adjusting the pH of the redistilled water is preferably concentrated HNO3The dosage of the secondary distilled water is preferably 200 mL; the addition rate of the mixed solution of tetra-n-butyl titanate and isopropanol is preferably 2 mL/min.
After the hydrolysis reaction is finished, the pH value of the solution after the hydrolysis reaction is finished is preferably adjusted to 2.5 in the invention, so as to prevent the change of acidity and the precipitation phenomenon of tetra-n-butyl titanate. After the pH adjustment is finished, the solution after the hydrolysis reaction is preferably stirred in a reflux device at the constant temperature of 75 ℃ for 24 hours to obtain TiO2And (3) sol. In the invention, the stirring speed is preferably 300-500 r/min, and more preferably 400 r/min.
To obtain TiO2After sol-gel, the application will coat the carbon with Fe3O4And TiO2The sols were mixed to obtain a mixture. The invention covers the carbon with Fe3O4And TiO2The operation of mixing the sol is not particularly limited, and a technical scheme for preparing a mixture, which is well known to those skilled in the art, may be employed. In the present invention, the carbon-coated Fe3O4Mass of and TiO2The volume ratio of the sol is preferably 1 (40-50), more preferably 1 (40-45).
After the mixture is obtained, the mixture is subjected to ultrasonic treatment to obtain the magnetic carbon-supported TiO2A photocatalyst. In the invention, the rotation speed of the ultrasonic is preferably 1300-1600 r/min, and more preferably 1400-1500 r/min; the ultrasonic treatment time is preferably 40-80 min, and more preferably 50-60 min.
After the ultrasonic treatment is finished, the invention preferably carries out distillation and drying on the ultrasonic treated product in sequence to obtain the magnetic carbon-supported TiO2A photocatalyst. The distillation and drying operation is not particularly limited in the present invention, and the distillation and drying technical scheme known to those skilled in the art can be adopted. In the invention, the distillation is preferably reduced pressure distillation, so that the product can be distilled at a lower temperature, and the product is prevented from being decomposed; and a high-temperature heating device is not needed, so that energy is saved. In the invention, the distillation temperature is preferably 60-75 ℃, and more preferably 65-75 ℃. In the invention, the drying temperature is preferably 60-80 ℃, and more preferably 60 ℃; the drying time is preferably 40-80 min, and more preferably 60-70 min.
The magnetic carbon-supported TiO prepared by the preparation method provided by the invention2The photocatalyst has higher photocatalytic performance and recycling rate, and the preparation method is simple to operate, mild in reaction conditions and suitable for large-scale production.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Carbon coated Fe3O4The preparation of (1):
0.75g of FeCl was taken30.5g of polyvinylpyrrolidone is put into 50mL of distilled water (the mass ratio of the ferric chloride to the polyvinylpyrrolidone is 1.5:1, and the volume ratio of the total mass of the ferric chloride to the polyvinylpyrrolidone to the water is 1.25 g:50 mL), stirred for 30min at the rotating speed of 200r/min, and then 12.5mL of 80% hydrazine hydrate aqueous solution and 15mL of 2 mol.L are added-1Hydrogen and oxygen ofDissolving sodium solution (the mass ratio of ferric chloride to hydrazine hydrate is 1:1, the mass ratio of ferric chloride to sodium hydroxide is 1:8, keeping at 180 ℃ for 6h, cooling, centrifuging at 1500r/min for 10min, and washing with distilled water and anhydrous ethanol for 3 times to obtain Fe3O4；
Mixing 1.35g glucose with the above Fe3O4Mixing (carbon source with Fe3O4The mass ratio of the substances is 9:1), adding 400mL of distilled water, keeping the temperature in an oven at 180 ℃ for 12h after glucose is completely dissolved, cooling to room temperature, centrifuging at a rotating speed of 1500r/min for 10min, washing with distilled water and ethanol for three times respectively, and drying in the oven at 60 ℃ for 60min to obtain carbon-coated Fe3O4Is denoted as Fe3O4-a PC binary complex;
(2)TiO2preparing sol:
taking 24mL of tetra-n-butyl titanate in 8mL of isopropanol solution (the volume ratio of the tetra-n-butyl titanate to the isopropanol is 3:1), adding the mixed solution to the concentrated HNO at the speed of 2mL/min3Stirring 200mL of secondary distilled water with the pH value adjusted to 2.5 at the rotating speed of 400r/min until the tetrabutyl titanate is completely hydrolyzed, then adjusting the pH value of the solution after reaction to 2.5, and finally stirring in a reflux device at the constant temperature of 75 ℃ for 24 hours to obtain TiO2Sol, wherein the stirring speed is 400 r/min;
(3) magnetic carbon-supported TiO2Preparation of the photocatalyst:
coating 1g of carbon with Fe3O4And 40ml of TiO2Sol (carbon coated Fe)3O4Mass of and TiO2The volume ratio of the sol is 1:40), performing ultrasonic treatment for 60min at the rotating speed of 1500r/min, performing reduced pressure distillation at 75 ℃ to obtain powder, and drying at 60 ℃ for 60min to obtain magnetic carbon-supported TiO2Photocatalyst, noted as Fe3O4-PC-TiO2A ternary complex.
Comparative example 1
Using the same starting materials and preparation as in example 1, glucose was replaced with starch and carbon coating was preparedFe3O4In the process, after the starch is completely dissolved, the temperature is kept for 6h in an oven at 180 ℃.
Example 2
Using the same starting materials and preparation method as in example 1, glucose was replaced by starch, and a carbon source was added to Fe3O4The ratio of the amounts of substances of (a) is replaced by 18: 1.
Example 3
Using the same starting materials and preparation method as in example 1, glucose was replaced by starch, and a carbon source was added to Fe3O4Is replaced by 36:1, and in the preparation of carbon-coated Fe3O4In the process, after the starch is completely dissolved, the temperature is kept for 24 hours in an oven at 180 ℃.
Example 4
Using the same raw materials and preparation methods as in example 1, a carbon source was mixed with Fe3O4Is replaced by 18:1, and in the preparation of carbon-coated Fe3O4In the process, after the starch is completely dissolved, the temperature is kept for 24 hours in an oven at 180 ℃.
Example 5
Using the same raw materials and preparation methods as in example 1, a carbon source was mixed with Fe3O4Is replaced by 36:1, and in the preparation of carbon-coated Fe3O4In the process, after the starch is completely dissolved, the temperature is kept for 6h in an oven at 180 ℃.
Example 6
Using the same raw materials and preparation method as in example 1, glucose was replaced with sucrose, and Fe was coated with carbon in preparation of carbon3O4In the process, after the starch is completely dissolved, the temperature is kept for 24 hours in an oven at 180 ℃.
Example 7
Using the same starting materials and preparation method as in example 1, glucose was replaced with sucrose, and a carbon source was added with Fe3O4Is replaced by 18:1, and in the preparation of carbon-coated Fe3O4In the process, after the starch is completely dissolved, the temperature is kept for 6h in an oven at 180 ℃.
Example 8
Using the same starting materials and preparation method as in example 1, glucose was replaced with sucrose, and a carbon source was added with Fe3O4The ratio of the amounts of substances of (a) is replaced by 36: 1.
FIGS. 1 to 4 show Fe obtained in example 13O4、TiO2Carbon-coated Fe3O4And magnetic carbon-supported TiO2SEM image of photocatalyst. FIG. 1 is Fe3O4The SEM image of (1) shows that the sample presents cluster-shaped spherical shapes and is distributed tightly and regularly; FIG. 2 is TiO2The SEM image of (1) can see that the sample has no clear structure, is irregularly distributed and has black spots, and is probably titanium atoms; FIG. 3 is a carbon-coated Fe3O4SEM picture of (1), Fe can be seen3O4The agglomerated mixture is wrapped in a carbon material; FIG. 4 shows the magnetic carbon-supported TiO prepared in example 12In the SEM image of the photocatalyst, the sample can be seen to be in a random block shape.
FIGS. 5 to 8 show Fe obtained in example 13O4、TiO2Carbon-coated Fe3O4And magnetic carbon-supported TiO2EDS energy spectrum of photocatalyst. It can be seen that FIG. 5 contains Fe element and O element, indicating that Fe is obtained3O4FIG. 6 contains Ti and O, indicating that TiO is obtained2FIG. 7 shows that the content of C element is higher than that of the former element in addition to Fe element and O element, indicating that Fe3O4The carbon layer is arranged on the outer layer of the nano particle, and the carbon layer contains Fe, O, C and Ti elements in figure 8 at the same time, which shows that the magnetic carbon-supported TiO is obtained2A photocatalyst.
FIGS. 9 to 10 show Fe obtained in example 13O4Binary complexes of-PC with Fe3O4-PC-TiO2TEM image of ternary complex, FIG. 9 shows Fe3O4The agglomerated Fe particles are coated in the carbon material, and no single Fe is observed3O4Particles and carbon spheres, illustrating the method for preparing carbon-coated Fe3O4Is very effective. Fe can be clearly seen from FIG. 103O4Carbon layer and TiO2Fe doped with a carbon layer3O4And TiO2Tightly combined togetherTogether.
FIG. 11 shows Fe obtained in example 13O4、Fe3O4-PC binary complex and Fe3O4-PC-TiO2Pore size distribution of ternary complex. As can be seen from the figure, Fe is present in 3 different materials3O4、Fe3O4The peak width of the-PC binary compound is not wide, which indicates that the material is in a non-porous or less-porous state, and Fe3O4-PC-TiO2When the aperture of the ternary complex is 2-7 nm, the number of the pores is increased along with the increase of the aperture, which shows that the number of the pores in the area is large and the aperture is uniform, and the pores with the largest number are distributed at the position of 4 nm. Table 1 shows the pore size parameters of the 3 materials, as can be seen from Table 1, Fe3O4-PC-TiO2The ternary compound has large specific surface area and pore volume, other materials are small, and Fe3O4-PC-TiO2The pore diameter of the ternary complex is the smallest, which indicates the Fe obtained finally3O4-PC-TiO2Ternary complex phase ratio of Fe3O4And Fe3O4The PC binary compound has a small pore structure, but has uniform pore diameter and a large number, and lays a foundation for good adsorption performance in the later period.
TABLE 1 Fe3O4、Fe3O4-PC binary complex and Fe3O4-PC-TiO2Pore size structural parameters of ternary complexes
FIG. 12 shows Fe obtained in example 13O4、Fe3O4-PC binary complex and Fe3O4-PC-TiO2The magnetic hysteresis curve chart of the ternary compound is obtained by measuring the magnetic property of a material by using a vibration sample magnetometer VSM. In the figure, curve a represents Fe3O4The initial magnetic effect was that the saturation magnetization was 2.9804emu · g-1. With Fe3O4Carbon material and TiO2The saturation magnetization of the material decreases in sequence, and the curves b and c are Fe3O4Binary complexes of-PC with Fe3O4-PC-TiO2The magnetic performance effect and saturation intensity of the ternary complex are respectively 1.6002emu g-1And 0.5984emu g-1The saturation magnetization is caused by coating the carbon material and TiO2But gradually decreases due to the combined effect of the blocking of magnetization by the cladding layer and the decrease in the proportion of the magnetic component.
FIG. 13 shows Fe obtained in example 13O4、Fe3O4-PC binary complex and Fe3O4-PC-TiO2Adsorption-desorption isotherm diagram of the ternary complex. Wherein, the curves a and b are respectively magnetic nucleus Fe3O4、Fe3O4An adsorption-desorption isotherm of a binary compound of-PC, of type III, with a concave isotherm, both of which are at N2The relative pressure of (A) after 0.6-0.7 shows that the adsorption quantity is along with the relative pressure P/P0The curve is concave because the interaction between the molecules of the adsorbate is stronger than that between the adsorbate and the adsorbent, and the heat of adsorption of the first layer is smaller than the heat of liquefaction of the adsorbate, so that the adsorbate is difficult to adsorb at the initial stage of adsorption, and the adsorption is self-accelerated along with the proceeding of the adsorption process, and the number of adsorption layers is not limited. Curve c is Fe3O4-PC-TiO2The adsorption-desorption isotherm of the ternary complex belongs to type IV, N2When the relative pressure of the pressure sensor is between 0.4 and 0.7, H appears on an adsorption-desorption isotherm2A type hysteresis loop, which indicates that the ternary complex has rich mesoporous structure, N2Capillary condensation exists in the pore channels, and adsorption and desorption are irreversible processes.
FIG. 14 shows a magnetic carbon-supported TiO prepared in example 1 of the present invention2Recovery and recycle of the photocatalyst are plotted. It can be seen that after repeated recycling, the magnetic carbon-supported TiO prepared by the invention2The recovery rate of the photocatalyst still exceeds 98.00 percent, the first recovery rate is as high as 99.12 percent, the subsequent recovery rate is basically stable, and the recovery rate begins to decline after the photocatalyst is recycled for 7 times. At the same time, recycle the first 7 timesThe complete catalytic degradation time of the methylene blue is kept within 10min all the time, and the complete catalytic degradation time is prolonged from the 8 th time of recycling, which shows that the catalytic performance of the material is reduced.
FIG. 15 shows the magnetic carbon-supported TiO prepared in example 12Distribution of photocatalyst in Water, FIGS. 16-17 show the magnetic carbon-supported TiO prepared in example 12And (3) distribution of the photocatalyst under an external magnetic field. An appropriate amount of the magnetic carbon-supported TiO prepared in example 1 was taken2The photocatalyst is placed in water, and after 10min of ultrasonic treatment, the magnetic carbon carries TiO2The distribution of the photocatalyst in water is shown in fig. 15. Taking the magnet on the sample side, the sample was attracted to the magnet side, and only a small amount of the sample was dispersed in the water, as shown in fig. 16, 17. Thus, the magnetic carbon-supported TiO prepared by the invention2The photocatalyst has stronger magnetism, and is beneficial to the recycling of samples.
Performance testing
1. Determination of carbon coating ratio
(1) Iron standard solution (10 mg. mL)-1) The preparation of (1): take 0.8gNH4Fe(SO4)2·12H2O, using 30mL of 2 mol. L-1Dissolving the HCl solution, transferring the solution into a 1L volumetric flask, diluting the solution to a scale with deionized water, and shaking up; then, 50mL of the solution was taken out and put into a 500mL volumetric flask, and 20mL of 2 mol. L was added-1Diluting the HCl solution to a scale with deionized water, and shaking up for later use;
10 percent of hydroxylammonium hydrochloride aqueous solution and 0.15 percent of phenanthroline hydrochloride aqueous solution for later use.
(2) Drawing an iron standard curve: respectively taking 0mL, 2.0mL, 4.0 mL, 6.0 mL, 8.0 mL, 10.0mL and 12.0mL of the iron standard solution in a 50mL volumetric flask, and then adding 1mL of 10% hydroxylammonium chloride aqueous solution and 5mL of 1 mol.L-1The sodium acetate aqueous solution and 2mL of 0.15 percent o-diazaphenanthrene aqueous solution are subjected to constant volume and standing for 10 min. Measuring absorbance of each solution at 510nm wavelength with 0mL iron standard solution as blank, and making standard curve to obtain linear equation of y-225.56 x +0.0236, R2＝0.9908。
(3) Sample detection: 1g of Fe is taken3O4And (3) soaking the binary-PC compound in a beaker by using concentrated HCl for 3h, then diluting to 1000mL, centrifuging the sample liquid at the rotating speed of 1500r/min for 0.5h to obtain filtrate, and metering to 1000 mL. 50mL of the solution was diluted 50 times, and 1mL of 10% aqueous solution of hydroxylammonium chloride and 5mL of 1 mol. L were added in this order-12mL of 0.15% o-diazaphenanthrene aqueous solution; diluting the mixture to a scale with deionized water, standing for 10min, measuring absorbance at the wavelength of 510nm, and calculating the carbon coating rate.
(4) Calculating the carbon coating rate: carbon coating rate m2/m1In the formula m1Is Fe3O4Mass of (c), m2Is undissolved Fe3O4The quality of (c).
2.TiO2Determination of the load factor
(1) Titanium Standard solution (100. mu.g.mL)-1) The preparation of (1): 0.2g of TiO was taken2、5g(NH4)2SO48mL of concentrated H2SO4Heating and digesting; after cooling, the mixture is transferred to a 100mL volumetric flask to be prepared to constant volume for standby.
(2) Drawing a titanium standard curve: respectively taking 0, 2.0, 4.0, 6.0, 8.0 and 10.0mL of titanium standard solution in a 50mL volumetric flask, and adding 20mL of concentrated H2SO4:H2Shaking the solution with O1: 1, and adding 5mL of 30% H2O2And (5) shaking up the solution to a constant volume. Measuring absorbance at 410nm, and drawing standard curve to obtain linear equation of y-14163 x +0.0875, R2＝0.9942。
(3) And (3) sample determination: 0.1g of Fe is taken3O4-PC-TiO2The ternary complex was placed in a small beaker and 5g (NH) was added4)2SO4And 8mL of concentrated H2SO4Mixing, standing for 7min, heating to boil, and dissolving TiO therein2And separating and then fixing the volume to 100 mL. Draw 5mL of the solution from it and place it in a 50mL volumetric flask, add 20mL of concentrated H2SO4:H2To the solution of 1:1, 5mL of 30% H was added2O2And shaking up to constant volume. The absorbance was measured at a wavelength of 410nm, and the TiO was calculated2The load factor.
(4)TiO2And (3) load rate calculation: TiO 22Load factor m4/m3In the formula m3Is Fe3O4-PC-TiO2Mass of ternary complex, m4Is TiO2The quality of (c).
TABLE 2 magnetic carbon-supported TiO prepared in examples 1-8 and comparative example 12Carbon coating ratio of photocatalyst and TiO2Rate of load
3. Determination of catalytic Properties
(1) Drawing a methylene blue standard curve: when the concentration of the methylene blue solution is 0-21 mg.L-1In the range, the characteristic absorption peak wavelength λ is 664 nm. Preparing methylene blue solutions with a series of concentrations: 0. 0.2, 1, 2, 3, 5, 10 mg.L-1Measuring the absorbance at 664nm and drawing a standard curve to obtain a linear equation of y-0.104 x +0.071, R2＝0.9914。
(2) And (3) testing the catalytic performance of the material: taking 0.5g of ternary complex in a conical flask, adding 50ml of 0.01g.L-1The methylene blue solution is placed in a dark box device and is magnetically stirred for 30min at the rotating speed of 400r/min, so that the materials are fully adsorbed. The static light catalytic oxidation is carried out on methylene blue by using a 500W and 365nm mercury lamp as an ultraviolet light source and a 23W incandescent lamp as a visible light source. Recovering materials with magnet every 10min, centrifuging supernatant, and measuring absorbance of the centrifuged clarified sample solution with ultraviolet spectrophotometer at a wavelength of 664 nm. Recovering, washing, drying and weighing.
The degradation rate μ of methylene blue can be calculated by the following formula:
μ＝(C0-C)×100％/C0
in the formula: c0Is the initial concentration of the methylene blue solution, and C is the concentration of the methylene blue solution at time t.
TABLE 3 magnetic carbon-supported TiO prepared in examples 1-8 and comparative example 12Catalytic performance of photocatalyst
| 0min | 10min | 20min | 30min | 40min | 50min | 60min | 70min | 80min | 90min | |
| Example 1 | 1.028 | 0.023 | 0 | / | / | / | / | / | / | / |
| Comparative example 1 | / | / | / | / | / | / | / | / | / | / |
| Example 2 | 1.028 | 0.903 | 0.756 | 0.719 | 0.68 | 0.614 | 0.523 | 0.12 | 0.077 | 0.025 |
| Example 3 | 1.028 | 0.848 | 0.64 | 0.594 | 0.5 | 0.464 | 0.379 | 0.321 | 0.19 | 0.149 |
| Example 4 | 1.028 | 0.15 | 0.244 | 0.106 | 0.107 | 0.111 | 0.082 | 0.09 | 0.067 | 0.059 |
| Example 5 | 1.028 | 0.368 | 0.338 | 0.327 | 0.234 | 0.265 | 0.302 | 0.34 | 0.28 | 0.156 |
| Example 6 | 1.028 | 0.004 | 0 | / | / | / | / | / | / | / |
| Example 7 | 1.028 | 0.36 | 0.282 | 0.17 | 0.132 | 0.095 | 0.064 | 0.044 | 0.026 | 0.024 |
| Example 8 | 1.028 | 0.156 | 0.13 | 0.129 | 0.316 | 0.171 | 0.145 | 0.196 | 0.616 | 0.407 |
The results in Table 3 show that the magnetic carbon-supported TiO prepared in examples 1 and 62The photocatalyst has good catalytic degradation performance on methylene blue under ultraviolet illumination, catalytic reaction can be completed within 10min, and the degradation rates respectively reach 97.76% and 99.61%. Comparative example 1 magnetic carbon-supported TiO prepared because carbon coating could not be completed2The photocatalyst has poor catalytic performance, and thus methylene blue cannot be catalytically degraded. Meanwhile, the catalytic performance of the material under the natural illumination condition is further tested, and the magnetic carbon-supported TiO prepared in the example 1 is found to be under the natural illumination condition2The photocatalyst can also complete the catalytic degradation of methylene blue within 10 min; and the magnetic carbon-supported TiO prepared in example 62In the presence of a photocatalystThe methylene blue was still not completely degraded after 90 min. As can be seen, the magnetic carbon-supported TiO prepared in example 12The light response interval of the photocatalyst realizes effective transfer from an ultraviolet region to a visible region.
As can be seen from the above examples, the magnetic carbon-supported TiO provided by the invention2The photocatalyst has higher photocatalytic performance and recycling rate, and the degradation rate of methylene blue can reach 99.61%. Also, the magnetic carbon-supported TiO provided by the invention2The recovery rate of the photocatalyst can reach 98.57%, and the photocatalyst still has a good catalytic effect after being recycled for 8 times.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. Magnetic carbon-supported TiO2Photocatalyst of Fe3O4Coated with said Fe3O4Carbon material on surface, and TiO supported on surface of the carbon material2。
2. The magnetic carbon-supported TiO of claim 12A photocatalyst, characterized in that said Fe3O4The particle size of the carbon material is 15-45 nm, and the thickness of the carbon material is 1-20 nm.
3. The magnetic carbon-supported TiO of claim 12Photocatalyst, characterized in that the TiO2The particle size of (A) is 83-121 nm; magnetic carbon supported TiO2Mass of photocatalyst, said TiO2The loading rate of (A) is more than 79%.
4. The magnetic TiO supported on carbon according to claim 1 to 32The preparation method of the photocatalyst comprises the following steps:
preparing carbon-coated Fe by a hydrothermal method3O4；
Coating the carbon with Fe3O4And TiO2Mixing the sol and obtaining the magnetic carbon-carried TiO by ultrasonic2A photocatalyst.
5. The process according to claim 4, characterized in that the hydrothermal process is in particular:
a. mixing ferric chloride, polyvinylpyrrolidone and water to obtain a mixed solution;
b. mixing the mixed solution obtained in the step a with hydrazine hydrate and sodium hydroxide, and carrying out oxidation-reduction reaction to obtain Fe3O4；
c. The Fe obtained in the step b is3O4Mixing with carbon source and water, and heating to obtain carbon-coated Fe3O4。
6. The method according to claim 5, wherein the ratio of the amount of ferric chloride in step a to the amount of hydrazine hydrate in step b is (1-3: 1; the mass ratio of ferric chloride in the step a to sodium hydroxide in the step b is 1 (4-8).
7. The method according to claim 5, wherein the carbon source in step c comprises starch, glucose or sucrose.
8. The method according to claim 5, wherein the carbon source is Fe in step c3O4The ratio of the amounts of the substances (9-36) to (1).
9. The preparation method according to claim 5, wherein the heating temperature in the step c is 180-200 ℃ and the heating time is 6-24 h.
10. The method according to claim 4, wherein the carbon-coated Fe3O4Mass of and TiO2The volume ratio of the sol is 1 (40-50).
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