CN107570194B - Fe/Co-Nx/TiO 2 photocatalyst and preparation method and application thereof - Google Patents
Fe/Co-Nx/TiO 2 photocatalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a Fe/Co-Nx/TiO 2 photocatalyst, which contains Fe/Co-Nx chelate on a crystal face of TiO 2 {001 }.
Description
Technical Field
The invention relates to a Fe/Co-Nx/TiO 2 photocatalyst, and also relates to a preparation method and application of the Fe/Co-Nx/TiO 2 photocatalyst, belonging to the technical field of photocatalysts.
Background
in recent years, Fenton reagent is considered to be an effective catalyst for degrading sulfonamides, but the Fenton reagent cannot be put into practical application due to the requirement of the dosage of H 2 O 2, although TiO 2 can degrade antibiotics well under the condition of ultraviolet light, TiO 2 cannot respond to visible light, and the application of the Fenton reagent is greatly limited.
Since Yang et al prepared anatase TiO 2 with 47% {001} crystal face, research on TiO 2 (001) is increasing, but most of research is only on regulation and control of {001} crystal face proportion, namely increasing the {001} crystal face proportion, and few research on modified photocatalytic performance is carried out.
Disclosure of Invention
The invention aims to solve the technical problem of providing a Fe/Co-Nx/TiO 2 photocatalyst which has excellent catalytic degradation performance on antibiotic sulfathiazole in a water body under visible light and ultraviolet light.
the invention also aims to solve the technical problem of providing a preparation method of the Fe/Co-Nx/TiO 2 photocatalyst.
The invention finally aims to solve the technical problem of providing the application of the Fe/Co-Nx/TiO 2 photocatalyst in the aspect of catalyzing and degrading the sulfathiazole in the water body under the visible light.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
A Fe/Co-Nx/TiO 2 photocatalyst contains Fe/Co-Nx chelate on the crystal face of TiO 2 {001 }.
according to the preparation method of the Fe/Co-Nx/TiO 2 photocatalyst, Fe/CoPcS and TiO 2 nanosheets in required mass ratio are placed at high temperature for pyrolysis reaction to obtain the Fe/Co-Nx/TiO 2 nanomaterial containing the Fe/Co-Nx chelate on the crystal face of TiO 2 {001 }. Fe/Co-Nx/TiO 2 is in a sheet-shaped nanostructure.
Wherein the TiO 2 contains a {001} crystal face in a proportion of 70-80%.
Wherein the temperature of the pyrolysis reaction is 600-800 ℃.
the preparation method of the Fe/Co-Nx/TiO 2 photocatalyst specifically comprises the following steps:
Step 1, preparing Fe/CoPcS, namely adding required amounts of sulfonated cobalt phthalocyanine and ferrous sulfate heptahydrate into methanol, performing ultrasonic treatment for a period of time, and calcining the mixed material in an N 2 atmosphere for a period of time to obtain Fe/CoPcS;
Step 2, preparing TiO 2 nanosheets with high {001} crystal face ratio, namely mixing required amount of butyl titanate, hydrofluoric acid and water according to a certain ratio, reacting at a certain temperature, centrifuging the product after reaction, cleaning, drying and grinding after centrifugation to obtain TiO 2 nanosheets with high {001} crystal face ratio;
And 3, adding the Fe/CoPcS prepared in the step 1 and the TiO 2 nanosheet prepared in the step 2 into methanol according to a required mass ratio, performing ultrasonic treatment, then placing the mixed material at a high temperature for pyrolysis reaction, and grinding a product after the pyrolysis reaction to obtain the Fe/Co-Nx/TiO 2 nanomaterial.
In the step 1, the adding mass ratio of the sulfonated cobalt phthalocyanine to the ferrous sulfate is 3: 2.
in the step 2, the mixing volume ratio of the butyl titanate, the hydrofluoric acid and the water is 5:1:1, the reaction temperature is 170-180 ℃, and the reaction time is 20-24 hours.
In step 3, the mass ratio of the Fe/CoPcS to the TiO 2 nanosheets is 1: 4.
In the step 3, the pyrolysis reaction temperature is 600-800 ℃, and the pyrolysis reaction time is 2-3 h.
The Fe/Co-Nx/TiO 2 photocatalyst is applied to the aspect of catalyzing and degrading the sulfathiazole in the water body under the visible light.
The preparation principle of the modified TiO 2 is that Fe/CoPcS forms an Fe/Co-Nx active center (Fe/Co-Nx active center) under a pyrolysis condition (above 600 ℃) and forms a heterojunction with TiO 2 to reduce the forbidden bandwidth of TiO 2 and broaden the response of the heterojunction to visible light, the Fe/Co-Nx can prolong the bond length of O 2 and reduce the bond energy to promote oxygen molecules to be easily attacked by electrons to generate superoxide radicals, meanwhile, due to the formation of the heterojunction, the separation of electron hole pairs is promoted, water molecules are oxidized into hydroxyl radicals by holes on a {001} crystal face, and sulfathiazole is finally oxidized into metabolic products under the action of the hydroxyl radicals and the superoxide radicals.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
The modified Fe/Co-Nx/TiO 2 photocatalyst has high degradation capability on sulfathiazole in water under visible light and ultraviolet light, and meanwhile, the degraded product has lower toxicity.
Drawings
FIG. 1 is a process flow diagram of the preparation method of the Fe/Co-Nx/TiO 2 photocatalyst of the present invention;
FIG. 2 is a graph comparing the results of the degradation experiments of various substances on sulfathiazole under visible light;
FIG. 3 is a schematic diagram of the structure of the Fe/Co-Nx/TiO 2 photocatalyst of the present invention;
FIG. 4 is a structural representation (SEM) of TiO 2 with a high {001} crystallographic plane fraction in accordance with the present invention;
FIG. 5 is a structural representation (SEM) of the Fe/Co-Nx/TiO 2 photocatalyst of the present invention.
Detailed Description
The technical solutions of the present invention are further described below with reference to the accompanying drawings, but the scope of the claimed invention is not limited thereto.
The preparation method of the Fe/Co-Nx/TiO2 photocatalyst comprises the steps of dissolving FeSO 4 & 7H 2 O and sulfonated cobalt phthalocyanine (CoPcS) in methanol, carrying out ultrasonic treatment for a certain time, then placing the solution in a tube furnace to calcine the solution to form Fe/CoPcS, synthesizing TiO 2 with a high {001} crystal face ratio by using a hydrothermal method, and loading the Fe/CoPcS on a TiO 2 {001} crystal face at a high temperature to synthesize the Fe/Co-Nx/TiO 2 (001) nano photocatalyst.
Example 1
The preparation method of the Fe/Co-Nx/TiO 2 photocatalyst specifically comprises the following steps:
step 1, preparing Fe/Co-Nx nano particles, namely weighing 0.4g of ferrous sulfate heptahydrate and 0.6g of cobalt phthalocyanine sulfonate, placing the ferrous sulfate heptahydrate and the cobalt phthalocyanine sulfonate into 4ml of methanol, carrying out ultrasonic treatment for 10min, placing the obtained mixture into a tubular furnace, calcining for 2h under the protection of N 2 atmosphere, wherein the calcining temperature is 300 ℃, and grinding to obtain Fe/CoPcS;
step 2, respectively measuring 25mL of butyl titanate, 5mL of hydrofluoric acid and 5mL of deionized water, placing the mixture in a polytetrafluoroethylene container, uniformly mixing and stirring the mixture, reacting the mixture in a reaction kettle at 180 ℃ for 24 hours, centrifugally separating the obtained product, respectively cleaning the product for 3 times by using the deionized water and absolute ethyl alcohol, drying the product, and grinding the product to obtain a TiO 2 (001) nanosheet;
And 3, weighing 50mgFe/CoPcS and 200mgTiO 2 (001) nanosheets, placing the nanosheets into 10mL of methanol, carrying out ultrasonic treatment for 15min, placing the mixed material into a tubular furnace, carrying out pyrolysis for 2h at 600 ℃, and grinding to obtain Fe/Co-Nx/TiO 2 (001).
Example 2
the preparation method of the Fe/Co-Nx/TiO 2 photocatalyst specifically comprises the following steps:
Step 1, preparing Fe/Co-Nx nano particles, namely weighing 0.4g of ferrous sulfate heptahydrate and 0.6g of cobalt phthalocyanine sulfonate, placing the ferrous sulfate heptahydrate and the cobalt phthalocyanine sulfonate into 4ml of methanol, carrying out ultrasonic treatment for 10min, placing the obtained mixture into a tubular furnace, calcining for 2h under the protection of N 2 atmosphere, wherein the calcining temperature is 300 ℃, and grinding to obtain Fe/CoPcS;
Step 2, respectively measuring 25mL of butyl titanate, 5mL of hydrofluoric acid and 5mL of deionized water, placing the mixture in a polytetrafluoroethylene container, uniformly mixing and stirring the mixture, reacting the mixture in a reaction kettle at 170 ℃ for 20 hours, centrifugally separating the obtained product, respectively cleaning the product for 3 times by using the deionized water and absolute ethyl alcohol, drying the product, and grinding the product to obtain a TiO 2 (001) nanosheet;
And 3, weighing 50mgFe/CoPcS and 200mgTiO 2 (001) nanosheets, placing the nanosheets into 10mL of methanol, carrying out ultrasonic treatment for 15min, placing the mixed material into a tubular furnace, carrying out pyrolysis for 3h at 800 ℃, and grinding to obtain Fe/Co-Nx/TiO 2 (001).
Comparative example 1
a preparation method of a TiO 2 (001) nanosheet comprises the specific operation modes of respectively measuring 25mL of butyl titanate, 5mL of hydrofluoric acid and 5mL of deionized water, placing the mixture in a polytetrafluoroethylene container, uniformly mixing and stirring, reacting in a reaction kettle at 180 ℃ for 24 hours, centrifugally separating the obtained product, respectively cleaning for 3 times by using the deionized water and absolute ethyl alcohol, drying, and grinding to obtain the TiO 2 (001) nanosheet.
The self-degradation ability of sulfathiazole in the absence of catalyst, the degradation ability of the Fe/Co-Nx/TiO 2 (001) photocatalyst prepared in example 1 to sulfathiazole in the solution, the degradation ability of the TiO 2 (001) photocatalyst prepared in comparative example 1 to sulfathiazole in the solution, and the degradation ability of the Fe/Co-Nx/TiO 2 (001) photocatalyst prepared in example 1 to sulfathiazole in the solution were measured in the absence of oxygen, respectively, under visible light, and the measurement results are shown in FIG. 2.
100mL of the sulfathiazole solution with the initial concentration of 10mg/L are placed under a 300w xenon lamp for irradiation for 18h (air is introduced). Samples were taken every 3h, filtered through a 0.45 micron filter head, diluted 20-fold and measured for sulfathiazole concentration using LC-MS/MS.
100mL of sulfathiazole solution with the initial concentration of 10mg/L is taken, 50mg of TiO 2 (001) photocatalyst prepared in comparative example 1 is added into the solution, the solution is stirred for 30min to reach the adsorption and desorption equilibrium, then the solution is placed under a 300w xenon lamp for irradiation for 18h (air is introduced), samples are taken every 3h, after filtration by a 0.45 micron filter head, the solution is diluted by 20 times, and the concentration of the sulfathiazole is measured by LC-MS/MS.
100mL of sulfathiazole solution with the initial concentration of 10mg/L is taken, 50mg of Fe/Co-Nx/TiO 2 (001) photocatalyst prepared in the example 1 is added into the solution, stirred for 30min to reach the adsorption and desorption equilibrium, placed under a 300w xenon lamp to be irradiated for 18h (air is introduced), sampling is carried out every 3h, after filtering is carried out by a 0.45 micron filter head, the solution is diluted by 20 times, and the concentration of the sulfathiazole is measured by LC-MS/MS.
100mL of a sulfathiazole solution with the initial concentration of 10mg/L is taken, 0.1g of the Fe/Co-Nx/TiO 2 (001) photocatalyst prepared in the example 1 is added into the solution, stirred for 30min to reach the adsorption and desorption equilibrium, placed under a 300w xenon lamp for irradiation for 18h (N 2 is introduced), sampled every 3h, filtered by a 0.45 micron filter head, diluted by 20 times and the concentration of the sulfathiazole is measured by LC-MS/MS, which is shown in figure 2.
as can be seen from FIG. 2, sulfathiazole is hardly degraded under the condition of no catalyst, when TiO 2 (001) nanosheets are added, the degradation rate is only 10%, and the removal rate can reach 84.5% by using the modified photocatalyst Fe/Co-Nx/TiO 2 (001), which indicates that the Fe/Co-Nx/TiO 2 (001) nanosheets photocatalyst of the invention have extremely strong degradation capability on the sulfathiazole serving as an antibiotic drug in water.
the results of the degradation experiments of the sulfathiazole by the substances under visible light are shown in table 1.
TABLE 1
。
the Fe/Co-Nx/TiO 2 photocatalyst firstly synthesizes Fe/CoPcS, then the Fe/CoPcS is compounded to the surface of TiO 2 with a high-proportion {001} crystal face through a pyrolysis method, and an active center Fe/Co-Nx is formed on the {001} crystal face under a high-temperature condition so as to obtain the Fe/Co-Nx/TiO 2 (001) photocatalyst.
It should be understood that the above examples are only for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And such obvious variations or modifications which fall within the spirit of the invention are intended to be covered by the scope of the present invention.
Claims (8)
1. A Fe/Co-Nx/TiO 2 photocatalyst is characterized in that the photocatalyst contains Fe/Co-Nx chelate on the crystal face of TiO 2 {001 };
the photocatalyst is prepared by a method comprising the following steps of carrying out pyrolysis reaction on Fe/CoPcS and TiO 2 nanosheets at a required mass ratio at a high temperature to obtain a Fe/Co-Nx/TiO 2 nanomaterial with a TiO 2 {001} crystal surface containing Fe/Co-Nx chelate, wherein the temperature of the pyrolysis reaction is 600-800 ℃.
2. the Fe/Co-Nx/TiO 2 photocatalyst as claimed in claim 1, wherein the TiO 2 contains {001} crystal face in a proportion of 70-80%.
3. the Fe/Co-Nx/TiO 2 photocatalyst of claim 1, which is prepared by the following method:
step 1, preparing Fe/CoPcS, namely adding required amounts of sulfonated cobalt phthalocyanine and ferrous sulfate heptahydrate into methanol, performing ultrasonic treatment for a period of time, and calcining the mixed material in an N 2 atmosphere for a period of time to obtain Fe/CoPcS;
Step 2, preparing TiO 2 nanosheets with high {001} crystal face ratio, namely mixing required amount of butyl titanate, hydrofluoric acid and water according to a certain ratio, reacting at a certain temperature, centrifuging the product after reaction, cleaning, drying and grinding after centrifugation to obtain TiO 2 nanosheets with high {001} crystal face ratio;
And 3, adding the Fe/CoPcS prepared in the step 1 and the TiO 2 nanosheet prepared in the step 2 into methanol according to a required mass ratio, performing ultrasonic treatment, then placing the mixed material at a high temperature for pyrolysis reaction, and grinding a product after the pyrolysis reaction to obtain the Fe/Co-Nx/TiO 2 nanomaterial, wherein the pyrolysis reaction temperature is 600-800 ℃.
4. The Fe/Co-Nx/TiO 2 photocatalyst as claimed in claim 3, wherein in step 1, the mass ratio of sulfonated cobalt phthalocyanine sulfonate to ferrous sulfate heptahydrate is 3: 2.
5. The Fe/Co-Nx/TiO 2 photocatalyst of claim 3, wherein in the step 2, the mixing volume ratio of the butyl titanate, the hydrofluoric acid and the water is 5:1, the reaction temperature is 170-180 ℃, and the reaction time is 20-24 h.
6. The Fe/Co-Nx/TiO 2 photocatalyst as claimed in claim 3, wherein in step 3, the mass ratio of Fe/CoPcS to TiO 2 is 1: 4.
7. The Fe/Co-Nx/TiO 2 photocatalyst as claimed in claim 3, wherein in step 3, the pyrolysis reaction time is 2-3 h.
8. The use of the Fe/Co-Nx/TiO 2 photocatalyst of claim 1 in the catalytic degradation of sulfathiazole in water under visible light.
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| CN109908899A (en) * | 2019-03-14 | 2019-06-21 | 浙江师范大学 | A kind of TiO2Load the preparation method and applications of monatomic Co catalyst |
| CN110227458B (en) * | 2019-07-22 | 2022-04-22 | 四川轻化工大学 | Copper-doped mesoporous titanium dioxide composite material and application thereof |
| CN113231105B (en) * | 2021-05-31 | 2022-03-29 | 华中科技大学 | Manganese dioxide loaded metal phthalocyanine composite material, preparation and application in degradation of antibiotics |
| CN115672302A (en) * | 2022-10-08 | 2023-02-03 | 深圳市华科创智技术有限公司 | Three-dimensional foam graphene-TiO 2 -silver nanowire composite material and preparation method and application thereof |
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