CN115608391A - g-C 3 N 4 Load {100} CeO 2 Heterojunction material, preparation method and application thereof - Google Patents
g-C 3 N 4 Load {100} CeO 2 Heterojunction material, preparation method and application thereof Download PDFInfo
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- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention relates to the field of photocatalytic materials, in particular to g-C 3 N 4 Load {100} CeO 2 Heterojunction materials, methods of making and uses thereof. The preparation method is to prepare the graphite carbon nitride (g-C) 3 N 4 ) Then {100} CeO is prepared 2 Then construct a solution of g-C 3 N 4 And {100} CeO 2 A combined heterojunction material. Preparation of g-C according to the invention 3 N 4 /{100}CeO 2 The method is simple and easy to implement and has high catalytic performance. Prepared by the inventiong-C of 3 N 4 /{100}CeO 2 As a catalyst, the purity {100} CeO can be greatly improved 2 The high-efficiency degradation of tetracycline can be realized, and the ratio of pure {100} CeO is higher than that of pure {100} 2 The photocatalytic performance of the material can be improved by more than 7 times, so that the problem of environmental pollution caused by tetracycline antibiotic wastewater is solved.
Description
Technical Field
The invention relates to the field of photocatalytic materials, in particular to g-C 3 N 4 Load {100} CeO 2 Heterojunction materials, methods of making and uses thereof.
Background
At present, the using amount of antibiotics in China is at the forefront of the world, and the abuse condition is very severe. Antibiotics are detected in water and soil for many times, which brings great potential safety hazard to ecological environment and human health. In terms of life, if people drink water or food polluted by antibiotics for a long time, the antibiotics are finally enriched on human bodies through food chains, thereby causing great threat to human health, and possibly causing diseases, such as teratogenesis, carcinogenesis, joint diseases, endocrine disorders, central nervous system defect, sensitization and possible photosensitivity change, and seriously interfering with the normal functions of the human bodies. There are three main methods for treating antibiotic wastewater, physical, biological and chemical methods. In recent years, semiconductor photocatalysis technology is considered to be a promising environmental purification technology due to the advantages of no toxicity, environmental protection, strong oxidizability and the like. The heterojunction photocatalytic system is receiving wide attention because it can improve the mobility of photon-generated carriers and show excellent photocatalytic performance. Cerium oxide (CeO) 2 ) Is one of rich rare earth oxides, has high oxygen storage capacity and is easy to remove Ce 4+ Reduction to Ce 3+ And has abundant oxygen vacancy, thus being regarded as a semiconductor catalyst for high-efficiency photocatalytic degradation of organic pollutants. Cubic CeO having {100} crystal plane therein 2 Because different exposed crystal faces show different photocatalytic performance differences, carriers are easy to recombine, the mobility is low, the oxygen vacancy forming energy is small, and the photocatalytic performance is always limited.
Disclosure of Invention
Aiming at the prior artIn question, it is an object of the present invention to provide a g-C 3 N 4 Load {100} CeO 2 Heterojunction material, preparation method and application of photocatalytic degradation of tetracycline.
The purpose of the invention is realized by adopting the following technical scheme:
in a first aspect, the invention discloses a g-C 3 N 4 Load {100} CeO 2 The preparation method of the heterojunction material comprises the following steps:
step 1, g-C 3 N 4 The preparation of (1):
weighing urea, placing the urea in a crucible, placing the crucible in a muffle furnace for sintering, cooling to obtain a product, and grinding to obtain g-C 3 N 4 ；
weighing Ce (NO) 3 ) 3 ·6H 2 Dissolving O in aqueous solution of sodium hydroxide, ultrasonically stirring and uniformly mixing at room temperature, pouring into a reaction kettle with tetrafluoroethylene as a lining, sealing, reacting at high temperature, cooling to room temperature, filtering, collecting precipitate, washing with deionized water and absolute ethyl alcohol for three times respectively, drying in vacuum, and calcining in a muffle furnace to obtain {100} CeO 2 A sample;
step 3, g-C 3 N 4 /{100}CeO 2 The preparation of (1):
weighing {100} CeO respectively 2 And g-C 3 N 4 Placing in a beaker filled with methanol, sealing, ultrasonically treating, placing in a fume hood, stirring until methanol is completely volatilized, calcining the obtained sample in a muffle furnace, cooling to room temperature, and collecting the sample for later use to obtain g-C 3 N 4 Load {100} CeO 2 Of (2), i.e. g-C 3 N 4 /{100}CeO 2 。
Preferably, in the step 1, the crucible is an alumina crucible, the atmosphere in the sintering process is air, the sintering temperature is 550 ℃, the sintering time is 4h, and the temperature rise rate is 5 ℃/min.
Preferably, in said step 2, ce (NO) 3 ) 3 ·6H 2 Substance of OThe amount of (B) was 3.0mmol; the concentration of the aqueous solution of sodium hydroxide was 6mol/L, and the volume was 60mL.
Preferably, in the step 2, the temperature of the reaction kettle is 180 ℃, and the reaction time is 24h.
Preferably, in the step 2, the temperature of the vacuum drying is 60 ℃, and the drying time is 12h.
Preferably, in the step 2, the atmosphere for calcining in the muffle furnace is air, the calcining temperature is 400 ℃, the heating rate is 5 ℃/min, and the calcining time is 4h.
Preferably, in the step 3, {100} CeO 2 And g-C 3 N 4 The mass ratio of (A) to (B) is 5 to 30.
More preferably, {100} CeO in said step 3 2 And g-C 3 N 4 The mass ratio of (1) is 25.
Preferably, in the step 3, the volume of the methanol is 50mL, the ultrasonic time is 1h, and the stirring time is 24h.
Preferably, in the step 3, the calcining temperature in the muffle furnace is 150 ℃, the calcining time is 4h, and the heating rate is 2 ℃/min.
In a second aspect, the invention discloses g-C prepared by the method 3 N 4 Load {100} CeO 2 Heterojunction materials and application thereof in photocatalytic degradation of tetracycline.
The invention has the beneficial effects that:
1. the preparation method and the material provided by the invention firstly prepare the graphite carbon nitride (g-C) 3 N 4 ) Then {100} CeO is prepared 2 Then construct a solution of g-C 3 N 4 And {100} CeO 2 Bonded heterojunction materials, the invention preparing g-C 3 N 4 /{100}CeO 2 The method is simple and easy to implement and has high catalytic performance.
2. The preparation method and the material provided by the invention are realized by adding g-C with different masses 3 N 4 To obtain g-C 3 N 4 5%,15%,25%,30% by mass of g-C 3 N 4 /{100}CeO 2 Wherein g-C 3 N 4 The highest tetracycline degradation efficiency was found at a mass ratio of 25% (labeled as CCN-25).
3. g-C prepared by the invention 3 N 4 /{100}CeO 2 As a catalyst, the purity {100} CeO can be greatly improved 2 The high-efficiency degradation of tetracycline can be realized, and the catalyst is similar to pure {100} CeO 2 Compared with the material, the photocatalytic performance of the material can be improved by more than 7 times, so that the problem of environmental pollution caused by tetracycline antibiotic wastewater is solved.
Drawings
The invention is further illustrated by means of the attached drawings, but the embodiments in the drawings do not constitute any limitation to the invention, and for a person skilled in the art, other drawings can be obtained on the basis of the following drawings without inventive effort.
FIG. 1 is an X-ray diffraction pattern and a Fourier infrared transform pattern of catalyst CCN-25 prepared in example 3 of the present invention; wherein (a) CCN-25 and CeO 2 X-ray diffraction patterns of (a); (b) CCN-25 and CeO 2 Fourier infrared transform atlas;
FIG. 2 is a TEM image, a HRTEM image and an EDX scanning element spectrum of CCN-25 as a catalyst prepared in example 3 of the present invention; wherein, (a) TEM image, (b) HRTEM image, (c) - (h) EDX scanning element spectrogram;
FIG. 3 is a graph of a photocatalytic tetracycline degradation assay; wherein, (a) the catalyst prepared by different methods is used for photocatalytic degradation of tetracycline test chart; (b) Is the photocatalytic activity diagram of the catalyst CCN-25 prepared in the embodiment 3 of the invention after 4 cycles.
Detailed Description
For the purpose of more clearly illustrating the present invention and more clearly understanding the technical features, objects and advantages of the present invention, the technical solutions of the present invention will now be described in detail below, but the present invention should not be construed as being limited to the implementable scope of the present invention.
The materials used in the present invention include all chemicals including cerous nitrate hexahydrate, sodium hydroxide and ethanol, etc. were used without further purification. Experiment ofThe ultrapure water used had a resistivity of 18.25 M.OMEGA.cm -1 。
The material characterization instrument was as follows: transmission Electron Microscopy (TEM), high Resolution TEM (HRTEM) tests were performed on a 200kV JEM-2100F electron microscope. The crystal structure was determined by a PANalytical X' Pert Powder X-ray diffractometer. Tetracycline photocatalytic degradation experiments were performed using 300W Xe lamp from the kindey, zhongzhi, inc. The chemical bonds and chemical groups in the sample were analytically determined by Thermo 6700 Fourier Infrared Spectroscopy (FT-IR) of Saimer fly, USA, in the range of 400-4000cm -1 KBr was used as diluent. The absorbance of the sample to tetracycline was measured using a Carry 60 model UV/Vis Spectrophotometer from Agilent, USA. The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
The invention is described in further detail below with reference to the figures and examples.
Example 1
Example provides g-C 3 N 4 /{100}CeO 2 A photocatalytic heterojunction material is used for efficiently degrading tetracycline and increasing {100} CeO 2 Photocatalytic performance. The specific preparation method of the photocatalyst comprises the following steps:
step 1, g-C 3 N 4 The preparation of (1): putting urea into an alumina crucible with a cover, putting the alumina crucible into a muffle furnace, calcining for 4 hours at 550 ℃ in the air atmosphere at the heating rate of 5 ℃/min to obtain g-C 3 N 4 And (4) collecting the sample after the sample is cooled to room temperature, and grinding the sample for later use.
Step 3, g-C 3 N 4 /{100}CeO 2 The preparation of (1): then according to {100} CeO 2 And g-C 3 N 4 The mass ratio of (1) to (100) is 5. Calcining the obtained sample in a muffle furnace at 150 ℃ for 4h at the heating rate of 2 ℃/min, cooling to room temperature, and collecting the sample for later use to obtain g-C 3 N 4 /{100}CeO 2 And is marked as CCN-5.
Example 2
Example provides g-C 3 N 4 /{100}CeO 2 Photocatalytic heterojunction materials, preparation methods and applications thereof, substantially the same as those of example 1, except that {100} CeO 2 And g-C 3 N 4 Is 15 to 100 and is marked as CCN-15.
Example 3
Example provides g-C 3 N 4 /{100}CeO 2 Photocatalytic heterojunction materials, preparation methods and applications thereof, substantially the same as those of example 1, except that {100} CeO 2 And g-C 3 N 4 Is 25 to 100, and is marked as CCN-25.
Example 4
Example provides g-C 3 N 4 /{100}CeO 2 Photocatalytic heterojunction materials, preparation methods and applications thereof, essentially identical to those of example 1, except that {100} CeO 2 And g-C 3 N 4 Is 30 to 100, and is marked as CCN-30.
Comparative example
{100} CeO 2 Photocatalytic material was prepared in the same manner as in example 1 using "{100} CeO in step 2 2 Preparation of (1) ".
To illustrate the invention more clearly, the catalyst materials prepared in inventive examples 1-4, comparative example, were tested:
1. testing the performance of the photocatalytic degradation of tetracycline:
taking tetracycline hydrochloride as a target pollutant, weighing a certain amount of tetracycline hydrochloride by using a high-precision electroanalytical balance, accurately preparing a tetracycline aqueous solution with the concentration of 30mg/L by using a volumetric flask, then weighing 100mL of the solution in a 250mL photocatalytic reactor, then adding a 30mg catalyst sample and uniformly dispersing, putting a magnetic stirrer and stirring for 0.5h in the dark to ensure that the catalyst and the target pollutant reach adsorption balance, and taking 2.5mL of the solution sample immediately after dark treatment. Immediately turning on a xenon lamp light source after dark treatment, illuminating for 1h, absorbing 2.5mL of the solution by using a syringe injector every 15min during the illumination reaction, filtering by using a microporous filter membrane, and taking the clear liquid for later use.
In the performance test of photocatalytic degradation of tetracycline, the light source current is fixedly set to be 15A, a proper stirring speed is selected to be set as a fixed value, the distance between a reaction solution page and a light source lamp socket is 10cm, a circulating water pump is utilized to keep the reaction temperature at 25 ℃, and the same reaction conditions are kept for each photocatalytic reaction.
2. Calculation of degradation rate of tetracycline:
the absorbance of the sample to tetracycline was measured using a Carry 60 model UV/Vis spectrophotometer from Agilent, USA, and the absorbance at 357nm was recorded.
General formula: degradation rate (%) = (1-C) t /C 0 ) x 100%, calculating the degradation rate of TC.
Wherein C 0 Absorbance of TC to reach adsorption equilibrium, C t Absorbance of TC was determined for timed sampling.
3. For the detection results and explanations:
(1) The XRD pattern (figure 1. (a)) shows that the diffraction peak of CCN-25 is well matched with the diffraction peak of cerium dioxide (JCPDS 34-0394) and has no other impurity peak, and indicates that {100} CeO is contained in the CCN-25 composite photocatalytic material 2 。
Fourier Infrared transform Spectroscopy (FIG. 1. (b)) shows g-C 3 N 4 With CeO 2 Is successfully compounded through a chemical bondRather than a simple physical connection.
(2) In FIG. 2, TEM is used to analyze the morphology of the sample, and {100} CeO in the CCN-25 composite photocatalytic material 2 Is cubic and has a side length of about 20nm, and g-C is shown in the figure 3 N 4 Is in the form of a film and carries {100} CeO on the upper surface 2 Particles of 0.27nm lattice spacing and belonging to CeO 2 {100} crystal plane. The CCN-25 is subjected to element scanning by EDX, and an EDX map shows that the CCN-25 contains four elements of C, N, ce and O, and further shows that g-C 3 N 4 /{100}CeO 2 The construction of the heterojunction was successful. Among them, there is a partial image that cannot be displayed due to color restriction, and the following is explained here: FIG. 2 (e) shows cyan fluorescence, which represents element C; (f) the picture shows that yellow fluorescence exists and represents N element; (g) green fluorescence exists in the figure, and represents Ce element; the purple fluorescence in the picture represents the element O.
(3) The results of the CCN-25 photocatalytic tetracycline degradation tests (FIG. 3 (a)), g-C 3 N 4 Load {100} CeO 2 Can effectively improve {100} CeO 2 The efficiency of photocatalytic degradation of tetracycline. When g-C 3 N 4 The photocatalytic enhancement efficiency reaches the maximum when the load is 25 percent, and is 89.47 percent, and the photocatalytic enhancement efficiency is about pure {100} CeO 2 7 times of the total weight of the product.
After four cycles, the degradation efficiency of CCN-25 is reduced from 89.47% to 81.27%, which shows that the photocatalytic activity of CCN-25 also maintains a better stability after 4 cycles (FIG. 3 (b)).
Preparation of g-C provided by the invention 3 N 4 /{100}CeO 2 The method is simple and easy to implement and has high catalytic performance. g-C prepared by the invention 3 N 4 /{100}CeO 2 As a catalyst, the purity {100} CeO can be greatly improved 2 The high-efficiency degradation of tetracycline can be realized, and the ratio of pure {100} CeO is higher than that of pure {100} 2 The photocatalytic performance of the material can be improved by more than 7 times, so that the problem of environmental pollution caused by tetracycline antibiotic wastewater is solved.
It should be noted that, within the scope of the components, ratios and process parameters described in the present invention, other components, ratios or values may be specifically selected to achieve the technical effects described in the present invention, and therefore, they are not listed one by one.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. g-C 3 N 4 Load {100} CeO 2 The preparation method of the heterojunction material is characterized by comprising the following steps of:
step 1, g-C 3 N 4 The preparation of (1):
weighing urea, placing the urea in a crucible, placing the crucible in a muffle furnace for sintering, cooling to obtain a product, and grinding to obtain g-C 3 N 4 ；
Step 2, {100} CeO 2 The preparation of (1):
weighing Ce (NO) 3 ) 3 ·6H 2 Dissolving O in aqueous solution of sodium hydroxide, ultrasonically stirring and uniformly mixing at room temperature, pouring into a reaction kettle with tetrafluoroethylene as a lining, sealing, reacting at high temperature, cooling to room temperature, filtering, collecting precipitate, washing with deionized water and absolute ethyl alcohol for three times respectively, drying in vacuum, and calcining in a muffle furnace to obtain {100} CeO 2 A sample;
step 3, g-C 3 N 4 /{100}CeO 2 The preparation of (1):
weighing {100} CeO respectively 2 And g-C 3 N 4 Placing in a beaker filled with methanol, sealing, ultrasonically treating, placing in a fume hood, stirring until methanol is completely volatilized, calcining the obtained sample in a muffle furnace, cooling to room temperature, and collecting the sample for later use to obtain g-C 3 N 4 Load {100} CeO 2 Of (2), i.e. g-C 3 N 4 /{100}CeO 2 。
2.g-C according to claim 1 3 N 4 Load {100} CeO 2 The preparation method of the heterojunction material is characterized in that in the step 1, the crucible is an alumina crucible, the atmosphere in the sintering process is air, the sintering temperature is 550 ℃, the sintering time is 4h, and the heating rate is 5 ℃/min.
3. g-C according to claim 1 3 N 4 Load {100} CeO 2 The preparation method of the heterojunction material is characterized in that in the step 2, ce (NO) 3 ) 3 ·6H 2 The amount of O species was 3.0mmol; the concentration of the aqueous solution of sodium hydroxide was 6mol/L, and the volume was 60mL.
4. g-C according to claim 1 3 N 4 Load {100} CeO 2 The preparation method of the heterojunction material is characterized in that in the step 2, the temperature of a reaction kettle is 180 ℃, and the reaction time is 24 hours; the temperature of vacuum drying is 60 ℃, and the drying time is 12h.
5. g-C according to claim 1 3 N 4 Load {100} CeO 2 The preparation method of the heterojunction material is characterized in that in the step 2, the calcining atmosphere in the muffle furnace is air, the calcining temperature is 400 ℃, the heating rate is 5 ℃/min, and the calcining time is 4h.
6. g-C according to claim 1 3 N 4 Load {100} CeO 2 A method for preparing a heterojunction material, wherein in step 3, {100} CeO 2 And g-C 3 N 4 The mass ratio of (A) to (B) is 5 to 30.
7. g-C according to claim 1 3 N 4 Load {100} CeO 2 The preparation method of the heterojunction material is characterized in that in the step 3, the volume of methanol is 50mL, the ultrasonic time is 1h, and the stirring time is 24h.
8. The g-C of claim 1 3 N 4 Load {100} CeO 2 The preparation method of the heterojunction material is characterized in that in the step 3, the calcining temperature in the muffle furnace is 150 ℃, the calcining time is 4h, and the heating rate is 2 ℃/min.
9. g-C 3 N 4 Load {100} CeO 2 A heterojunction material, characterized in that said g-C 3 N 4 Load {100} CeO 2 A heterojunction material comprising the g-C of any one of claims 1 to 8 3 N 4 Load {100} CeO 2 The heterojunction material is prepared by the preparation method.
10. A composition of g-C as claimed in claim 9 3 N 4 Load {100} CeO 2 Use of a heterojunction material, characterized in that said g-C is applied 3 N 4 Load {100} CeO 2 The heterojunction material is applied to photocatalytic degradation of tetracycline.
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