CN116764659A - Cerium dioxide-nitrogen doped carbon nitride composite photocatalytic material and preparation method and application thereof - Google Patents
Cerium dioxide-nitrogen doped carbon nitride composite photocatalytic material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of advanced oxidation treatment of organic matters, and particularly relates to a cerium dioxide-nitrogen doped carbon nitride composite photocatalytic material, and a preparation method and application thereof. The photocatalytic material comprises cerium dioxide and nitrogen-doped carbon nitride, and the cerium dioxide is of a sheet structure; the mass percentage of the ceria in the photocatalytic material is 0.5-1.5%. Mixing the cerium dioxide-nitrogen doped carbon nitride composite photocatalytic material with wastewater containing polyvinyl alcohol, performing dark treatment, and performing photocatalytic degradation reaction under illumination after reaching adsorption saturation. The cerium oxide-nitrogen doped carbon nitride composite photocatalytic material has the advantages of good dispersibility and easiness in recycling, and is a novel composite photocatalytic material with excellent photocatalytic performance, environment friendliness and wide application range.
Description
Technical Field
The invention belongs to the field of advanced oxidation treatment of organic matters, and particularly relates to a cerium dioxide-nitrogen doped carbon nitride composite photocatalytic material, and a preparation method and application thereof.
Background
As an important industrial raw material, the polyvinyl alcohol has good physical and chemical properties, is widely applied to the production of products such as coating, adhesive, paper processing, emulsifying agent, dispersing agent and the like, has application range throughout the industries such as steel, textile, food, medicine, building, papermaking, high molecular chemical industry and the like, and is vigorously developed in recent years, so that the rapid increase of the polyvinyl alcohol productivity is promoted. However, because the polyvinyl alcohol belongs to typical refractory polymer substances, the polyvinyl alcohol wastewater has high COD and poor biodegradability, and the direct discharge can seriously pollute water. The polyvinyl alcohol is not toxic, but difficult to biodegrade, and the larger surface activity of the polyvinyl alcohol can increase the foam on the surface of the polluted water body, increase the viscosity and be unfavorable for the reoxygenation of the water body, thereby inhibiting the respiratory activity of aquatic organisms. In addition, the discharge of wastewater containing polyvinyl alcohol into water body can promote the release and migration of deposited heavy metals, enhance the activity of the heavy metals and cause more serious environmental problems. Therefore, finding a method for effectively removing polyvinyl alcohol in an aqueous environment has become an urgent task.
As an emerging advanced oxidation-reduction technology, the photocatalysis technology has the technical characteristics of utilizing green energy, deeply reacting at room temperature, having broad spectrum, thoroughly purifying, long service life of photocatalyst and the likeCharacterization is considered a reliable and efficient method. In the prior art, aiming at the photocatalytic degradation of polyvinyl alcohol in water, the method mainly focuses on TiO 2 And modified research thereof to obtain good polyvinyl alcohol degradation efficiency. However, in these studies, there are some common problems: (1) Is limited by TiO 2 The larger forbidden bandwidth has limited light absorption performance, and can only be excited by ultraviolet light to realize photocatalytic degradation. However, the ultraviolet light only occupies 7% of the solar radiation energy, while the visible light and the infrared light respectively occupy 50% and 43% of the solar radiation energy, so that the TiO 2 Solar radiation energy cannot be fully utilized, and practical application is limited; (2) TiO is adopted 2 Photocatalytic degradation is limited by rapid recombination of photogenerated carriers, the degradation efficiency of the photocatalytic material on polyvinyl alcohol is not ideal in a short time, and the degradation efficiency of the polyvinyl alcohol is only 50% due to ultraviolet irradiation for 4 hours; (3) To improve TiO 2 Many studies have been conducted on modification of TiO with metal ions and noble metals 2 The surface of the polymer is provided with improved activity of photocatalytic degradation of polyvinyl alcohol. However, the load of the hetero atoms inevitably introduces impurities and structural defects, which have adverse effects on the stability of the catalyst; in addition, noble metals can also limit the large-scale application of materials. Thus, it remains a difficult challenge to obtain an economically efficient, degradable, recyclable photocatalytic material for polyvinyl alcohol treatment.
In recent years, graphene carbon nitride (carbon nitride for short) is widely applied to the fields of photocatalytic water decomposition, carbon dioxide reduction, nitrogen fixation, artificial photosynthesis, environmental remediation and the like by virtue of the characteristics of proper energy band structure, excellent thermal and chemical stability, accessibility of constituent elements, environmental friendliness and the like. However, the carbon nitride monomer obtained by directly calcining the precursor is limited by its high photo-generated carrier recombination rate and limited visible light absorption range (lambda <470 nm), and its photocatalytic activity is not ideal. To overcome these difficulties, various methods of element doping, promoter loading, construction of heterojunction, etc. are used to optimize the photocatalytic performance of carbon nitride monomers. The element doping can effectively adjust the carbon nitride energy band structure and the light absorption performance, and the supported cocatalyst can effectively improve the separation efficiency of the photogenerated carriers. However, impurities and structural defects are inevitably introduced in the process of element doping and cocatalyst loading, so that the stability of the photocatalyst is affected. Therefore, the construction of the carbon nitride-based photocatalyst with good light absorption performance, high quantum efficiency and strong catalytic performance stability has important significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a ceria-nitrogen doped carbon nitride composite photocatalytic material, a preparation method and application thereof, wherein the ceria-nitrogen doped carbon nitride composite photocatalytic material is used for treating polyvinyl alcohol in water, and the ceria-nitrogen doped carbon nitride composite photocatalytic material has the advantages of simple operation, short period, easy recycling and high degradation efficiency.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides a cerium dioxide-nitrogen doped carbon nitride composite photocatalytic material, which comprises cerium dioxide and nitrogen doped carbon nitride, wherein the cerium dioxide is of a sheet structure; the mass percentage of the ceria in the photocatalytic material is 0.5-1.5%.
In another aspect, the present invention provides a method for preparing a ceria-nitrogen doped carbon nitride composite photocatalytic material according to claim 1, characterized in that it comprises the following steps:
s1, dissolving cerium salt in deionized water, adding a nitrogen-containing compound, carrying out ultrasonic treatment, and stirring to obtain a cerium salt precursor;
s2, carrying out hydrothermal reaction on the cerium salt precursor obtained in the step S1 to obtain basic cerium carbonate slurry, cooling and removing supernatant, washing, filtering and drying the rest slurry to obtain the basic cerium carbonate precursor;
s3, calcining the basic cerium carbonate precursor obtained in the step S2, and grinding to obtain cerium oxide nano particles;
s4, mixing citric acid with deionized water, and stirring at constant temperature until water evaporates to obtain citric acid powder;
and S5, mixing the cerium oxide nano particles obtained in the step S3 with the citric acid powder obtained in the step S4, adding urea, grinding, calcining, washing, filtering and drying to obtain the cerium oxide-nitrogen doped carbon nitride composite photocatalytic material.
In the above technical scheme, in step S1, the cerium salt is cerium nitrate hexahydrate, the nitrogen-containing compound is hexamethylenetetramine, or the cerium salt is cerium carbonate, and the nitrogen-containing compound is ammonia water; the mass ratio of cerium salt to nitrogen-containing compound is 1:1.5-2.5; the ultrasonic time is 5-15 min; stirring is carried out at the rotating speed of 600-800 r/min for 5-7 h.
In the above technical scheme, in the step S2, the hydrothermal reaction temperature is 140-180 ℃ and the hydrothermal reaction time is 9-15 hours; the drying temperature is 60-80 ℃ and the drying time is 12-20 h.
In the above technical scheme, in the step S3, the calcination temperature is 500-600 ℃, the heating rate is 2-5 ℃/min, and the calcination time is 2-4 h; the grinding time is 10-20 min.
In the above technical scheme, in the step S4, the constant temperature stirring temperature is 60-70 ℃, the time is 4-6 h, and the stirring rotation speed is 1000-1200 r/min; the dosage ratio of citric acid to deionized water is 1g:20ml.
In the above technical solution, in step S5, the mass ratio of ceria, citric acid powder, and urea is 6-12: 0.5 to 1.5:100; the calcination temperature is 500-600 ℃, the temperature rising rate in the calcination process is 2-5 ℃/min, and the calcination time is 2-4 h; grinding time is 20-40 min; the drying temperature is 60-80 ℃ and the drying time is 12-20 h.
The invention also provides an application of the ceria-nitrogen doped carbon nitride composite photocatalytic material in treating polyvinyl alcohol in water, and the application method comprises the following steps:
mixing the cerium dioxide-nitrogen doped carbon nitride composite photocatalytic material with wastewater containing polyvinyl alcohol, performing dark treatment, and performing photocatalytic degradation reaction under illumination after reaching adsorption saturation.
According to the technical scheme, the concentration of the polyvinyl alcohol in the wastewater containing the polyvinyl alcohol is 10-30 mg/L; the mass ratio of the ceria-nitrogen doped carbon nitride composite photocatalytic material to the polyvinyl alcohol is 9-15: 1.
according to the technical scheme, further, the dark treatment is carried out by stirring for 30-60 min under the dark condition; the photocatalytic degradation reaction is carried out under the stirring condition with the rotating speed of 400-1000 r/min, the photocatalytic degradation reaction is carried out under the illumination condition with the wavelength of 420-850 nm, and the time of the photocatalytic degradation reaction is 60-90 min.
The beneficial effects of the invention are as follows:
1. the invention relates to a cerium oxide-nitrogen doped carbon nitride composite photocatalytic material, which comprises cerium oxide and nitrogen doped carbon nitride, wherein the nitrogen doped carbon nitride material is prepared by doping nitrogen element in carbon nitride, and cerium oxide is loaded on the nitrogen doped carbon nitride material. Compared with other doped elements, the doping of the nitrogen element can not only adjust the inherent optical/electrical properties of the carbon nitride monomer material and enhance the light absorption performance of the carbon nitride monomer, but also avoid introducing foreign impurities and defects and not affect the stability of the photocatalyst; in order to inhibit the recombination of photogenerated carriers during photocatalysis, inexpensive, stable ceria was introduced. Since the conduction band position of ceria is lower than that of carbon nitride, coupling with carbon nitride is expected to collect photo-generated electrons onto ceria during the reaction, thereby promoting separation of photo-generated electron hole pairs. On the other hand benefit from Ce 3+ (4f 1 5d 0 ) Ce (Ce) 4+ (4f 0 5d 0 ) Unique electronic structure, original Ce in cerium oxide 4+ Is easily positioned by Ce 3+ Substituted with Ce 4+ Stable and compatible, and can be mutually converted. Thus Ce is provided with 4+ /Ce 3+ The existence of the redox couple can serve as a charge transfer medium to further promote electron transfer, thereby improving the photocatalytic activity. Compared with a carbon nitride monomer material, the ceria-nitrogen doped carbon nitride composite photocatalytic material has the advantages of reduced electron-hole recombination rate, widened photoresponse range, enhanced stability and better photocatalytic performance. The ceria-nitrogen doped carbon nitride composite photocatalytic material has the advantages of strong stability, wide photoresponse range and electron-The hole separation efficiency is high, the photocatalysis performance is excellent, the environment is friendly, and the like.
2. The invention relates to a preparation method of a cerium oxide-nitrogen doped carbon nitride composite photocatalytic material, which comprises the steps of firstly synthesizing a cerium oxide monomer by taking cerium salt and a nitrogen-containing compound as raw materials through a hydrothermal-calcining method, and then directly calcining mixed raw materials of cerium oxide, citric acid and urea to prepare the cerium oxide-nitrogen doped carbon nitride composite photocatalytic material with excellent electronic conduction performance and photocatalytic performance. The preparation method of the cerium oxide-nitrogen doped carbon nitride composite photocatalytic material is simple in process flow, green and environment-friendly, does not need special equipment, does not influence the crystal form of cerium oxide, can ensure that the properties of the synthetic material are not changed, is suitable for large-scale preparation, and is convenient for industrial utilization.
3. When the ceria-nitrogen doped carbon nitride composite photocatalytic material is used for treating polyvinyl alcohol in water, the ceria-nitrogen doped carbon nitride composite photocatalytic material can be uniformly dispersed in wastewater, so that good dispersibility is shown, and the ceria-nitrogen doped carbon nitride composite photocatalytic material is ensured to be fully contacted with the polyvinyl alcohol which is an organic pollutant to be treated; meanwhile, the ceria-nitrogen doped carbon nitride composite photocatalytic material can be separated from the reaction solution through a simple centrifugation process, so that the ceria-nitrogen doped carbon nitride composite photocatalytic material is convenient to recycle; in addition, the degradation efficiency of the ceria-nitrogen doped carbon nitride composite photocatalytic material for the polyvinyl alcohol in 1h reaches 73.09%, so that the polyvinyl alcohol is effectively and rapidly degraded.
In conclusion, the cerium oxide-nitrogen doped carbon nitride composite photocatalytic material has the advantages of good dispersibility and easiness in recycling, and is a novel composite photocatalytic material with excellent photocatalytic performance, environment friendliness and wide application range.
Drawings
FIG. 1 is a TEM image of the ceria-nitrogen doped carbon nitride composite photocatalytic material produced in example 2;
FIG. 2 is a graph showing the degradation effect of the ceria-nitrogen doped carbon nitride composite photocatalytic material polyvinyl alcohol prepared in example 1;
FIG. 3 is a graph showing the degradation effect of the ceria-nitrogen doped carbon nitride composite photocatalytic material prepared in example 2 on polyvinyl alcohol under different water source environments, wherein DW is pure water, TW is tap water, LW is lake water, and RW is river water;
FIG. 4 is a graph showing the degradation effect of the cerium oxide-nitrogen doped carbon nitride composite photocatalytic material prepared in example 3 on polyvinyl alcohol under different ionic conditions.
Detailed Description
The invention is further described below in connection with the drawings and the specific preferred embodiments, but the scope of protection of the invention is not limited thereby.
The materials and instruments used in the examples below were all commercially available and the starting materials were analytically pure. In the following examples, the data obtained are all average values of three or more repeated tests unless otherwise specified.
Example 1
The mass ratio of the cerium oxide-nitrogen doped carbon nitride composite photocatalytic material to the polyvinyl alcohol in the polyvinyl alcohol solution is 9:1, adding a ceria-nitrogen doped carbon nitride composite photocatalytic material into a polyvinyl alcohol solution with an initial concentration of 10mg/L, stirring for 30min under a dark condition, namely, carrying out dark treatment for 30min, carrying out photocatalytic degradation reaction on the polyvinyl alcohol solution under an illumination condition with a wavelength of 420-800 nm at a rotating speed of 800r/min for 60min after the adsorption balance of the polyvinyl alcohol is achieved, sampling and testing the concentration of the polyvinyl alcohol when the photocatalytic treatment is carried out for 0min, 15min, 30min, 45min and 60min, and carrying out solid-liquid separation after the reaction is completed, thus completing the degradation of the polyvinyl alcohol.
In this embodiment, the ceria-nitrogen doped carbon nitride composite photocatalytic material includes ceria and nitrogen doped carbon nitride, wherein the nitrogen doped carbon nitride material is doped with nitrogen element in carbon nitride, and ceria is supported on the nitrogen doped carbon nitride material, and the mass percentage of ceria in the ceria-nitrogen doped carbon nitride composite photocatalytic material is 1.
In this embodiment, the preparation method of the ceria-nitrogen doped carbon nitride composite photocatalytic material includes the following steps:
1. preparation of cerium oxide monomer material
(1) 6.5g of cerium carbonate (Ce 2 (CO 3 ) 3 ) Dissolving in 80ml deionized water, and carrying out ultrasonic treatment for 10min to obtain cerium carbonate solution, wherein the concentration of the cerium carbonate solution is 0.215mol/L;
(2) Adding 20ml of ammonia water into the cerium carbonate solution prepared in the step (1), and stirring for 6 hours under the condition of 750r/min of rotating speed to obtain cerium carbonate/ammonia water precursor mixed solution;
(3) Transferring the cerium carbonate/ammonia water precursor mixed solution obtained in the step (2) into a reaction kettle, performing hydrothermal reaction for 12 hours at 160 ℃, cooling the obtained product to room temperature, repeatedly cleaning with deionized water and ethanol, and drying in a baking oven at 70 ℃ for 16 hours to obtain a basic cerium carbonate precursor;
(4) Transferring the basic cerium carbonate precursor obtained in the step (3) to a crucible, placing the crucible in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, calcining at 550 ℃ for 2 hours, after the calcining is finished, cooling the material to room temperature, respectively cleaning the material for three times by using deionized water and absolute ethyl alcohol, drying the material in a blast drying box for 12 hours, and grinding the material for 10 minutes after the drying is finished to obtain powder, thus obtaining the cerium oxide nano particles.
2. Preparing a cerium oxide-nitrogen doped carbon nitride composite photocatalytic material:
(1) Citric acid (C) 6 H 8 O 7 ·H 2 O) dissolving in 20ml of deionized water, and stirring for 15min at the rotating speed of 600r/min to obtain a citric acid solution; then stirring and evaporating the obtained citric acid for 4 hours at 60 ℃ and 1200r/min to obtain citric acid powder;
(2) Uniformly mixing 90mg of cerium oxide obtained in the step (1) with 10mg of citric acid powder obtained in the step (2), adding 10g of urea, and grinding for 40min to obtain a cerium oxide/citric acid/urea precursor;
(3) Transferring the ceria/citric acid/urea precursor obtained in the step (2) into a crucible, heating to 550 ℃ at a heating rate of 2 ℃/min, calcining at 550 ℃ for 3 hours, cooling the obtained product to room temperature, repeatedly washing with deionized water and ethanol, and drying at 70 ℃ for 16 hours to obtain the ceria-nitrogen doped carbon nitride composite photocatalytic material, namely CeNCN1, wherein the mass percentage of ceria in the ceria-nitrogen doped carbon nitride composite photocatalytic material is 1%.
Fig. 2 is a graph showing the degradation effect of ceria-nitrogen doped carbon nitride composite photocatalytic material (CeNCN 1) on polyvinyl alcohol in example 1 of the present invention. As can be seen from FIG. 2, the ceria-nitrogen doped carbon nitride composite photocatalytic material has a good photocatalytic effect on polyvinyl alcohol, and the removal rate of the material on the polyvinyl alcohol within 60min is 73.09%. On one hand, the cerium oxide-nitrogen doped carbon nitride composite photocatalytic material is characterized in that nitrogen doping effectively widens the photoresponse range of the photocatalytic material. On the other hand, since the conduction band position of ceria is lower than that of carbon nitride, coupling with carbon nitride can collect photo-generated electrons onto ceria during the reaction, thereby promoting separation of photo-generated electron hole pairs. In addition, benefit from Ce 3+ (4f 1 5d 0 ) Ce (Ce) 4+ (4f 0 5d 0 ) Unique electronic structure, original Ce in cerium oxide 4+ Is easily positioned by Ce 3+ Substituted with Ce 4+ Stable and compatible, and can be mutually converted. Thus Ce is provided with 4+ /Ce 3+ The presence of redox couples may further facilitate electron transfer as a charge transfer medium.
Example 2
The mass ratio of the cerium oxide-nitrogen doped carbon nitride composite photocatalytic material to the polyvinyl alcohol in the polyvinyl alcohol solution is 15:1, taking 4 parts of cerium oxide-nitrogen doped carbon nitride composite photocatalytic material, respectively adding the materials into four solutions of polyvinyl alcohol pure water (DW), tap Water (TW), lake Water (LW) and River Water (RW) with initial concentration of 30mg/L, stirring for 60min under dark conditions, namely, carrying out dark treatment for 60min, carrying out photocatalytic treatment for 90min under stirring with the rotation speed of 400r/min and under illumination with the wavelength of 420-850 nm after the adsorption balance of the polyvinyl alcohol is reached, sampling and testing the concentration of the polyvinyl alcohol when the photocatalytic treatment is carried out for 0min, 15min, 30min, 45min, 60min, 75min and 90min, and carrying out solid-liquid separation after the reaction is completed, thus completing the degradation of the polyvinyl alcohol.
In this embodiment, the ceria-nitrogen doped carbon nitride composite photocatalytic material includes ceria and nitrogen doped carbon nitride, wherein the nitrogen doped carbon nitride material is doped with nitrogen element in carbon nitride, and ceria is supported on the nitrogen doped carbon nitride material, and the mass percentage of ceria in the ceria-nitrogen doped carbon nitride composite photocatalytic material is 0.5.
In this embodiment, the preparation method of the ceria-nitrogen doped carbon nitride composite photocatalytic material includes the following steps:
1. preparation of cerium oxide monomer material
(1) 5g of cerium nitrate hexahydrate (Ce (NO) 3 ) 3 ·6H 2 O) dissolving in 70ml of deionized water, and carrying out ultrasonic treatment for 5min to obtain cerium nitrate solution, wherein the concentration of the cerium nitrate solution is 0.165mol/L;
(2) Adding 8.2g of hexamethylenetetramine into the cerium nitrate solution prepared in the step (1), and stirring for 7 hours at the rotating speed of 650r/min to obtain cerium nitrate/hexamethylenetetramine precursor mixed solution;
(3) Transferring the cerium nitrate/hexamethylenetetramine precursor mixed solution obtained in the step (2) into a reaction kettle, carrying out hydrothermal reaction for 9 hours at 180 ℃, cooling the obtained product to room temperature, repeatedly cleaning with deionized water and ethanol, and drying in an oven at 80 ℃ for 12 hours to obtain a basic cerium carbonate precursor;
(4) Transferring the basic cerium carbonate precursor obtained in the step (3) to a crucible, placing the crucible in a muffle furnace, heating to 600 ℃ at a heating rate of 5 ℃/min, calcining at 600 ℃ for 2 hours, after the calcining is finished, cooling the material to room temperature, respectively cleaning the material for three times by using deionized water and absolute ethyl alcohol, drying the material in a forced air drying box for 12 hours, and grinding the material for 15 minutes after the drying is finished to obtain powder, thus obtaining the cerium oxide nano particles.
2. Preparing a cerium oxide-nitrogen doped carbon nitride composite photocatalytic material:
(1) Citric acid (C) 6 H 8 O 7 ·H 2 O) dissolving in 20ml of deionized water, and stirring for 15min at the rotating speed of 600r/min to obtain a citric acid solution; subsequently the obtained lemon is subjected toStirring and evaporating acid at 70 ℃ under 1100r/min for 5h to obtain citric acid powder;
(2) Uniformly mixing 60mg of cerium oxide obtained in the step (1) with 15mg of citric acid powder obtained in the step (2.1), adding 10g of urea, and grinding for 30min to obtain a cerium oxide/citric acid/urea precursor;
(3) Transferring the ceria/citric acid/urea precursor obtained in the step (2) into a crucible, heating to 600 ℃ at a heating rate of 2 ℃/min, calcining at 600 ℃ for 2 hours, cooling the obtained product to room temperature, repeatedly washing with deionized water and ethanol, and drying at 80 ℃ for 12 hours to obtain the ceria-nitrogen doped carbon nitride composite photocatalytic material, namely CeNCN2, wherein the mass percentage of ceria in the ceria-nitrogen doped carbon nitride composite photocatalytic material is 0.5%.
Fig. 3 is a graph showing the degradation effect of ceria-nitrogen doped carbon nitride composite photocatalytic material (CeNCN 2) according to example 2 on polyvinyl alcohol under different water source environments, wherein DW is pure water, TW is tap water, LW is lake water, and RW is river water. In fig. 3, the ordinate is the ratio of the concentration of polyvinyl alcohol after degradation at a certain time to its initial concentration. As can be seen from the graph 3, the removal rates of the cerium oxide-nitrogen doped carbon nitride composite photocatalytic material (CeNCN 2) prepared by the invention on the polyvinyl alcohol in pure water, tap water, lake water and river water are 86.39%, 80.93%, 68.61% and 69.89%, respectively, which shows that the cerium oxide-nitrogen doped carbon nitride composite photocatalytic material has high-efficiency photocatalytic performance on the polyvinyl alcohol in different water source environments, can realize effective degradation on the polyvinyl alcohol in different water environments, and also shows that the cerium oxide-nitrogen doped carbon nitride composite photocatalytic material can be widely used for treating the polyvinyl alcohol in different water source environments, and has good application prospect and good practical availability in the photocatalysis field.
Example 3
The mass ratio of the cerium oxide-nitrogen doped carbon nitride composite photocatalytic material to the polyvinyl alcohol in the polyvinyl alcohol solution is 12:1, 5 parts of cerium oxide-nitrogen doped carbon nitride composite photocatalytic material are respectively added into a catalyst containing SO 4 2- 、CO 3 2- 、Cl - 、NO 3 - Is a polyvinyl alcohol solution (the concentration of polyvinyl alcohol in the polyvinyl alcohol solution is 20mg/L, SO) 4 2- 、CO 3 2- 、Cl - 、NO 3 - The concentration of (2) is 0.5 mmol/L) is stirred for 30min under dark condition, namely, dark treatment is carried out for 30min, after the adsorption balance of the polyvinyl alcohol is achieved, the photocatalytic degradation reaction is carried out for 60min under the stirring condition with the rotating speed of 1000r/min and the illumination condition with the wavelength of 420 nm-800 nm, the concentration of the polyvinyl alcohol is sampled and measured when the photocatalytic treatment is carried out for 0min, 15min, 30min, 45min and 60min, and the solid-liquid separation is carried out after the reaction is completed, so that the degradation of the polyvinyl alcohol is completed.
In this embodiment, the ceria-nitrogen doped carbon nitride composite photocatalytic material includes ceria and nitrogen doped carbon nitride, wherein the nitrogen doped carbon nitride material is doped with nitrogen element in carbon nitride, and ceria is supported on the nitrogen doped carbon nitride material, and the mass percentage of ceria in the ceria-nitrogen doped carbon nitride composite photocatalytic material is 1.5%.
In this embodiment, the preparation method of the ceria-nitrogen doped carbon nitride composite photocatalytic material includes the following steps:
1. preparation of cerium oxide monomer material
(1) 1.5g of cerium nitrate hexahydrate (Ce (NO) 3 ) 3 ·6H 2 O) dissolving in 30ml of deionized water, and carrying out ultrasonic treatment for 15min to obtain cerium nitrate solution, wherein the concentration of the cerium nitrate solution is 0.165mol/L;
(2) 2.8g of hexamethylenetetramine is added into the cerium nitrate solution prepared in the step (1), and the mixture is stirred for 5 hours under the condition of the rotating speed of 800r/min, so as to obtain cerium nitrate/hexamethylenetetramine precursor mixed solution.
(3) Transferring the cerium nitrate/hexamethylenetetramine precursor mixed solution obtained in the step (2) into a reaction kettle, carrying out hydrothermal reaction for 15 hours at 140 ℃, cooling the obtained product to room temperature, repeatedly cleaning with deionized water and ethanol, and drying in a 60 ℃ oven for 20 hours to obtain a basic cerium carbonate precursor;
(4) Transferring the basic cerium carbonate precursor obtained in the step (3) to a crucible, placing the crucible in a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, and calcining at 500 ℃ for 4 hours. After the calcination is finished and the material is cooled to room temperature, the material is respectively washed three times by deionized water and absolute ethyl alcohol, and is dried in a blast drying box for 12 hours. And after the drying is finished, grinding the material for 20min to obtain powder, and obtaining the cerium oxide nano particles.
2. Preparing a cerium oxide-nitrogen doped carbon nitride composite photocatalytic material:
(1) Citric acid (C) 6 H 8 O 7 ·H 2 O) dissolving in 20ml of deionized water, and stirring for 15min at the rotating speed of 600r/min to obtain a citric acid solution; then stirring and evaporating the obtained citric acid for 6 hours at the temperature of 80 ℃ and the speed of 1000r/min to obtain citric acid powder;
(2) Uniformly mixing 120mg of cerium oxide obtained in the step (1) with 5mg of citric acid powder obtained in the step (2.1), adding 10g of urea, and grinding for 20min to obtain a cerium oxide/citric acid/urea precursor;
(3) Transferring the cerium oxide/citric acid/urea precursor obtained in the step (2) into a crucible, heating to 500 ℃ at a heating rate of 5 ℃/min, calcining at 500 ℃ for 4 hours, cooling the obtained product to room temperature, repeatedly washing with deionized water and ethanol, and drying at 60 ℃ for 20 hours to obtain the cerium oxide-nitrogen doped carbon nitride composite photocatalytic material, namely CeNCN3, wherein the mass percentage of cerium oxide in the cerium oxide-nitrogen doped carbon nitride composite photocatalytic material is 1.5.
Fig. 4 is a graph showing the degradation effect of ceria-nitrogen doped carbon nitride composite photocatalytic material (CeNCN 3) of example 3 on polyvinyl alcohol under different ion conditions. In fig. 4, the ordinate is the ratio of the concentration of polyvinyl alcohol after degradation at a certain time to its initial concentration. As can be seen from FIG. 4, the ceria-nitrogen doped carbon nitride composite photocatalytic material prepared by the present invention is in deionized water and in SO-containing water 4 2- 、CO 3 2- 、Cl - 、NO 3 - The removal rates of polyvinyl alcohol in the water body are 71.07%, 65.83%, 73.66% and 66.41% respectively, except the polyvinyl alcoholCu of competitive relationship 2+ In addition, the cerium oxide-nitrogen doped carbon nitride composite photocatalytic material has high photocatalytic performance, which shows that the cerium oxide-nitrogen doped carbon nitride composite photocatalytic material has good practical applicability.
The above examples are only preferred embodiments of the present invention and are not limiting of the implementation. The protection scope of the present invention shall be subject to the scope defined by the claims. Other variations or modifications may be made in the various forms based on the above description. Obvious variations or modifications of the embodiments are within the scope of the invention.
Claims (10)
1. The cerium dioxide-nitrogen doped carbon nitride composite photocatalytic material is characterized by comprising cerium dioxide and nitrogen doped carbon nitride, wherein the cerium dioxide is of a sheet structure; the mass percentage of the ceria in the photocatalytic material is 0.5-1.5%.
2. A method for preparing the ceria-nitrogen doped carbon nitride composite photocatalytic material according to claim 1, characterized in that it comprises the steps of:
s1, dissolving cerium salt in deionized water, adding a nitrogen-containing compound, carrying out ultrasonic treatment, and stirring to obtain a cerium salt precursor;
s2, carrying out hydrothermal reaction on the cerium salt precursor obtained in the step S1 to obtain basic cerium carbonate slurry, cooling and removing supernatant, washing, filtering and drying the rest slurry to obtain the basic cerium carbonate precursor;
s3, calcining the basic cerium carbonate precursor obtained in the step S2, and grinding to obtain cerium oxide nano particles;
s4, mixing citric acid with deionized water, and stirring at constant temperature until water evaporates to obtain citric acid powder;
and S5, mixing the cerium oxide nano particles obtained in the step S3 with the citric acid powder obtained in the step S4, adding urea, grinding, calcining, washing, filtering and drying to obtain the cerium oxide-nitrogen doped carbon nitride composite photocatalytic material.
3. The method according to claim 2, wherein in the step S1, the cerium salt is cerium nitrate hexahydrate, the nitrogen-containing compound is hexamethylenetetramine, or the cerium salt is cerium carbonate, and the nitrogen-containing compound is ammonia water;
the mass ratio of cerium salt to nitrogen-containing compound is 1:1.5-2.5;
the ultrasonic time is 5-15 min;
stirring is carried out at the rotating speed of 600-800 r/min for 5-7 h.
4. The method according to claim 2, wherein in the step S2, the hydrothermal reaction temperature is 140 to 180 ℃ and the hydrothermal reaction time is 9 to 15 hours;
the drying temperature is 60-80 ℃ and the drying time is 12-20 h.
5. The method according to claim 2, wherein in the step S3, the calcination temperature is 500-600 ℃, the temperature rising rate is 2-5 ℃/min, and the calcination time is 2-4 h;
the grinding time is 10-20 min.
6. The method according to claim 2, wherein in the step S4, the constant stirring temperature is 60-70 ℃ for 4-6 hours at a stirring speed of 1000-1200 r/min;
the dosage ratio of citric acid to deionized water is 1g:20ml.
7. The method according to claim 2, wherein in the step S5, the mass ratio of ceria, citric acid powder, urea is 6-12: 0.5 to 1.5:100;
the calcination temperature is 500-600 ℃, the temperature rising rate in the calcination process is 2-5 ℃/min, and the calcination time is 2-4 h;
grinding time is 20-40 min;
the drying temperature is 60-80 ℃ and the drying time is 12-20 h.
8. Use of the ceria-nitrogen doped carbon nitride composite photocatalytic material according to claim 1 or the ceria-nitrogen doped carbon nitride composite photocatalytic material produced by the production method according to any one of claims 2 to 7 for treating polyvinyl alcohol in water, characterized in that the application method comprises the steps of: mixing the cerium dioxide-nitrogen doped carbon nitride composite photocatalytic material with wastewater containing polyvinyl alcohol, performing dark treatment, and performing photocatalytic degradation reaction under illumination after reaching adsorption saturation.
9. The use according to claim 8, wherein the concentration of polyvinyl alcohol in the polyvinyl alcohol-containing wastewater is 10-30 mg/L;
the mass ratio of the ceria-nitrogen doped carbon nitride composite photocatalytic material to the polyvinyl alcohol is 9-15: 1.
10. the use according to claim 8, wherein the darkening treatment is stirring under dark conditions for 30-60 min;
the photocatalytic degradation reaction is carried out under the stirring condition with the rotating speed of 400-1000 r/min, the photocatalytic degradation reaction is carried out under the illumination condition with the wavelength of 420-850 nm, and the time of the photocatalytic degradation reaction is 60-90 min.
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