CN112264071A - g-C3N4@CeO2Preparation method and application of composite catalyst - Google Patents
g-C3N4@CeO2Preparation method and application of composite catalyst Download PDFInfo
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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
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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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
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention provides a g-C3N4@CeO2The preparation method of the composite catalyst and the application thereof, the preparation method comprises the following steps: dispersing a graphite-phase carbon nitride monomer material in deionized water, and performing ultrasonic treatment to obtain a dispersion liquid I; dispersing a cerium dioxide monomer material in deionized water, and performing ultrasonic treatment to obtain a dispersion liquid II: dropwise adding the dispersion liquid I to the dispersion liquid II under stirring to obtain a mixed dispersion liquid; continuously stirring the obtained mixed dispersion liquid to obtain a dispersion solution of a reaction product; centrifuging and drying the reaction product to obtain a product containing g-C3N45-35 wt% of the composite catalyst. g-C obtained by the invention3N4/CeO2The composite catalyst material has excellent propertiesThe activity of visible light irradiation at room temperature has high-efficiency catalytic degradation effect on formaldehyde, thereby achieving the purpose of removing formaldehyde.
Description
Technical Field
The invention belongs to the technical field of nano composite materials, and particularly relates to g-C3N4@CeO2A preparation method and application of the composite catalyst.
Background
At present, in the aspect of treating and purifying indoor air, particularly, there are a plurality of methods and approaches for removing formaldehyde in the indoor air, and the more mature methods are as follows: adsorption (including physical adsorption and chemical adsorption), green plant absorption and purification, thermal catalytic decomposition and photocatalytic oxidative degradation. The formaldehyde in the indoor air is adsorbed by a physical and chemical method to purify the formaldehyde, on one hand, a large amount of adsorbent needs to be provided (the adsorbent needs to be replaced at regular time), and on the other hand, the physical and chemical method is long in time consumption and cannot be put into practical application on a large scale. The formaldehyde in the indoor air is purified through a biological way (such as absorption by green plants), on one hand, a large number of plants with good absorption effect on the formaldehyde are needed to purify the air, and on the other hand, the biological way purifies the indoor air for a relatively long time, so that the aim of purifying the formaldehyde in the indoor air through the biological way cannot be effectively realized at present. The purpose of purifying indoor air by decomposing formaldehyde through thermal catalysis needs to be realized, so that not only special instruments and equipment are additionally provided, but also a large amount of energy is consumed, and the cost is greatly increased while formaldehyde is efficiently removed. The photocatalytic decomposition of formaldehyde in indoor air is a good choice and approach, firstly, the formaldehyde in indoor air treated by the photocatalyst can effectively utilize indoor light energy, and the aim of purifying the indoor air can be achieved without providing extra energy and special devices, and the photocatalyst responding to visible light at room temperature is greatly concerned by extensive researchers. The design, research, development and preparation of the catalyst which is efficient, stable, non-toxic, harmless, convenient to recycle and low in cost are key influencing factors for degrading formaldehyde under the irradiation of visible light at room temperature. The efficient removal of formaldehyde from indoor air by visible light at room temperature is a research hotspot, and particularly, a non-noble metal auxiliary catalyst is important to research. The catalyst can achieve the effect of efficiently purifying formaldehyde in indoor air only under specific conditions and when energy is additionally provided. Therefore, the photocatalyst which is low in cost, simple in preparation method, green and environment-friendly, convenient to recycle and environment-friendly through design and preparation has a far-reaching research significance.
Disclosure of Invention
The invention provides g-C for making up the defects in the prior art3N4@CeO2Preparation method and application of composite catalyst, wherein the catalyst is rare earth oxide cerium dioxide (CeO)2) Graphite phase carbon nitride (g-C) with non-metallic polymer3N4) The prepared catalyst has greatly reduced preparation cost and the obtained g-C is not loaded with noble metal such as Pt and the like3N4/CeO2The composite catalyst material has excellent room-temperature visible light irradiation activity and has efficient catalytic degradation effect on formaldehyde, thereby achieving the purpose of removing formaldehyde.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a g-C3N4@CeO2The preparation method of the composite catalyst comprises the following steps:
mixing graphite phase carbon nitride (g-C)3N4) Dispersing a monomer material in deionized water, and performing ultrasonic treatment to obtain a dispersion liquid I;
cerium oxide (CeO)2) Dispersing the monomer material in deionized water, and performing ultrasonic treatment to obtain a dispersion liquid II:
dropwise adding the dispersion liquid I into the dispersion liquid II under stirring to obtain a mixed dispersion liquid;
continuously stirring the obtained mixed dispersion liquid for a period of time to obtain a dispersion solution of a reaction product;
centrifuging and drying the reaction product to obtain a product containing g-C3N45-35 wt% of the composite catalyst.
According to the invention, wherein g-C3N4Monomer material and CeO2The mass ratio of the monomer materials is 1: 1-10.
According to the preparation method of the catalyst, the dispersion liquid is dropwise added to the dispersion liquid II under the stirring state, and the dropwise adding time is 0.05-0.5 h.
According to the preparation method of the catalyst, the obtained mixed dispersion liquid is continuously stirred for 0.2-0.8 h to obtain the dispersion liquid of the reaction product.
According to the preparation method of the catalyst, the g-C3N4Dispersing the monomer material in deionized water, and carrying out ultrasonic treatment for 0.25-0.75 h to obtain a dispersion liquid I; and/or, the CeO2Dispersing the monomer material in deionized water, and carrying out ultrasonic treatment for 0.05-45 h to obtain a dispersion liquid II.
According to the preparation method of the catalyst of the present invention, the cerium oxide (CeO)2) The precursor of the monomer material is selected from one or more of cerium nitrate hexahydrate, cerium sulfate and cerium chloride, and preferably the cerium nitrate hexahydrate; and/or, the CeO2The monomer material is prepared by a calcination method.
According to the preparation method of the catalyst, the g-C3N4The precursor of the monomer material is selected from thiourea, melamine, urea and dicyanodiamine, and is preferably melamine; and/or, said g-C3N4The monomer material is prepared by a calcination method.
In a preferred embodiment, said g-C3N4The preparation method of the monomer material comprises the following steps:
g to C3N4Drying the precursor of the monomer material at 40-80 ℃ for 12-36 h to obtain dry solid powder;
calcining the dried solid powder at 500-650 ℃ for 1-6 h, wherein the temperature programming condition is 1-5 ℃/min;
grinding the calcined product naturally cooled to room temperature to obtain the graphite-phase carbon nitride (g-C) prepared by the calcination method3N4) A monomeric material.
In a preferred embodiment, the CeO2The preparation method of the monomer material comprises the following steps:
adding CeO2Calcining a precursor of the monomer material at 400-600 ℃ for 2-6 h, raising the temperature by a program at 1-5 ℃/min, and fully grinding the calcined product naturally cooled to room temperature to obtain the dioxygenAnd (3) a cerium oxide nano material.
In a preferred embodiment, said g-C3N4@CeO2The preparation method of the composite catalyst comprises the following steps:
mixing a certain mass of graphite phase carbon nitride (g-C)3N4) Dispersing the monomer material in deionized water, and carrying out ultrasonic treatment for 0.25-0.75 h to obtain a dispersion liquid I;
mixing a certain mass of cerium dioxide (CeO)2) Dispersing the monomer material in deionized water, and carrying out ultrasonic treatment for 0.05-45 h to obtain a dispersion liquid II;
dropwise adding the dispersion liquid I into the dispersion liquid II while stirring to obtain a dispersion liquid III, and continuously stirring for 0.2-0.8 h to obtain a mixed solution;
purifying the mixed solution by centrifugation, and drying the centrifuged product at 60-80 ℃ for 10-30 h to obtain g-C3N4@CeO2And (3) compounding a catalyst.
In a preferred embodiment, the centrifugation time is 3-15 min, and the centrifugation speed is 2000-6000 r/min.
In another aspect of the present invention, there is provided g-C prepared by the above-mentioned preparation method3N4@CeO2And (3) compounding a catalyst.
In still another aspect of the present invention, there is provided g-C prepared by the above-mentioned preparation method3N4@CeO2The composite catalyst is used for degrading formaldehyde under the irradiation of visible light, especially at room temperature, such as 20-40 ℃, and preferably irradiation of a fluorescent lamp and the like.
The technical scheme provided by the invention has the following beneficial effects:
according to the technical scheme, the g-C prepared by the electrostatic self-assembly method3N4/CeO2The composite catalyst material can be used for efficiently catalyzing and degrading formaldehyde under the irradiation of room temperature visible light. The catalytic degradation test of formaldehyde shows that the obtained g-C3N4/CeO2The composite catalyst material has obvious enhancement to formaldehyde under the irradiation of visible light (such as fluorescent lamp and the like)The degradation activity can be realized, and the formaldehyde can be completely catalytically degraded into non-toxic and harmless carbon dioxide and water at room temperature.
Drawings
FIG. 1 is an X-ray diffraction pattern of a prepared monomer material or composite catalyst provided in examples one, two and four of the present invention;
FIG. 2 is a TEM image of a prepared composite catalyst provided in example four of the present invention;
FIG. 3 is a diagram of an experimental apparatus for testing the performance of the catalyst prepared by the present invention in photocatalytic degradation of formaldehyde;
FIGS. 4 and 5 are graphs comparing the results of the decrease in formaldehyde concentration (FIG. 4) and the increase in carbon dioxide concentration (FIG. 5) in the catalytic oxidation of formaldehyde under a fluorescent lamp at room temperature by the catalysts provided in examples one, two, three, four, five and first comparative examples of the present invention.
Fig. 6 is a graph showing the result of the stability performance of the composite catalyst material prepared in the fourth embodiment of the present invention in the visible light at room temperature for the catalytic degradation of formaldehyde.
The labels in FIG. 3 are illustrated as follows: 1. an infrared spectrum gas detector 2, a computer 3, a fluorescent lamp switch 4, a small electric fan switch 5, a small electric fan 6, a sample containing watch glass 7, a fluorescent lamp tube 8, a gas outlet hole 9, a watch glass cover pull wire hole 10, a gas inlet hole 11, a formaldehyde solution injection hole 12, an organic box body 13, a box body side cabin door 14 and a box body front cabin door.
Detailed Description
In order to better understand the technical solutions, the technical solutions of the present application are described in detail with specific embodiments below, and it should be understood that the specific features in the embodiments and examples of the present application are detailed descriptions of the technical solutions of the present application, but not limitations of the technical solutions of the present application, and the technical features in the embodiments and examples of the present application may be combined with each other without conflict. It should be understood that the term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Aiming at the defects of the existing catalyst and technology, the cerium dioxide is used as a rare earth oxide reserve with abundant reserves, and has excellent physical and chemical properties such as stable chemical properties, no toxicity, no harm, environmental friendliness and the like. The graphite-phase carbon nitride is a non-metallic polymer material with visible light response, and has the advantages of wide and cheap raw material sources, simple and feasible preparation process and the like. The embodiment of the invention utilizes the advantages of two monomer materials of cerium dioxide and graphite phase carbon nitride, selects the monomer materials as the catalyst monomer materials for photocatalytic degradation of formaldehyde at room temperature, and uses cerium dioxide (CeO)2) Monomer material as main catalyst and graphite phase carbon nitride (g-C)3N4) The g-C is prepared by taking a monomer material as a cocatalyst through an electrostatic self-assembly method3N4/CeO2The composite catalyst material is used as a material for efficiently degrading formaldehyde under visible light.
The embodiment of the invention mainly comprises the following steps: g-C3N4@CeO2The preparation method of the composite catalyst comprises the following steps:
mixing graphite phase carbon nitride (g-C)3N4) Dispersing a monomer material in deionized water, and performing ultrasonic treatment to obtain a dispersion liquid I;
cerium oxide (CeO)2) Dispersing the monomer material in deionized water, and performing ultrasonic treatment to obtain a dispersion liquid II:
dropwise adding the dispersion liquid I into the dispersion liquid II under stirring to obtain a mixed dispersion liquid;
continuously stirring the obtained mixed dispersion liquid to obtain a dispersion solution of a reaction product;
centrifuging and drying the reaction product to obtain a product containing g-C3N4The mass ratio is 5-35 wt% of the composite catalyst.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the examples of the present invention are commercially available or can be prepared by an existing method. The preparation method is described in detail below.
Example one
50.0g of melamine (C)2H4N4) Pouring into a clean beaker, then placing the beaker into an electric heating air blast drying oven, drying for 24h at 60 ℃, sealing the beaker filled with melamine after drying by using a preservative film, and then placing the beaker into a dryer. Weighing 8.0g of dry melamine, pouring the dry melamine into a clean ceramic crucible, covering the ceramic crucible with a cover, then placing the ceramic crucible into a muffle furnace, regulating the temperature to 580 ℃ at programmed temperature, then keeping the temperature at 580 ℃ for 4 hours at the programmed temperature rise rate of 2 ℃/min, naturally cooling the ceramic crucible to room temperature after calcination, taking out the ceramic crucible, fully grinding the calcined product, transferring the ground product into a sample tube, and attaching a label to the sample tube to obtain the graphite-phase carbon nitride (g-C) prepared by the calcination method3N4) A monomeric catalyst material. For use in the following examples.
Example two
Accurately weighing 4.3422g of cerous nitrate hexahydrate by using an analytical balance, pouring the weighed cerous nitrate hexahydrate into a clean ceramic crucible, covering a cover, then putting the crucible into a muffle furnace, calcining at 500 ℃ for 240min, programming the temperature rise rate to 2 ℃/min, taking out the ceramic crucible after the crucible is naturally cooled to room temperature, taking out the calcined product, fully grinding to obtain light yellow powder, and finally obtaining the nano cerium dioxide (CeO) prepared by a calcination method2) A material. For use in the following examples.
EXAMPLE III
0.04g of graphite phase carbon nitride (g-C)3N4) The monomer material was dispersed in 50mL of deionized water and then the contents of g-C were3N4Placing the beaker in an ultrasonic instrument, and carrying out ultrasonic treatment for 30min to obtain a dispersion liquid I; 0.36g of cerium oxide (CeO)2) The monomer material was dispersed in 50mL of deionized water and then charged with CeO2Beaker ofPlacing the mixture in an ultrasonic instrument, performing ultrasonic treatment for 10min to obtain dispersion liquid II, placing a beaker filled with the dispersion liquid II on a magnetic stirrer, dropwise adding the dispersion liquid I into the dispersion liquid II within 15min by using a rubber head dropper under strong stirring, continuously performing strong stirring for 30min to obtain mixed solution III, finally separating a product in the mixed solution III from deionized water through centrifugal treatment, pouring a supernatant into a waste liquid cylinder, obtaining a lower-layer precipitation product, namely a product prepared by an electrostatic self-assembly method, placing the centrifugal product in an electric hot blast drying box, drying overnight at 80 ℃, fully grinding the obtained dried product, transferring the sample into a sample tube, attaching a label, and finally obtaining graphite-phase carbon nitride (g-C)3N4) g-C of 10% content3N4/CeO2A composite catalyst material.
Example four
0.08g of graphite phase carbon nitride (g-C)3N4) The monomer material was dispersed in 50mL of deionized water and then the contents of g-C were3N4Placing the beaker in an ultrasonic instrument, and carrying out ultrasonic treatment for 30min to obtain a dispersion liquid I; 0.32g of cerium oxide (CeO)2) The monomer material was dispersed in 50mL of deionized water and then charged with CeO2Placing the beaker in an ultrasonic instrument, performing ultrasonic treatment for 10min to obtain a dispersion liquid II, then placing the beaker filled with the dispersion liquid II on a magnetic stirrer, dropwise adding the dispersion liquid I into the dispersion liquid II within 15min by using a rubber head dropper under strong stirring, then continuing strong stirring for 30min to obtain a mixed solution III, finally separating a product in the mixed solution III from deionized water through centrifugal treatment, pouring a supernatant into a waste liquid tank, placing a lower-layer precipitation product which is a product prepared by an electrostatic self-assembly method, then placing the centrifugal product in an electric hot blast drying box for overnight drying at 80 ℃, fully grinding the obtained dried product, transferring the ground dried product into a sample tube, attaching a label to the sample tube, and finally obtaining graphite-phase carbon nitride (g-C)3N4) g-C with a content of 20%3N4/CeO2A composite catalyst material.
EXAMPLE five
0.12g of graphite phase nitrogenCarbon (g-C)3N4) The monomer material was dispersed in 50mL of deionized water and then the contents of g-C were3N4Placing the beaker in an ultrasonic instrument, and carrying out ultrasonic treatment for 30min to obtain a dispersion liquid I; 0.28g of cerium oxide (CeO)2) The monomer material was dispersed in 50mL of deionized water and then charged with CeO2Placing the beaker in an ultrasonic instrument, performing ultrasonic treatment for 10min to obtain a dispersion liquid II, then placing the beaker filled with the dispersion liquid II on a magnetic stirrer, dropwise adding the dispersion liquid I into the dispersion liquid II within 15min by using a rubber head dropper under strong stirring, then continuing strong stirring for 30min to obtain a mixed solution III, finally separating a product in the mixed solution III from deionized water through centrifugal treatment, pouring a supernatant into a waste liquid tank, placing a lower-layer precipitation product which is a product prepared by an electrostatic self-assembly method, then placing the centrifugal product in an electric hot blast drying box for overnight drying at 80 ℃, fully grinding the obtained dried product, transferring the ground dried product into a sample tube, attaching a label to the sample tube, and finally obtaining graphite-phase carbon nitride (g-C)3N4) g-C of 30% content3N4/CeO2A composite catalyst material.
Comparative example 1
Commercially available cerium oxide (CeO) was purchased from national pharmaceutical group chemical agents Co., Ltd2)。
The catalyst materials prepared in the first, second and fourth examples were analyzed by X-ray diffraction (XRD) and Transmission Electron Microscope (TEM), respectively, and the results are shown in fig. 1 and 2, respectively, from which it can be seen that the monomer materials and composite catalyst materials prepared in the first, second and fourth examples have typical graphite-phase carbon nitride (g-C)3N4) Phase Structure (JCPDS No:50-1250) and cerium oxide (CeO)2) Phase structure (JCPDS No: 34-0394). FIG. 2 is a high-resolution characterization of the morphology of the composite catalyst material prepared in example IV. FIG. 3 is a diagram of an experimental device for catalytic degradation of formaldehyde by applying the prepared monomer or composite catalyst material and the catalyst material obtained in the comparative example under the irradiation of visible light at room temperature. FIGS. 4 and 5 are examplesComparative examples a graph comparing the room temperature formaldehyde removal performance of the monomer and composite catalyst materials prepared in example one, example two, example three, example four, and example five with the commercial ceria catalyst material prepared in comparative example one. It can be observed from the figure that the formaldehyde concentration decreases and the carbon dioxide concentration increases, indicating that formaldehyde is completely oxidized to carbon dioxide and water. The results show that the graphite phase carbon nitride (g-C) prepared in the first example3N4) Monomeric material and ceria (CeO) prepared in example two2) Monomer materials comparison, g-C prepared in example three, example four and example five3N4/CeO2The catalytic activity of the composite catalyst material to formaldehyde under the irradiation of a fluorescent lamp is obviously improved. Fig. 6 is a bar chart of data obtained from the photocatalytic stability test of the composite catalyst material prepared in the fourth example, and the specific operation steps are as follows: g-C from example four3N4/CeO2And (3) carrying out stability test on the composite catalyst material, sealing and storing the watch glass filled with the sample in a drying box by using a preservative film after each test, pricking holes on the preservative film by using an injector needle on the surface of the preservative film after 24 hours, then placing the watch glass in an electrothermal blowing drying box, carrying out heat treatment for 10min at 80 ℃, continuously carrying out photocatalytic degradation formaldehyde test on the sample after the heat treatment, and repeating the above operations for many times until the catalytic performance of the catalyst on formaldehyde is obviously reduced.
The graphite phase carbon nitride (g-C) prepared in example one3N4) Monomeric material and ceria (CeO) prepared in example two2) Monomer materials, example three, example four and example five g-C prepared by an electrostatic self-assembly method3N4/CeO2Composite catalyst material and commercial cerium oxide (CeO) obtained in comparative example I2) Catalyst materials Formaldehyde catalysis experiment was performed at room temperature, specifically, 0.1g of the monomer or composite catalyst materials prepared in example one, example two, example three, example four and example five and commercial cerium oxide (CeO) obtained in comparative example one were taken2) Catalyst is evenly spread and dispersed inA14 cm diameter petri dish was then placed in a 13L plexiglass reactor containing a 5W fan and a 20W fluorescent lamp. Injecting a 37% formaldehyde solution into the organic glass reactor, removing the glass cover and simultaneously turning on the fluorescent lamp for irradiation when the formaldehyde volatilizes until the concentration is balanced, so that the composite catalyst is mutually contacted with the formaldehyde under the irradiation of the fluorescent lamp, and the concentration change of the formaldehyde is monitored on line by a multi-component gas analyzer (INNOVA air Tech Instruments Model 1412 i). The monomer or composite catalyst materials prepared in examples one, two, three, four and five and the commercial ceria (CeO) obtained in comparative example one2) The data of the activity of the catalyst material in photocatalytic oxidation degradation of formaldehyde under the irradiation of a fluorescent lamp at room temperature are shown in Table 1.
TABLE 1 Activity of the hybrid catalyst at room temperature
As can be seen from Table 1, the nano-photocatalyst materials prepared in example one, example two, example three, example four and example five and the nano-photocatalyst material purchased in comparative example all showed significant photocatalytic degradation activity for formaldehyde under irradiation of a fluorescent lamp at room temperature, and the formaldehyde removal rate was stronger for all samples than the samples prepared in comparative example, which had the highest formaldehyde removal rate under no-light test due to commercial cerium oxide (CeO)2) Has the best adsorption effect on formaldehyde under the condition of no light. Meanwhile, by comparing the data of the optical test and the dark test of the composite catalyst samples prepared in the third, fourth and fifth examples under the irradiation of the fluorescent lamp at room temperature, it can be known that the photocatalytic activity of the catalyst materials prepared in the third, fourth and fifth examples of the present invention to formaldehyde under the irradiation of the fluorescent lamp at room temperature is significantly improved.From the above table, the root reason why the carbon dioxide generation rate is greater than the formaldehyde removal rate is that: in a closed reaction system, along with the continuous progress of the photocatalytic reaction, formaldehyde adsorbed on the inner wall of the box body is continuously desorbed and released to enter the reaction system, and carbon dioxide in the reaction system comes from the degradation of the formaldehyde. The reduction of the formaldehyde concentration and the increase of the carbon dioxide concentration are comprehensively compared, so that the catalytic degradation activity of the catalyst on formaldehyde can be obtained by comparison. Wherein g-C obtained in the fourth preparation of the invention3N4/CeO2The composite catalyst material has the highest visible light response degradation activity on formaldehyde (conversion of formaldehyde to carbon dioxide is considered to be complete degradation of formaldehyde).
g-C from example four3N4/CeO2The activity of the composite catalyst in the catalytic test of formaldehyde is shown in table 2 and fig. 6, which is repeated for a plurality of times (after the test is finished, the sample is stored in a sealed way, and before the next test, the sample is subjected to heat treatment in an electrothermal blowing dry box at 80 ℃ for 10 min).
Table 2 shows the activity of the photocatalyst prepared in the second embodiment of the present invention in catalyzing formaldehyde repeatedly
As can be seen from the data in Table 2 and shown in FIG. 6, g-C was prepared from example four3N4/CeO2After the composite catalyst repeatedly catalyzes and degrades formaldehyde for many times under visible light at room temperature, the catalytic degradation activity of the composite catalyst on formaldehyde is still kept above 70% (the generation rate of carbon dioxide is greater than the reduction rate of formaldehyde, namely formaldehyde attached to the surface of a test box body is degraded by the catalyst), which indicates that the prepared nano photocatalyst material has good physical and chemical stability.
It is obvious that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and that various other modifications and variations can be made by those skilled in the art based on the above description.
Claims (10)
1. g-C3N4@CeO2The preparation method of the composite catalyst is characterized by comprising the following steps: the method comprises the following steps:
g to C3N4Dispersing a monomer material in deionized water, and performing ultrasonic treatment to obtain a dispersion liquid I;
adding CeO2Dispersing the monomer material in deionized water, and performing ultrasonic treatment to obtain a dispersion liquid II:
dropwise adding the dispersion liquid I into the dispersion liquid II under stirring to obtain a mixed dispersion liquid;
continuously stirring the obtained mixed dispersion liquid to obtain a dispersion solution of a reaction product;
centrifuging and drying the reaction product to obtain a product containing g-C3N45-35 wt% of the composite catalyst.
2. g-C according to claim 13N4@CeO2The preparation method of the composite catalyst is characterized by comprising the following steps: the g to C3N4Monomer material and CeO2The mass ratio of the monomer materials is 1: 1-10.
3. g-C according to claim 1 or 23N4@CeO2The preparation method of the composite catalyst is characterized by comprising the following steps: dropwise adding the dispersion liquid I into the dispersion liquid II under the stirring state, wherein the dropwise adding time is 0.05-0.5 h; and/or continuously stirring the obtained mixed dispersion liquid for 0.2-0.8 h to obtain a dispersion solution of the reaction product.
4. According tog-C as claimed in any of claims 1 to 33N4@CeO2The preparation method of the composite catalyst is characterized by comprising the following steps: subjecting said g-C to3N4Dispersing the monomer material in deionized water, and carrying out ultrasonic treatment for 0.25-0.75 h to obtain a dispersion liquid I; and/or, the CeO2Dispersing the monomer material in deionized water, and carrying out ultrasonic treatment for 0.05-45 h to obtain a dispersion liquid II.
5. g-C according to any of claims 1 to 43N4@CeO2The preparation method of the composite catalyst is characterized by comprising the following steps: the precursor of the cerium dioxide monomer material is selected from one or more of cerium nitrate hexahydrate, cerium sulfate and cerium chloride, and preferably, the cerium nitrate hexahydrate; and/or, the CeO2The monomer material is prepared by a calcining method; and/or, said g-C3N4The precursor of the monomer material is selected from thiourea, melamine, urea and dicyanodiamine, and is preferably melamine; and/or, said g-C3N4The monomer material is prepared by a calcination method.
6. g-C according to claim 53N4@CeO2The preparation method of the composite catalyst is characterized by comprising the following steps: the g to C3N4The preparation method of the monomer material comprises the following steps:
g to C3N4Drying the precursor of the monomer material at 40-80 ℃ for 12-36 h to obtain dry solid powder;
calcining the dried solid powder at 500-650 ℃ for 1-6 h, and carrying out temperature programming at 1-5 ℃/min;
grinding the calcined product naturally cooled to room temperature to obtain the g-C prepared by the calcining method3N4A monomeric material.
7. g-C according to claim 53N4@CeO2The preparation method of the composite catalyst is characterized by comprising the following steps: the CeO2Single-body materialThe preparation method of the material comprises the following steps:
adding CeO2And calcining the precursor of the monomer material at 400-600 ℃ for 2-6 h, and grinding to obtain the cerium dioxide nano material, wherein the temperature programming condition is 1-5 ℃/min.
8. g-C according to any of claims 1-73N4@CeO2The preparation method of the composite catalyst is characterized by comprising the following steps: the g to C3N4@CeO2The preparation method of the composite catalyst comprises the following steps:
g to C3N4Dispersing the monomer material in deionized water, and carrying out ultrasonic treatment for 0.25-0.75 h to obtain a dispersion liquid I;
adding CeO2Dispersing the monomer material in deionized water, and carrying out ultrasonic treatment for 0.05-0.45 h to obtain a dispersion liquid II; the g to C3N4Monomer material and CeO2The mass ratio of the monomer materials is 1: 1-10;
dropwise adding the dispersion liquid I into the dispersion liquid II while stirring to obtain a dispersion liquid III, and continuously stirring for 0.2-0.8 h to obtain a mixed solution;
purifying the mixed solution by centrifugation, and drying the centrifuged product at 60-80 ℃ for 10-30 h to obtain g-C3N4@CeO2And (3) compounding a catalyst.
9. g-C obtained by the preparation process according to claims 1-83N4@CeO2And (3) compounding a catalyst.
10. g-C obtained by the preparation process according to claims 1-83N4@CeO2The application of the composite catalyst is characterized in that: subjecting said g-C to3N4@CeO2The composite catalyst is used for degrading formaldehyde under the irradiation of room temperature visible light.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113548686A (en) * | 2021-06-04 | 2021-10-26 | 江汉大学 | Cerium dioxide nano material and preparation method and application thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110694666A (en) * | 2019-11-07 | 2020-01-17 | 江汉大学 | C3N4@CeO2Supported low-content gold catalyst and preparation method and application thereof |
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-
2020
- 2020-10-26 CN CN202011158105.1A patent/CN112264071B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110694666A (en) * | 2019-11-07 | 2020-01-17 | 江汉大学 | C3N4@CeO2Supported low-content gold catalyst and preparation method and application thereof |
| CN111704155A (en) * | 2020-01-20 | 2020-09-25 | 中国石油大学(华东) | CeO (CeO)2/g-C3N4Humidity sensor of hybrid membrane and preparation method and application thereof |
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| CN114950520B (en) * | 2022-04-11 | 2023-10-03 | 湖北工业大学 | CeO (CeO) 2 Na, K doped g-C 3 N 4 Fenton-like catalytic material and preparation method and application thereof |
| CN114832848A (en) * | 2022-04-27 | 2022-08-02 | 中山市洁鼎过滤制品有限公司 | Catalyst and preparation method and application thereof |
| CN114832848B (en) * | 2022-04-27 | 2024-03-26 | 中山市洁鼎过滤制品有限公司 | Catalyst and preparation method and application thereof |
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