CN113649052A - Graphite-phase carbon nitride-based photocatalytic composite material and preparation and application thereof - Google Patents
Graphite-phase carbon nitride-based photocatalytic composite material and preparation and application thereof Download PDFInfo
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B01D—SEPARATION
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- 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
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Abstract
The invention discloses a graphite phase carbon nitride based photocatalytic composite material and preparation and application thereof, comprising the steps of dissolving polyvinylpyrrolidone into N, N-dimethylformamide containing oleic acid, and adding molybdenum disulfide powder; stirring, ultrasonically crushing and centrifuging to obtain MoS2A nanosheet dispersion; mixing melamine powder, thioacetamide and sodium chloride/potassium chloride, and performing thermal polycondensation to obtain a dark yellow product, namely S-doped g-C prepared from molten salt3N4(ii) a Doping S with g-C3N4Adding water, ultrasonic pulverizing, and centrifuging to obtain modified g-C with few layers3N4Powder; modifying g-C with few layers3N4Powder and MoS2Mixing the nano-sheet dispersion liquid and preparing a mixed liquid, and carrying out hydrothermal treatment on the mixed liquidTreating, performing solid-liquid separation on the mixed solution after full reaction to obtain lower-layer precipitate to obtain MoS2/g‑C3N4A photocatalytic composite material. The application of the photocatalyst in formaldehyde treatment can effectively control the harm of formaldehyde to human bodies and broaden the research range of photocatalytic materials.
Description
Technical Field
The invention relates to a composite photocatalyst, and in particular relates to a graphite-phase carbon nitride-based photocatalytic composite material as well as preparation and application thereof.
Background
The VOC of the indoor coating furniture slowly volatilizes, which has extremely bad influence on the living environment of people and seriously harms the healthy life of people. Formaldehyde is most typical of indoor air pollutants. The pollution of the formaldehyde is treated, on one hand, the generation of a source is required to be reduced, the content of pollutants such as formaldehyde in materials in the production and processing process is controlled, a novel pollution-free material is developed, products containing high harmful substances are forbidden to enter the market, and on the other hand, the pollutant removal efficiency is improved. At present, ventilation, filtration and adsorption methods are the main means for purifying indoor pollutants, but the pollutants cannot be completely degraded. The photocatalysis mode is one of the most effective methods for degrading formaldehyde in a room. According to the photocatalysis mechanism, when the photocatalyst is irradiated by light, the generated photoproduced electrons and photoproduced holes can generate hydroxyl free radicals (OH) and superoxide free radicals (O) in the surface oxidation process2 -) Active OH and O2 -The OH can obtain hydrogen in formaldehyde to generate hydroxyl radical (& CHO), the hydroxyl radical is further oxidized to carboxylic acid, and the carboxylic acid is finally oxidized and decomposed to generate CO2And H2And O. The reaction can realize the self-purification of indoor air, and if a heterojunction photocatalyst with high activity is used, the aim of effectively degrading formaldehyde can be achieved.
Although the existing photocatalyst for treating formaldehyde pollution has certain effect, most of the used materials comprise heavy metal substances or the equipment requirement is high, so that the cost is high. Therefore, the preparation of the photocatalyst which is cheap, low in cost, simple in process and capable of achieving the optimal performance is the key of large-scale production.
Disclosure of Invention
The invention aims to provide a graphite phase carbon nitride base (g-C)3N4Base) photocatalytic composite materials and their preparation and use. The g-C3N4The base composite photocatalyst can realize the effective separation of photo-generated electron hole pairs, promote the improvement of the photocatalytic efficiency and further enhance the performance of degrading formaldehyde.
The technical scheme adopted by the invention is as follows:
a preparation method of a graphite-phase carbon nitride-based photocatalytic composite material comprises the following steps:
dissolving polyvinylpyrrolidone into N, N-dimethylformamide containing oleic acid, and adding molybdenum disulfide powder; stirring, ultrasonically crushing, centrifuging, washing the obtained supernatant to obtain water-dispersed MoS2A nanosheet dispersion;
mixing melamine powder, thioacetamide and sodium chloride/potassium chloride, and performing thermal polycondensation to obtain a dark yellow product, namely S-doped g-C prepared from molten salt3N4；
Doping S with g-C3N4Adding water, ultrasonic pulverizing, centrifuging, collecting upper layer dispersion, rotary evaporating, collecting lower layer solid, drying, and grinding to obtain modified g-C with few layers3N4Powder;
modifying g-C with few layers3N4Powder and MoS2Mixing the nano-sheet dispersion liquid and preparing a mixed liquid, carrying out hydrothermal treatment on the mixed liquid, carrying out solid-liquid separation on the mixed liquid after full reaction to obtain a lower-layer precipitate to obtain MoS2/g-C3N4A photocatalytic composite material.
As a further improvement of the invention, the mass ratio of the polyvinylpyrrolidone, the oleic acid and the molybdenum disulfide powder is 1: 1: 1.
as a further development of the invention, the amount of thioacetamide added does not exceed 20% by weight of the total mass of melamine powder and thioacetamide.
As a further improvement of the invention, the mass ratio of Na salt to K salt in the sodium chloride/potassium chloride is 9: 11.
As a further improvement of the invention, the conditions of the thermal polycondensation reaction are:
heating to 550 ℃ from 120min, heating at a rate of 4-6 ℃/min, and reacting at 550 ℃ for 150-200 min.
As a further improvement of the method, the hydrothermal condition is 130-150 ℃, and the reaction is carried out for 10-13 h and then natural cooling is carried out.
As a further improvement of the invention, the few-layer modified g-C3N4Powder and MoS2The solid-to-liquid ratio of the nano-sheet dispersion liquid is 1g/5-20 ml.
As a further improvement of the invention, the ultrasonic pulverization is carried out by adopting an ultrasonic cell pulverizer, the system temperature is kept at 50 ℃ during the treatment, and the ultrasonic treatment is carried out for 10 hours;
the rotating speed of the centrifugation is 5000rpm, and the centrifugation is carried out for 10 min.
A preparation method of a graphite-phase carbon nitride-based photocatalytic composite material is provided.
The graphite-phase carbon nitride-based photocatalytic composite material prepared by the method is applied to treatment of formaldehyde pollution.
The invention has the following advantages:
the g-C3N4The base composite photocatalyst firstly directly adjusts the g-C of a main catalyst by doping elements3N4And adjusting the g-C using a salt melt having a higher melting point3N4The polymerization process of (3) can increase the light absorption range and improve the crystallinity. And the two different semiconductors are compounded, under the irradiation of light, the generated photon-generated carriers can be separated due to the characteristic that electrons spontaneously flow to a lower potential, and holes can also be transferred to the semiconductors with the lower potential, so that the effective separation of photon-generated electron hole pairs can be realized, the photocatalytic efficiency is improved, and the formaldehyde degradation performance is further enhanced. The invention discloses a graphite-phase carbon nitride-based photocatalytic composite material by utilizing element doping, molten salt adjustment, liquid phase stripping and heterojunction compounding methods. Compared with other photocatalysts currently applied, the prepared stoneThe equipment, the process and the medicine adopted by the ink-phase carbon nitride-based photocatalytic composite material are cheaper, and the best performance is achieved at the same time of low cost. By the pair g-C3N4The modification of (2) enlarges the light absorption range, increases the specific surface area and obviously improves the light utilization rate. Simultaneously adopts a 2D-2D heterojunction construction mode to modify g-C3N4As the main catalyst, MoS2As a cocatalyst, electrons can be quickly transferred through an interface connected by chemical bonds, the flow direction of the electrons and holes is changed, the recombination probability of photon-generated carriers is greatly reduced, and the formaldehyde removal efficiency is effectively improved.
Drawings
FIG. 1 is an SEM image (2 μm) of a graphite-phase carbon nitride-based photocatalytic composite material obtained in example 2;
fig. 2 is an XRD pattern of the graphite-phase carbon nitride-based photocatalytic composite material obtained in example 2;
FIG. 3 shows the RhB degradation performance of the graphite-phase carbon nitride-based photocatalytic composite material obtained in example 2;
fig. 4 shows the formaldehyde degradation performance of the graphite-phase carbon nitride-based photocatalytic composite material obtained in the example 2.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Graphite phase carbon nitride material (g-C)3N4) The photocatalyst is a typical non-metal semiconductor material, has excellent thermal conductivity and thermal stability, and has a proper forbidden band width to enable the material to respond under visible light conditions, so the photocatalyst attracts attention in various fields as a new-generation semiconductor material and is expected to be an efficient and sustainable photocatalyst. But due to larger interlayer spacing (0.67nm), the transmission between photogenerated electron layers is limited, the quantity of electrons transferred to the surface of the material is reduced, and the conductivity is not highAnd poor carrier transport capability, which restricts the photocatalytic reaction and application. Therefore, for g-C3N4The modification is carried out effectively, the recombination rate of photo-generated electron-hole pairs is reduced, and the photocatalytic reaction activity is improved.
The invention aims to provide a preparation method of a graphite-phase carbon nitride-based photocatalytic composite material. The g-C3N4The base composite photocatalyst firstly directly adjusts the g-C of a main catalyst by doping elements3N4And adjusting the g-C using a salt melt having a higher melting point3N4The polymerization process of (3) can increase the light absorption range and improve the crystallinity. And the two different semiconductors are compounded, under the irradiation of light, the generated photon-generated carriers can be separated due to the characteristic that electrons spontaneously flow to a lower potential, and holes can also be transferred to the semiconductors with the lower potential, so that the effective separation of photon-generated electron hole pairs can be realized, the photocatalytic efficiency is improved, and the formaldehyde degradation performance is further enhanced.
The invention relates to a graphite-phase carbon nitride-based photocatalytic composite material, which is prepared by doping non-metallic elements and salt melt to original g-C3N4The modified semiconductor material is combined with another semiconductor material to effectively enhance the activity of degrading formaldehyde by photocatalysis.
The thermal polycondensation method is selected to prepare the g-C, and the method has the advantages of simple process, easy operation, suitability for mass production, good crystallinity of the obtained sample and suitability for the application of the sample3N4A material. Element doping is an effective method for directly adjusting the band structure, and can be used for g-C3N4And engineering transformation is carried out on the medium heptazine ring and the electronic structure. Relatively cheap non-metal element S is selected as a dopant, and the g-C can be preferentially replaced by the doping of the non-metal element S3N4The nitrogen atoms at the edge of the heptazine unit expand the visible light absorption range and enhance the oxidation-reduction capability in the photocatalytic reaction. And adjusting the g-C using a NaCl/KCl mixed salt melt having a higher melting point3N4Ensuring the active polyheptazineimide as g-C3N4Main component and improve knotAnd (4) crystallinity.
A few layers of nano materials are used in the field of photocatalysis, and due to the greatly improved specific surface area, more edge active sites can be obtained, the utilization efficiency of visible light is enhanced, and the photocatalysis effect is improved. Transition metal sulfides (TMDC), a typical 2D layered material, are widely used in storage, catalysis, sensing and other electrochemical devices due to their attractive chemical and electrochemical properties, molybdenum disulfide (MoS)2) Are typical representatives of transition metal sulfides. Nano-scale MoS2With a variable band layered structure, so as to have photocatalytic activity under visible light, and as a nanomaterial, a single-layer MoS2The photocatalyst has large specific surface area, can provide more photoelectron active sites, enhances the catalytic activity of the photoelectron active sites to adsorb more reactant molecules, and becomes a photocatalyst with great advantages. In addition, a single layer of MoS2The forbidden band width is about 1.90eV, the energy band difference and the light and g-C3N4Are well matched in energy level and are well suited as g-C3N4The cocatalyst of (1). With g-C3N4The compound is easy to form MoS through chemical bond connection at high temperature and high pressure2/g-C3N4The binary nano composite material can effectively enhance the visible light absorption. After combination at g-C3N4The photoelectrons excited above will first transfer to the MoS2On the single layer, the material is migrated to the surface of the material to react with pollutants, and the process hinders the recombination of photoproduction electrons and holes on the catalyst, so that the photocatalysis capability is stronger, and the photocatalysis efficiency of organic pollutants and air purification is effectively improved.
To realize MoS2Application of thin layer in large-scale photocatalysis field, high-quality and high-efficiency preparation of few-layer MoS2Especially the key. Liquid phase exfoliation has been common for the use of layered materials, but ultrasonic manipulation by directly adding the material to a corresponding solvent often does not yield the desired effect. In general, whether the polarity of the solvent matches the material directly affects the degree of dispersion and stability. In addition, the addition of the surfactant and the intercalation agent can also greatly improve the yield of the nano-sheet layer and obviously improve the dispersion stability. By comparing and select MoS2DMF with equivalent surface energy is used as a solvent, and the quality and the concentration of a dispersion solution of the prepared nanosheet are improved in a mode of combining a small-molecule intercalating agent and a large-molecule surfactant.
The graphite-phase carbon nitride-based photocatalytic composite material is characterized by comprising the following steps:
(1) 0.25g polyvinylpyrrolidone (PVP) was dissolved in 50ml N, N-Dimethylformamide (DMF) containing 0.25g oleic acid, 0.25g molybdenum disulfide (MoS) was added2) And (3) powder. The mixture is stirred for 20min by magnetic force and is subjected to ultrasonic treatment for 20min to be mixed uniformly, and then the mixture is transferred to an ultrasonic cell crusher to be subjected to ultrasonic pulse stripping, so that the temperature of the system is kept at 50 ℃ and the ultrasonic treatment is accumulated for 10 h. Centrifuging the mixture at 5000rpm for 10min after the pulverization is finished, and obtaining the supernatant which is MoS2A nanosheet dispersion. The dispersion was washed twice with DMF to remove excess PVP and oleic acid, and then deionized water (H) was used by rotary evaporation2O) replacing the original solvent DMF twice to obtain the water-dispersed MoS2A nanosheet dispersion.
(2) Firstly, weighing 3-5g of melamine powder, washing the melamine powder by using deionized water and filtering the melamine powder to remove soluble impurities in a precursor and influence of easily decomposed substances on a sample. Oven-dried and mashed at 80 deg.C, and then 0-2g Thioacetamide (TAA) is added to make the total amount of thioacetamide and melamine 5 g. And simultaneously adding 10g of sodium chloride/potassium chloride (NaCI/KCI) as mixed molten salt (the mass ratio of Na salt to K salt is controlled to be 9:11), mixing and grinding for 30min by using a mortar, pouring into a 50ml crucible with a cover, flatly laying the mixed powder in the crucible, then placing the crucible into a muffle furnace for 120min, heating to 550 ℃ (the heating rate is 4-6 ℃/min), reacting at the constant temperature for 150-200 min, and cooling along with the furnace to obtain a dark yellow product. Subsequently, the milled product was dispersed in deionized water to dissolve the salt, filtered again, and washed out the salt three times. Drying in a 50 ℃ oven, grinding and sieving to obtain dark yellow powder, namely S-doped g-C prepared from the molten salt3N4。
(3) Weighing 1g of the above modified g-C3N4Placing in a beaker with 500ml deionized water, and magnetically stirring for 20min to mix uniformly.Then ultrasonic pulse stripping is carried out by adopting an ultrasonic cell crusher, and the temperature of the system is kept at 50 ℃ for 10 hours of cumulative ultrasound. Centrifuging the mixture at 5000rpm for 10min after pulverizing to obtain supernatant as few-layer g-C3N4Dispersing, removing water by rotary evaporation, collecting lower layer solid, drying, and grinding to obtain modified g-C with less layer3N4And (3) powder.
Weighing 0.5g of the treated few-layer modified g-C3N4Powder and 2.5-10ml of the above MoS2The nano dispersion liquid is placed in a 100ml polytetrafluoroethylene lining reaction kettle, and is added with 45-52.5ml deionized water and then is magnetically stirred for 30 min. And carrying out hydrothermal treatment on the mixed solution, putting the reaction kettle into a constant-temperature oven at 130-150 ℃, reacting for 10-13 h, and naturally cooling. And then, carrying out solid-liquid separation on the mixed liquid in the reaction kettle by using a centrifugal machine to obtain a lower-layer precipitate. Washing the solid precipitate with deionized water for several times, and drying in a 50 ℃ oven for 12h to obtain MoS2/g-C3N4A photocatalytic composite material.
The graphite-phase carbon nitride-based photocatalytic composite material prepared by the method can be used as a high-efficiency photocatalyst to be applied to the treatment of formaldehyde pollution.
The graphite-phase carbon nitride-based photocatalytic composite material is prepared by doping and modifying thioacetamide with g-C3N4The polymerization process is regulated through a sodium chloride/potassium chloride mixed molten salt body, and the sodium chloride/potassium chloride mixed molten salt body is stripped into a two-dimensional structure and compounded with few layers of molybdenum disulfide to prepare a heterojunction interface which is beneficial to promoting the separation of charge carriers. The photocatalyst obtained by the invention not only expands the light absorption range and improves the crystallinity, but also realizes the effective separation of the photo-generated electron hole pairs, promotes the improvement of the photocatalytic efficiency and further enhances the performance of degrading formaldehyde. The equipment, process and medicine used for preparation are all cheaper, and the best performance is achieved at the same time of low cost. The application of the photocatalyst in formaldehyde treatment can effectively control the harm of formaldehyde to human bodies and broaden the research range of photocatalytic materials.
Example 1
0.25g of polyvinylpyrrolidone (PVP) was dissolved to a solution containing 025g oleic acid in 50ml N, N-Dimethylformamide (DMF), 0.25g molybdenum disulphide (MoS) is added2) And (3) powder. Magnetically stirring for 20min, performing ultrasonic treatment for 20min, transferring to ultrasonic cell crusher, and maintaining the temperature at 50 deg.C for 10 hr. After the end of the comminution the mixture is centrifuged for 10min at 5000rpm, the resulting supernatant is washed twice with DMF and deionized water (H) is used by rotary evaporation2O) replacing the original solvent DMF twice, and scoring the dispersion to obtain a product I.
4g of melamine powder are weighed out, washed with deionized water and filtered, dried in an oven at 80 ℃ and triturated, and 1g of Thioacetamide (TAA) are added. Meanwhile, 10g of sodium chloride/potassium chloride (NaCI/KCI) is added to serve as mixed molten salt (the mass ratio of Na salt to K salt is controlled to be 9:11), a mortar is used for mixing and grinding for 30min, the mixed molten salt is poured into a 50ml crucible with a cover, the mixed powder is flatly laid in the crucible, then the crucible is placed into a muffle furnace for 120min, the temperature is raised to 550 ℃ (the temperature raising rate is 5 ℃/min), the constant temperature reaction is carried out for 180min at the temperature, and furnace cooling is carried out to obtain a dark yellow product. The milled product was then dispersed in deionized water to dissolve the salts, filtered and repeated three times. The mixture was dried in an oven at 50 ℃ and ground and sieved, giving a dark yellow powder as product II.
Weighing 1g of the product II, placing the product II in a beaker with 500ml of deionized water, magnetically stirring for 20min, and then adopting an ultrasonic cell crusher to keep the temperature of the system at 50 ℃ for accumulating the ultrasonic for 10 h. After the completion of the pulverization, the mixture was centrifuged at 5000rpm for 10min, the upper dispersion was collected by rotary evaporation, and the lower solid was collected, dried and ground, and the obtained sample was designated as product III.
Weighing 0.5g of the product III and 5ml of the product I, placing the product III and the product I into a 100ml polytetrafluoroethylene-lined reaction kettle, supplementing 50ml of deionized water, and then carrying out magnetic stirring for 30 min. And (3) putting the reaction kettle into a constant-temperature oven at 140 ℃, reacting for 12h, and naturally cooling. And then, carrying out solid-liquid separation on the mixed liquid in the reaction kettle by using a centrifugal machine to obtain a lower-layer precipitate. Washing the solid precipitate with deionized water for several times, and drying in a 50 ℃ oven for 12h to obtain the target product.
Example 2
0.25g polyvinylpyrrolidone (PVP) was dissolved to a solution containing 0.25g oilTo 50ml of N, N-Dimethylformamide (DMF) of an acid was added 0.25g of molybdenum disulfide (MoS)2) And (3) powder. Magnetically stirring for 20min, performing ultrasonic treatment for 20min, transferring to ultrasonic cell crusher, and maintaining the temperature at 50 deg.C for 10 hr. After the end of the comminution the mixture is centrifuged for 10min at 5000rpm, the resulting supernatant is washed twice with DMF and deionized water (H) is used by rotary evaporation2O) replacing the original solvent DMF twice, and scoring the dispersion to obtain a product I.
3.5g of melamine powder are weighed out, washed with deionized water and filtered, dried in an oven at 80 ℃ and triturated, and 1.5g of Thioacetamide (TAA) are added. Meanwhile, 10g of sodium chloride/potassium chloride (NaCI/KCI) is added to serve as mixed molten salt (the mass ratio of Na salt to K salt is controlled to be 9:11), a mortar is used for mixing and grinding for 30min, the mixed molten salt is poured into a 50ml crucible with a cover, the mixed powder is flatly laid in the crucible, then the crucible is placed into a muffle furnace for 120min, the temperature is raised to 550 ℃ (the temperature raising rate is 5 ℃/min), the constant temperature reaction is carried out for 180min at the temperature, and furnace cooling is carried out to obtain a dark yellow product. The milled product was then dispersed in deionized water to dissolve the salts, filtered and repeated three times. The mixture was dried in an oven at 50 ℃ and ground and sieved, giving a dark yellow powder as product II.
Weighing 1g of the product II, placing the product II in a beaker with 500ml of deionized water, magnetically stirring for 20min, and then adopting an ultrasonic cell crusher to keep the temperature of the system at 50 ℃ for accumulating the ultrasonic for 10 h. After the completion of the pulverization, the mixture was centrifuged at 5000rpm for 10min, the upper dispersion was collected by rotary evaporation, and the lower solid was collected, dried and ground, and the obtained sample was designated as product III.
Weighing 0.5g of the product III and 5ml of the product I, placing the product III and the product I into a 100ml polytetrafluoroethylene-lined reaction kettle, supplementing 50ml of deionized water, and then carrying out magnetic stirring for 30 min. And (3) putting the reaction kettle into a constant-temperature oven at 140 ℃, reacting for 12h, and naturally cooling. And then, carrying out solid-liquid separation on the mixed liquid in the reaction kettle by using a centrifugal machine to obtain a lower-layer precipitate. Washing the solid precipitate with deionized water for several times, and drying in a 50 ℃ oven for 12h to obtain the target product.
Example 3
0.25g polyvinylpyrrolidone (PVP) was dissolved to contain 0.25g oleic acid50ml of N, N-Dimethylformamide (DMF), 0.25g of molybdenum disulfide (MoS) are added2) And (3) powder. Magnetically stirring for 20min, performing ultrasonic treatment for 20min, transferring to ultrasonic cell crusher, and maintaining the temperature at 50 deg.C for 10 hr. After the end of the comminution the mixture is centrifuged for 10min at 5000rpm, the resulting supernatant is washed twice with DMF and deionized water (H) is used by rotary evaporation2O) replacing the original solvent DMF twice, and scoring the dispersion to obtain a product I.
3g of melamine powder are weighed out, washed with deionized water and filtered, dried in an oven at 80 ℃ and triturated, and 2g of Thioacetamide (TAA) are added. Meanwhile, 10g of sodium chloride/potassium chloride (NaCI/KCI) is added to serve as mixed molten salt (the mass ratio of Na salt to K salt is controlled to be 9:11), a mortar is used for mixing and grinding for 30min, the mixed molten salt is poured into a 50ml crucible with a cover, the mixed powder is flatly laid in the crucible, then the crucible is placed into a muffle furnace for 120min, the temperature is raised to 550 ℃ (the temperature raising rate is 5 ℃/min), the constant temperature reaction is carried out for 180min at the temperature, and furnace cooling is carried out to obtain a dark yellow product. The milled product was then dispersed in deionized water to dissolve the salts, filtered and repeated three times. The mixture was dried in an oven at 50 ℃ and ground and sieved, giving a dark yellow powder as product II.
Weighing 1g of the product II, placing the product II in a beaker with 500ml of deionized water, magnetically stirring for 20min, and then adopting an ultrasonic cell crusher to keep the temperature of the system at 50 ℃ for accumulating the ultrasonic for 10 h. After the completion of the pulverization, the mixture was centrifuged at 5000rpm for 10min, the upper dispersion was collected by rotary evaporation, and the lower solid was collected, dried and ground, and the obtained sample was designated as product III.
Weighing 0.5g of the product III and 5ml of the product I, placing the product III and the product I into a 100ml polytetrafluoroethylene-lined reaction kettle, supplementing 50ml of deionized water, and then carrying out magnetic stirring for 30 min. And (3) putting the reaction kettle into a constant-temperature oven at 140 ℃, reacting for 12h, and naturally cooling. And then, carrying out solid-liquid separation on the mixed liquid in the reaction kettle by using a centrifugal machine to obtain a lower-layer precipitate. Washing the solid precipitate with deionized water for several times, and drying in a 50 ℃ oven for 12h to obtain the target product.
Example 4
0.25g of polyvinylpyrrolidone (PVP) was dissolved in 50ml containing 0.25g of oleic acidTo N, N-Dimethylformamide (DMF), 0.25g of molybdenum disulfide (MoS) was added2) And (3) powder. Magnetically stirring for 20min, performing ultrasonic treatment for 20min, transferring to ultrasonic cell crusher, and maintaining the temperature at 50 deg.C for 10 hr. After the end of the comminution the mixture is centrifuged for 10min at 5000rpm, the resulting supernatant is washed twice with DMF and deionized water (H) is used by rotary evaporation2O) replacing the original solvent DMF twice, and scoring the dispersion to obtain a product I.
3.5g of melamine powder are weighed out, washed with deionized water and filtered, dried in an oven at 80 ℃ and triturated, and 1.5g of Thioacetamide (TAA) are added. Meanwhile, 10g of sodium chloride/potassium chloride (NaCI/KCI) is added to serve as mixed molten salt (the mass ratio of Na salt to K salt is controlled to be 9:11), a mortar is used for mixing and grinding for 30min, the mixed molten salt is poured into a 50ml crucible with a cover, the mixed powder is flatly laid in the crucible, then the crucible is placed into a muffle furnace for 120min, the temperature is raised to 550 ℃ (the temperature raising rate is 5 ℃/min), the constant temperature reaction is carried out for 180min at the temperature, and furnace cooling is carried out to obtain a dark yellow product. The milled product was then dispersed in deionized water to dissolve the salts, filtered and repeated three times. The mixture was dried in an oven at 50 ℃ and ground and sieved, giving a dark yellow powder as product II.
Weighing 1g of the product II, placing the product II in a beaker with 500ml of deionized water, magnetically stirring for 20min, and then adopting an ultrasonic cell crusher to keep the temperature of the system at 50 ℃ for accumulating the ultrasonic for 10 h. After the completion of the pulverization, the mixture was centrifuged at 5000rpm for 10min, the upper dispersion was collected by rotary evaporation, and the lower solid was collected, dried and ground, and the obtained sample was designated as product III.
0.5g of product III and 2.5ml of product I are weighed out and placed in a 100ml reaction vessel lined with polytetrafluoroethylene, and magnetic stirring is carried out for 30min after 52.5ml of deionized water is added. And (3) putting the reaction kettle into a constant-temperature oven at 140 ℃, reacting for 12h, and naturally cooling. And then, carrying out solid-liquid separation on the mixed liquid in the reaction kettle by using a centrifugal machine to obtain a lower-layer precipitate. Washing the solid precipitate with deionized water for several times, and drying in a 50 ℃ oven for 12h to obtain the target product.
Example 5
0.25g of polyvinylpyrrolidone (PVP) was dissolved in 50m of oleic acidl N, N-Dimethylformamide (DMF), 0.25g of molybdenum disulfide (MoS) was added2) And (3) powder. Magnetically stirring for 20min, performing ultrasonic treatment for 20min, transferring to ultrasonic cell crusher, and maintaining the temperature at 50 deg.C for 10 hr. After the end of the comminution the mixture is centrifuged for 10min at 5000rpm, the resulting supernatant is washed twice with DMF and deionized water (H) is used by rotary evaporation2O) replacing the original solvent DMF twice, and scoring the dispersion to obtain a product I.
3.5g of melamine powder are weighed out, washed with deionized water and filtered, dried in an oven at 80 ℃ and triturated, and 1.5g of Thioacetamide (TAA) are added. Meanwhile, 10g of sodium chloride/potassium chloride (NaCI/KCI) is added to serve as mixed molten salt (the mass ratio of Na salt to K salt is controlled to be 9:11), a mortar is used for mixing and grinding for 30min, the mixed molten salt is poured into a 50ml crucible with a cover, the mixed powder is flatly laid in the crucible, then the crucible is placed into a muffle furnace for 120min, the temperature is raised to 550 ℃ (the temperature raising rate is 5 ℃/min), the constant temperature reaction is carried out for 180min at the temperature, and furnace cooling is carried out to obtain a dark yellow product. The milled product was then dispersed in deionized water to dissolve the salts, filtered and repeated three times. The mixture was dried in an oven at 50 ℃ and ground and sieved, giving a dark yellow powder as product II.
Weighing 1g of the product II, placing the product II in a beaker with 500ml of deionized water, magnetically stirring for 20min, and then adopting an ultrasonic cell crusher to keep the temperature of the system at 50 ℃ for accumulating the ultrasonic for 10 h. After the completion of the pulverization, the mixture was centrifuged at 5000rpm for 10min, the upper dispersion was collected by rotary evaporation, and the lower solid was collected, dried and ground, and the obtained sample was designated as product III.
0.5g of product III and 10ml of product I are weighed out and placed in a 100ml reaction kettle with a polytetrafluoroethylene lining, and after 45ml of deionized water is added, magnetic stirring is carried out for 30 min. And (3) putting the reaction kettle into a constant-temperature oven at 140 ℃, reacting for 12h, and naturally cooling. And then, carrying out solid-liquid separation on the mixed liquid in the reaction kettle by using a centrifugal machine to obtain a lower-layer precipitate. Washing the solid precipitate with deionized water for several times, and drying in a 50 ℃ oven for 12h to obtain the target product.
Example 6
0.25g of polyvinylpyrrolidone (PVP) was dissolved in 50ml containing 0.25g of oleic acidTo N, N-Dimethylformamide (DMF), 0.25g of molybdenum disulfide (MoS) was added2) And (3) powder. Magnetically stirring for 20min, performing ultrasonic treatment for 20min, transferring to ultrasonic cell crusher, and maintaining the temperature at 50 deg.C for 10 hr. After the end of the comminution the mixture is centrifuged for 10min at 5000rpm, the resulting supernatant is washed twice with DMF and deionized water (H) is used by rotary evaporation2O) replacing the original solvent DMF twice, and scoring the dispersion to obtain a product I.
3.5g of melamine powder are weighed out, washed with deionized water and filtered, dried in an oven at 80 ℃ and triturated, and 1.5g of Thioacetamide (TAA) are added. Meanwhile, 10g of sodium chloride/potassium chloride (NaCI/KCI) is added to serve as mixed molten salt (the mass ratio of Na salt to K salt is controlled to be 9:11), a mortar is used for mixing and grinding for 30min, the mixed molten salt is poured into a 50ml crucible with a cover, the mixed powder is flatly laid in the crucible, then the crucible is placed into a muffle furnace for 120min, the temperature is raised to 550 ℃ (the temperature raising rate is 3 ℃/min), the constant temperature reaction is carried out for 200min at the temperature, and furnace cooling is carried out to obtain a dark yellow product. The milled product was then dispersed in deionized water to dissolve the salts, filtered and repeated three times. The mixture was dried in an oven at 50 ℃ and ground and sieved, giving a dark yellow powder as product II.
Weighing 1g of the product II, placing the product II in a beaker with 500ml of deionized water, magnetically stirring for 20min, and then adopting an ultrasonic cell crusher to keep the temperature of the system at 50 ℃ for accumulating the ultrasonic for 10 h. After the completion of the pulverization, the mixture was centrifuged at 5000rpm for 10min, the upper dispersion was collected by rotary evaporation, and the lower solid was collected, dried and ground, and the obtained sample was designated as product III.
0.5g of product III and 10ml of product I are weighed out and placed in a 100ml reaction kettle with a polytetrafluoroethylene lining, and after 45ml of deionized water is added, magnetic stirring is carried out for 30 min. And (3) putting the reaction kettle into a constant-temperature oven at 130 ℃, reacting for 13h, and naturally cooling. And then, carrying out solid-liquid separation on the mixed liquid in the reaction kettle by using a centrifugal machine to obtain a lower-layer precipitate. Washing the solid precipitate with deionized water for several times, and drying in a 50 ℃ oven for 12h to obtain the target product.
Example 7
0.25g of polyvinylpyrrolidone (PVP) was dissolved in 50ml of N containing 0.25g of oleic acid,to N-Dimethylformamide (DMF), 0.25g of molybdenum disulfide (MoS) was added2) And (3) powder. Magnetically stirring for 20min, performing ultrasonic treatment for 20min, transferring to ultrasonic cell crusher, and maintaining the temperature at 50 deg.C for 10 hr. After the end of the comminution the mixture is centrifuged for 10min at 5000rpm, the resulting supernatant is washed twice with DMF and deionized water (H) is used by rotary evaporation2O) replacing the original solvent DMF twice, and scoring the dispersion to obtain a product I.
3.5g of melamine powder are weighed out, washed with deionized water and filtered, dried in an oven at 80 ℃ and triturated, and 1.5g of Thioacetamide (TAA) are added. Meanwhile, 10g of sodium chloride/potassium chloride (NaCI/KCI) is added to serve as mixed molten salt (the mass ratio of Na salt to K salt is controlled to be 9:11), a mortar is used for mixing and grinding for 30min, the mixed molten salt is poured into a 50ml crucible with a cover, the mixed powder is flatly laid in the crucible, then the crucible is placed into a muffle furnace for 120min, the temperature is raised to 550 ℃ (the temperature raising rate is 6 ℃/min), the constant temperature reaction is carried out for 150min at the temperature, and furnace cooling is carried out to obtain a dark yellow product. The milled product was then dispersed in deionized water to dissolve the salts, filtered and repeated three times. The mixture was dried in an oven at 50 ℃ and ground and sieved, giving a dark yellow powder as product II.
Weighing 1g of the product II, placing the product II in a beaker with 500ml of deionized water, magnetically stirring for 20min, and then adopting an ultrasonic cell crusher to keep the temperature of the system at 50 ℃ for accumulating the ultrasonic for 10 h. After the completion of the pulverization, the mixture was centrifuged at 5000rpm for 10min, the upper dispersion was collected by rotary evaporation, and the lower solid was collected, dried and ground, and the obtained sample was designated as product III.
0.5g of product III and 10ml of product I are weighed out and placed in a 100ml reaction kettle with a polytetrafluoroethylene lining, and after 45ml of deionized water is added, magnetic stirring is carried out for 30 min. And (3) putting the reaction kettle into a constant-temperature oven at 150 ℃, reacting for 11h, and naturally cooling. And then, carrying out solid-liquid separation on the mixed liquid in the reaction kettle by using a centrifugal machine to obtain a lower-layer precipitate. Washing the solid precipitate with deionized water for several times, and drying in a 50 ℃ oven for 12h to obtain the target product.
In order to characterize the morphological characteristics of the graphite-phase carbon nitride-based photocatalytic composite material, a field emission Scanning Electron Microscope (SEM) test was performed on the target product in example 2, and the result is shown in fig. 1. FIG. 1 SEM photograph (2 μm) of the graphite-phase carbon nitride-based photocatalytic composite material obtained in example 2
As can be seen, the sample morphology exhibits an aggregate state and holes appear, indicating a few layers of MoS2With layers g-C3N4Binding occurs gradually. The morphology still maintains g-C3N4Typically a layered structure.
In order to verify the crystal structure characteristics of the graphite-phase carbon nitride-based photocatalytic composite material, the target product in example 2 was subjected to an X-ray powder diffraction (XRD) test, and the results are shown in fig. 2. FIG. 2 XRD pattern of graphite-phase carbon nitride-based photocatalytic composite material obtained in example 2
As can be seen from the figure, the graphite phase carbon nitride based photocatalytic composite material has peak patterns and pure g-C at about 27.5 degrees and 13.3 degrees3N4Similar Bragg diffraction peaks, indicating that the crystal structure is not due to MoS2The nanolayer is destroyed by the addition. In contrast, by comparing the (002) diffraction peak at 27.5 °, it was found that the half-peak width of the composite material was slightly narrowed and the peak position was shifted leftward, and that the crystallinity was rather improved means MoS2And g-C3N4The sheet faces are bonded fairly tightly and the expansion of the layer spacing is attributed to the few layers of MoS2Go into g-C3N4Interlaminar, indicating successful recombination of the two semiconductors. In addition, it can be observed that the composite material exhibits intrinsic few-layer MoS at 39.5 °, 44.5 ° and 58.3 °2The weak diffraction peaks of the (103), (104) and (110) planes of (A) confirm MoS2Successful introduction of (1).
The degradation of organic dye is the most important index for reflecting the photocatalytic performance, so the performance of the target product can be evaluated by testing the degradation effect of rhodamine B (RhB). The specific test process is as follows:
0.1g of the prepared photocatalytic sample is added into 50ml of 20mg/l rhodamine B (RhB) solution, magnetic stirring is used for stirring for 30min under the dark condition to enable the solution to reach adsorption-desorption equilibrium, then a 300W xenon lamp is used for illumination under stirring, 1ml of sample is taken at intervals, and supernatant is centrifuged to test the concentration change of the rhodamine B under an ultraviolet visible spectrophotometer. The maximum absorption intensity at 553nm was measured and plotted to obtain a degradation curve, the results of which are shown in FIG. 3. FIG. 3 shows RhB degradation performance of the graphite-phase carbon nitride-based photocatalytic composite material obtained in example 2
As can be seen from the figure, the degradation rate of the composite material is obviously improved, nearly half of RhB can be removed within 10min, and the degradation efficiency reaches 82.9% after 1h, so that the separation of electron-hole pairs is further accelerated due to the formation of a heterojunction.
The performance of the target product is evaluated by testing the degradation effect of formaldehyde. The specific test process is as follows:
0.1g of prepared photocatalytic sample is uniformly placed in a culture dish, the culture dish is placed at the bottom of a 500ml cylindrical gas reactor, the upper part of the culture dish is sealed by light-transmitting quartz glass and covered by tinfoil paper to prevent light from transmitting, meanwhile, a side wall interface of the gas reactor is connected with an infrared spectrum gas detector (Innova 1512), and real-time monitoring of formaldehyde and CO in the gas reactor is started2、H2Concentration of gas components such as O. Before the reaction starts, 100ppm of formaldehyde gas is injected from a side wall interface, after the formaldehyde in the reactor is stable and reaches adsorption-desorption balance, the tin foil paper is taken away, a 300W xenon lamp is adopted for illumination, the photocatalytic reaction starts, and the detection interval of a gas detector is set to be 10 min. The results are shown in FIG. 4. FIG. 4 shows the formaldehyde degrading performance of the graphite-phase carbon nitride-based photocatalytic composite material obtained in example 2
As can be seen from the figure, the degradation efficiency of the composite material reaches 77.6% after 2h of illumination, which indicates that the electron migration generated by the coupling of the heterojunction interface is very effective for separating carriers, thereby generating more activity h+Participate in the oxidation reaction.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.
Claims (10)
1. A preparation method of a graphite-phase carbon nitride-based photocatalytic composite material is characterized by comprising the following steps:
dissolving polyvinylpyrrolidone into N, N-dimethylformamide containing oleic acid, and adding molybdenum disulfide powder; stirring, ultrasonically crushing, centrifuging, washing the obtained supernatant to obtain water-dispersed MoS2A nanosheet dispersion;
mixing melamine powder, thioacetamide and sodium chloride/potassium chloride, and performing thermal polycondensation to obtain a dark yellow product, namely S-doped g-C prepared from molten salt3N4；
Doping S with g-C3N4Adding water, ultrasonic pulverizing, centrifuging, collecting upper layer dispersion, rotary evaporating, collecting lower layer solid, drying, and grinding to obtain modified g-C with few layers3N4Powder;
modifying g-C with few layers3N4Powder and MoS2Mixing the nano-sheet dispersion liquid and preparing a mixed liquid, carrying out hydrothermal treatment on the mixed liquid, carrying out solid-liquid separation on the mixed liquid after full reaction to obtain a lower-layer precipitate to obtain MoS2/g-C3N4A photocatalytic composite material.
2. The method of claim 1, wherein the mass ratio of polyvinylpyrrolidone, oleic acid and molybdenum disulfide powder is 1: 1: 1.
3. the method of claim 1 wherein the thioacetamide is added in an amount of no more than 20 wt% based on the total mass of the melamine powder and the thioacetamide.
4. The method of claim 1 wherein the Na salt to K salt mass ratio of the sodium chloride/potassium chloride is 9: 11.
5. The method of claim 1 wherein the thermal polycondensation reaction is carried out under the following conditions:
heating to 550 ℃ from 120min, heating at a rate of 4-6 ℃/min, and reacting at 550 ℃ for 150-200 min.
6. The method of claim 1 wherein the step of preparing a graphite phase carbon nitride based photocatalytic composite material,
the hydrothermal condition is 130-150 ℃, and the reaction is carried out for 10-13 h and then the reaction is naturally cooled.
7. The method of claim 1 wherein the step of preparing a graphite phase carbon nitride based photocatalytic composite material,
the few-layer modified g-C3N4Powder and MoS2The solid-to-liquid ratio of the nano-sheet dispersion liquid is 1g/5-20 ml.
8. The method for preparing the graphite-phase carbon nitride-based photocatalytic composite material according to claim 1, wherein the ultrasonic pulverization is carried out by an ultrasonic cell pulverizer, wherein the system temperature is kept at 50 ℃ during the ultrasonic pulverization, and the ultrasonic treatment is carried out for 10 hours;
the rotating speed of the centrifugation is 5000rpm, and the centrifugation is carried out for 10 min.
9. A method for preparing a graphite-phase carbon nitride-based photocatalytic composite material, characterized by being prepared by the method of any one of claims 1 to 8.
10. Use of the graphite-phase carbon nitride-based photocatalytic composite material prepared by the method according to any one of claims 1 to 8 for treating formaldehyde pollution.
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