CN113649052B - 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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- 239000002131 composite material Substances 0.000 title claims abstract description 45
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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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
- B01J27/24—Nitrogen compounds
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- Health & Medical Sciences (AREA)
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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, ultrasonic pulverizing, and centrifuging to obtain MoS 2 A nanosheet dispersion; mixing melamine powder, thioacetamide and sodium chloride/potassium chloride, and performing thermal polycondensation reaction to obtain a dark yellow product, namely the S-doped g-C prepared by molten salt 3 N 4 The method comprises the steps of carrying out a first treatment on the surface of the S doping g-C 3 N 4 Adding water, ultrasonic pulverizing, centrifuging to obtain few-layer modified g-C 3 N 4 A powder; taking few layers of modified g-C 3 N 4 Powder and MoS 2 Mixing the nanosheet dispersion liquid, preparing a mixed liquid, performing hydrothermal treatment on the mixed liquid, performing solid-liquid separation on the mixed liquid after full reaction to obtain lower-layer sediment, and obtaining MoS 2 /g‑C 3 N 4 A photocatalytic composite material. The application of the method can effectively control the harm of formaldehyde to human bodies in the aspect of formaldehyde treatment, and widens the research range of photocatalytic materials.
Description
Technical Field
The invention relates to a composite photocatalyst, in particular to a graphite-phase carbon nitride-based photocatalytic composite material and preparation and application thereof.
Background
The VOC of the indoor paint furniture volatilizes slowly, which has bad influence on the living environment of people and seriously damages the healthy life of people. The most typical indoor air contaminant is formaldehyde. On one hand, the pollution of formaldehyde needs to be controlled by reducing the generation of the source, controlling the content of pollutants such as formaldehyde in materials in the production and processing process, developing novel pollution-free materials, prohibiting products containing high harmful substances from entering the market, and on the other hand, improving the pollutant removal efficiency. Currently, ventilation, filtration and adsorption are the main means of purifying indoor pollutants, but cannot thoroughly degrade the pollutants. Photocatalytic means is one of the most effective methods for degrading formaldehyde in a room. According to the photocatalysis mechanism, when the photocatalyst is irradiated, generated photo-generated electrons and photo-generated holes can generate hydroxyl free radicals (OH) and superoxide free radicals (O) in the surface oxidation process 2 - ) Activity OH and O 2 - Together with the oxidation, OH can obtain hydrogen in formaldehyde to generate hydrocarbon oxygen free radical (CHO), and then the hydrocarbon oxygen free radical is further oxidized into carboxylic acid, and the carboxylic acid is finally oxidized and decomposed to generate CO 2 And H 2 O. The self-purification of indoor air can be realized through the reaction, and the aim of effectively degrading formaldehyde can be achieved if a heterojunction photocatalyst with high activity is used.
The existing photocatalyst for treating formaldehyde pollution has certain effect, but most of materials used comprise heavy metal substances or equipment requirements are high, so that the photocatalyst is high in price. Therefore, the preparation of a photocatalyst which is cheaper, has low cost and simple process and achieves the best performance is the key of mass production.
Disclosure of Invention
The invention aims to provide a graphite phase carbon nitride base (g-C 3 N 4 Base) photocatalytic composite material, and its preparation and application. The g-C 3 N 4 The base composite photocatalyst can realize the effective separation of photo-generated electron hole pairs, promote the improvement of the photocatalysis efficiency, and further enhance the formaldehyde degradation performance.
The technical scheme adopted by the invention is as follows:
the preparation method of the 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, ultrasonic pulverizing, centrifuging, and washing the supernatant to obtain water-dispersed MoS 2 A nanosheet dispersion;
mixing melamine powder, thioacetamide and sodium chloride/potassium chloride, and performing thermal polycondensation reaction to obtain a dark yellow product, namely the S-doped g-C prepared by molten salt 3 N 4 ；
S doping g-C 3 N 4 Adding water, ultrasonic pulverizing, centrifuging, collecting upper dispersion, rotary evaporating, collecting lower solid, drying, and grinding to obtain few modified g-C 3 N 4 A powder;
taking few layers of modified g-C 3 N 4 Powder and MoS 2 Mixing the nanosheet dispersion liquid, preparing a mixed liquid, performing hydrothermal treatment on the mixed liquid, performing solid-liquid separation on the mixed liquid after full reaction to obtain lower-layer sediment, and obtaining MoS 2 /g-C 3 N 4 A photocatalytic composite material.
As a further improvement of the invention, the mass ratio of polyvinylpyrrolidone, oleic acid and molybdenum disulfide powder is 1:1:1.
as a further improvement of the invention, the thioacetamide is added in an amount of not more than 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 present invention, the conditions of the thermal polycondensation reaction are:
heating to 550 ℃ from 120min, heating rate is 4-6 ℃/min, and reacting for 150-200 min at 550 ℃ under constant temperature.
As a further improvement of the invention, the hydrothermal condition is 130-150 ℃, and the reaction is carried out for 10-13 h and then the reaction product is naturally cooled.
As an approach to the inventionOne-step improvement, the few-layer modified g-C 3 N 4 Powder and MoS 2 The solid-liquid ratio of the nano-sheet dispersion liquid is 1g/5-20ml.
As a further improvement of the invention, the ultrasonic crushing is processed by an ultrasonic cell crusher, the temperature of the system is kept at 50 ℃ during the processing, and the ultrasonic is accumulated for 10 hours;
the rotational speed of the centrifugation is 5000rpm, and the centrifugation is carried out for 10min.
A preparation method of a graphite-phase carbon nitride-based photocatalytic composite material is provided, and the graphite-phase carbon nitride-based photocatalytic composite material is prepared by the method.
The graphite-phase carbon nitride-based photocatalytic composite material prepared by the method is applied to formaldehyde pollution treatment.
The invention has the following advantages:
the g-C 3 N 4 The base composite photocatalyst directly adjusts the main catalyst g-C through element doping 3 N 4 And adjusting g-C using a salt melt having a higher melting point 3 N 4 And (3) the polymerization process of the polymer increases the light absorption range and improves the crystallinity. And then, the two different semiconductors are combined, and generated photo-generated carriers can be separated due to the characteristic that electrons spontaneously flow to a lower potential under the irradiation of light, and holes can be transferred to the semiconductor with the lower potential, so that the effective separation of photo-generated electron-hole pairs can be realized, the improvement of the photo-catalytic efficiency is promoted, 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 applied at present, the prepared graphite-phase carbon nitride-based photocatalytic composite material has the advantages that equipment, process and medicines are low in cost, and the optimal performance is achieved at the same time. By reacting g-C 3 N 4 The modification of the light-absorbing material can expand the light-absorbing range and increase the specific surface area, and the light utilization rate is obviously improved. Meanwhile, a 2D-2D heterojunction construction mode is adopted to modify g-C 3 N 4 As a main catalyst, moS 2 As a cocatalyst, electrons can be rapidly transferred through an interface of chemical bond connection, and the method is improvedThe flow direction of electrons and holes is changed, the recombination probability of photo-generated carriers is greatly reduced, and the formaldehyde removal efficiency is effectively improved.
Drawings
FIG. 1 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 degradation RhB properties of the graphite-phase carbon nitride-based photocatalytic composite material obtained in example 2;
FIG. 4 formaldehyde degrading properties of the graphite phase carbon nitride based photocatalytic composite material obtained in example 2.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Graphite phase carbon nitride material (g-C) 3 N 4 ) Is a typical nonmetallic semiconductor material, and has excellent thermal conductivity and thermal stability, and a proper forbidden bandwidth can enable the material to respond under the condition of visible light, so the material is attractive in various fields as a new-generation semiconductor material, and is expected to become a high-efficiency sustainable photocatalyst. However, due to the larger interlayer spacing (0.67 nm), the transfer between the photo-generated electron layers is limited, the electron quantity transferred to the surface of the material is reduced, and meanwhile, the carrier transmission capability is poor due to low conductivity, so that the photo-catalytic reaction and application of the material are restricted. Thus, g-C is required 3 N 4 Effective modification is carried out, 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-C 3 N 4 The base composite photocatalyst directly adjusts the main catalyst g-C through element doping 3 N 4 And adjusting g-C using a salt melt having a higher melting point 3 N 4 And (3) the polymerization process of the polymer increases the light absorption range and improves the crystallinity. And then, the two different semiconductors are combined, and generated photo-generated carriers can be separated due to the characteristic that electrons spontaneously flow to a lower potential under the irradiation of light, and holes can be transferred to the semiconductor with the lower potential, so that the effective separation of photo-generated electron-hole pairs can be realized, the improvement of the photo-catalytic efficiency is promoted, and the formaldehyde degradation performance is further enhanced.
The invention relates to a graphite phase carbon nitride based photocatalysis composite material, which uses nonmetallic element doping and salt melt to obtain original g-C 3 N 4 Modified and combined with another semiconductor material, the activity of degrading formaldehyde by photocatalysis is effectively enhanced.
Because the thermal polycondensation method has simple process, is easy to operate and suitable for mass production, and simultaneously obtains a sample with better crystallinity, the thermal polycondensation method is very suitable for the application of the sample, so the thermal polycondensation method is selected to prepare the g-C 3 N 4 A material. The element doping is an effective method for directly adjusting the energy band structure, and can be used for g-C 3 N 4 The mesoheptazine ring and the electronic structure are engineered. The relatively low-cost nonmetallic element S is selected as the doping agent, and the doping of the nonmetallic element S can replace g-C preferentially 3 N 4 And nitrogen atoms at the edge of the middle heptazine unit expand the visible light absorption range and enhance the oxidation-reduction capability in the photocatalytic reaction. And adjusting g-C using NaCl/KCl mixed salt melt with higher melting point 3 N 4 Ensuring active polyheptanoimide as g-C 3 N 4 The main component and the crystallinity are improved.
The few-layer nano material is used in the field of photocatalysis, and because of 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) are widely used as typical 2D layered materials in storage, catalysis, sensing and other electrochemical devices due to their attractive chemical and electrochemical properties, molybdenum disulfide (MoS 2 ) Is typical of transition metal sulfidesRepresentative of the type. Nanoscale MoS 2 Has a variable energy band layered structure, so that the material has photocatalytic activity under visible light, and is used as a nano material, and is single-layer MoS 2 The specific surface area is large, more photoelectron active sites can be provided, the catalytic activity of the photocatalyst is enhanced to adsorb more reactant molecules, and the photocatalyst becomes a very advantageous photocatalyst. In addition, a single layer MoS 2 The forbidden band width is about 1.90eV, the energy band difference is equal to the sum of light and g-C 3 N 4 Is very suitable as g-C 3 N 4 Is a catalyst promoter. It is combined with g-C 3 N 4 The MoS is formed by chemical bond connection easily in the process of compounding at high temperature and high pressure 2 /g-C 3 N 4 The binary nanocomposite can effectively enhance visible light absorption. After binding at g-C 3 N 4 The photoelectrons excited by the upper part are firstly transferred to MoS 2 On the monolayer, the catalyst migrates to the surface of the material to react with pollutants, and the process prevents the combination of photo-generated electrons and holes on the catalyst, so that the photocatalytic capability is stronger, and the photocatalytic efficiency of organic pollutants and air purification is effectively improved.
To realize MoS 2 Application of thin layer in large-scale photocatalysis field, high-quality and high-efficiency preparation of few-layer MoS 2 Particularly critical. Liquid phase exfoliation has been common for layered materials, but the application of ultrasonic operations with the direct addition of materials to the corresponding solvents often does not provide the desired results. In general, whether the polarity of the solvent matches that of the material directly affects the degree of dispersion and stability. In addition, the addition of surfactants and intercalating agents also greatly increases the nanoplatelet yield and significantly increases the dispersion stability. By comparison with MoS 2 DMF with equivalent surface energy is used as a solvent, and the quality and the concentration of dispersion liquid of the prepared nano-sheet are improved in a mode of combining a micromolecular intercalation agent and a macromolecular surfactant.
The graphite phase carbon nitride-based photocatalytic composite material is characterized by comprising the following steps of:
(1) 0.25g polyvinylpyrrolidone (PVP) was dissolved in 50ml N, N-Dimethylformamide (DMF) containing 0.25g oleic acid0.25g of molybdenum disulfide (MoS 2 ) And (3) powder. The mixture is stirred for 20min by magnetic force and is subjected to ultrasonic treatment for 20min to be uniformly mixed, and then the mixture is transferred to an ultrasonic cell grinder for ultrasonic pulse stripping, so that the system temperature is kept at 50 ℃ for accumulated ultrasonic treatment for 10h. Centrifuging the mixture at 5000rpm for 10min after pulverizing, and collecting supernatant 2 A nanosheet dispersion. The dispersion was washed twice with DMF to remove excess PVP and oleic acid, and deionized water (H) was used by rotary evaporation 2 O) replacing the original solvent DMF twice to obtain water-dispersed MoS 2 A nanosheet dispersion.
(2) Firstly, weighing 3-5g of melamine powder, washing with deionized water and filtering to remove the influences of soluble impurities and easily-decomposed substances in the precursor on a sample. Oven dried at 80deg.C and triturated, then 0-2g Thioacetamide (TAA) was added to give a total of 5g with melamine. Meanwhile, 10g of sodium chloride/potassium chloride (NaCI/KCI) is added as mixed molten salt (the mass ratio of Na salt to K salt is controlled to be 9:11), the mixed molten salt is mixed and ground for 30min by using a mortar, poured into a 50ml crucible with a cover, the mixed powder is tiled in the crucible, then placed into a muffle furnace for 120min to be heated to 550 ℃ (the heating rate is 4-6 ℃/min), and reacted for 150-200 min at constant temperature, and cooled along with the furnace, so that a dark yellow product is obtained. Subsequently, the milled product was dispersed in deionized water to dissolve the salt, and then filtered, and the salt was washed off three times repeatedly. Drying in oven at 50deg.C, grinding, sieving to obtain dark yellow powder which is S-doped g-C prepared from molten salt 3 N 4 。
(3) 1g of the modified g-C as described above was weighed out 3 N 4 Placed in a beaker containing 500ml deionized water and stirred magnetically for 20min to mix well. Then, an ultrasonic cell grinder is adopted to carry out ultrasonic pulse stripping, so that the system temperature is kept at 50 ℃ and accumulated ultrasonic is carried out for 10 hours. Centrifuging the mixture at 5000rpm for 10min after pulverizing, and collecting supernatant as few-layer g-C 3 N 4 Removing water from the dispersion by rotary evaporation, collecting lower layer solid, drying and grinding to obtain few modified g-C 3 N 4 And (3) powder.
Weighing 0.5g of treated few-layer modified g-C 3 N 4 Powder and 2.5-10mI the MoS described above 2 The nano dispersion is placed in a 100ml polytetrafluoroethylene lining reaction kettle, 45-52.5ml deionized water is added, and then magnetic stirring is carried out for 30min. Carrying out hydrothermal treatment on the mixed solution, putting the reaction kettle into a constant temperature oven with the temperature of 130-150 ℃, reacting for 10-13 h, and naturally cooling. Subsequently, the mixed liquid in the reaction vessel was subjected to solid-liquid separation using a centrifuge to obtain a lower precipitate. Washing the solid precipitate with deionized water for several times, and drying in oven at 50deg.C for 12 hr to obtain MoS 2 /g-C 3 N 4 A 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 formaldehyde pollution treatment.
The graphite phase carbon nitride based photocatalysis composite material is prepared by doping thioacetamide into modified g-C 3 N 4 And regulating the polymerization process through a sodium chloride/potassium chloride mixed molten salt body, and simultaneously stripping the mixed molten salt body into a two-dimensional structure to be compounded with a few layers of molybdenum disulfide, so as to prepare a heterojunction interface favorable for promoting charge carrier separation. The photocatalyst obtained by the invention not only expands the light absorption range and improves the crystallinity, but also realizes the effective separation of photo-generated electron hole pairs, promotes the improvement of the photocatalysis efficiency and further enhances the formaldehyde degradation performance. The equipment, the process and the medicines adopted in the preparation are relatively low in cost, and the optimal performance is achieved at the same time. The application of the catalyst in formaldehyde treatment can effectively control the harm of formaldehyde to human bodies and widen the research range of photocatalytic materials.
Example 1
0.25g polyvinylpyrrolidone (PVP) was dissolved in 50ml N, N-Dimethylformamide (DMF) containing 0.25g oleic acid, and 0.25g molybdenum disulfide (MoS) 2 ) And (3) powder. After magnetic stirring for 20min and ultrasonic treatment for 20min, the mixture is transferred to an ultrasonic cell grinder, and the system temperature is kept at 50 ℃ for accumulated ultrasonic treatment for 10h. After the completion of the pulverization, the mixture was centrifuged at 5000rpm for 10min, and the resulting supernatant was washed twice with DMF and was then subjected to rotary evaporation with deionized water (H 2 O) the original solvent DMF was replaced twice and the dispersion was recorded as 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) is added. Simultaneously adding 10g of sodium chloride/potassium chloride (NaCI/KCI) as mixed molten salt (controlling the mass ratio of Na salt to K salt to be 9:11), mixing and grinding for 30min by using a mortar, pouring into a 50ml crucible with a cover, spreading the mixed powder in the crucible, then placing into a muffle furnace for 120min to rise to 550 ℃ (the temperature rising rate is 5 ℃/min), reacting for 180min at constant temperature, 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, and then filtered and repeated three times. Drying in a 50 ℃ oven, grinding and sieving to obtain dark yellow powder which is marked as a product II.
1g of product II was weighed into a beaker with 500ml of deionized water added, magnetically stirred for 20min, and then sonicated for 10h with an ultrasonic cell disruptor to maintain the system temperature at 50 ℃. After the completion of the pulverization, the mixture was centrifuged at 5000rpm for 10 minutes, the upper dispersion was collected by rotary evaporation, and the lower solid was dried and pulverized, and the obtained sample was designated as product III.
Weighing 0.5g of product III and 5ml of product I, placing the mixture in a 100ml polytetrafluoroethylene lining reaction kettle, supplementing 50ml of deionized water, and magnetically stirring the mixture for 30min. The reaction kettle is put into a constant temperature oven at 140 ℃ to react for 12 hours and then is naturally cooled. Subsequently, the mixed liquid in the reaction vessel was subjected to solid-liquid separation using a centrifuge to obtain a lower precipitate. Washing the solid precipitate with deionized water for several times, and drying the solid precipitate for 12 hours in a 50 ℃ oven, wherein the obtained product is the target product.
Example 2
0.25g polyvinylpyrrolidone (PVP) was dissolved in 50ml N, N-Dimethylformamide (DMF) containing 0.25g oleic acid, and 0.25g molybdenum disulfide (MoS) 2 ) And (3) powder. After magnetic stirring for 20min and ultrasonic treatment for 20min, the mixture is transferred to an ultrasonic cell grinder, and the system temperature is kept at 50 ℃ for accumulated ultrasonic treatment for 10h. After the completion of the pulverization, the mixture was centrifuged at 5000rpm for 10min, and the resulting supernatant was washed twice with DMF and was then subjected to rotary evaporation with deionized water (H 2 O) the original solvent DMF was replaced twice and the dispersion was recorded as 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) is added. Simultaneously adding 10g of sodium chloride/potassium chloride (NaCI/KCI) as mixed molten salt (controlling the mass ratio of Na salt to K salt to be 9:11), mixing and grinding for 30min by using a mortar, pouring into a 50ml crucible with a cover, spreading the mixed powder in the crucible, then placing into a muffle furnace for 120min to rise to 550 ℃ (the temperature rising rate is 5 ℃/min), reacting for 180min at constant temperature, 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, and then filtered and repeated three times. Drying in a 50 ℃ oven, grinding and sieving to obtain dark yellow powder which is marked as a product II.
1g of product II was weighed into a beaker with 500ml of deionized water added, magnetically stirred for 20min, and then sonicated for 10h with an ultrasonic cell disruptor to maintain the system temperature at 50 ℃. After the completion of the pulverization, the mixture was centrifuged at 5000rpm for 10 minutes, the upper dispersion was collected by rotary evaporation, and the lower solid was dried and pulverized, and the obtained sample was designated as product III.
Weighing 0.5g of product III and 5ml of product I, placing the mixture in a 100ml polytetrafluoroethylene lining reaction kettle, supplementing 50ml of deionized water, and magnetically stirring the mixture for 30min. The reaction kettle is put into a constant temperature oven at 140 ℃ to react for 12 hours and then is naturally cooled. Subsequently, the mixed liquid in the reaction vessel was subjected to solid-liquid separation using a centrifuge to obtain a lower precipitate. Washing the solid precipitate with deionized water for several times, and drying the solid precipitate for 12 hours in a 50 ℃ oven, wherein the obtained product is the target product.
Example 3
0.25g polyvinylpyrrolidone (PVP) was dissolved in 50ml N, N-Dimethylformamide (DMF) containing 0.25g oleic acid, and 0.25g molybdenum disulfide (MoS) 2 ) And (3) powder. After magnetic stirring for 20min and ultrasonic treatment for 20min, the mixture is transferred to an ultrasonic cell grinder, and the system temperature is kept at 50 ℃ for accumulated ultrasonic treatment for 10h. After the completion of the pulverization, the mixture was centrifuged at 5000rpm for 10min, and the resulting supernatant was washed twice with DMF and was then subjected to rotary evaporation with deionized water (H 2 O) the original solvent DMF was replaced twice and the dispersion was recorded as 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. Simultaneously adding 10g of sodium chloride/potassium chloride (NaCI/KCI) as mixed molten salt (controlling the mass ratio of Na salt to K salt to be 9:11), mixing and grinding for 30min by using a mortar, pouring into a 50ml crucible with a cover, spreading the mixed powder in the crucible, then placing into a muffle furnace for 120min to rise to 550 ℃ (the temperature rising rate is 5 ℃/min), reacting for 180min at constant temperature, 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, and then filtered and repeated three times. Drying in a 50 ℃ oven, grinding and sieving to obtain dark yellow powder which is marked as a product II.
1g of product II was weighed into a beaker with 500ml of deionized water added, magnetically stirred for 20min, and then sonicated for 10h with an ultrasonic cell disruptor to maintain the system temperature at 50 ℃. After the completion of the pulverization, the mixture was centrifuged at 5000rpm for 10 minutes, the upper dispersion was collected by rotary evaporation, and the lower solid was dried and pulverized, and the obtained sample was designated as product III.
Weighing 0.5g of product III and 5ml of product I, placing the mixture in a 100ml polytetrafluoroethylene lining reaction kettle, supplementing 50ml of deionized water, and magnetically stirring the mixture for 30min. The reaction kettle is put into a constant temperature oven at 140 ℃ to react for 12 hours and then is naturally cooled. Subsequently, the mixed liquid in the reaction vessel was subjected to solid-liquid separation using a centrifuge to obtain a lower precipitate. Washing the solid precipitate with deionized water for several times, and drying the solid precipitate for 12 hours in a 50 ℃ oven, wherein the obtained product is the target product.
Example 4
0.25g polyvinylpyrrolidone (PVP) was dissolved in 50ml N, N-Dimethylformamide (DMF) containing 0.25g oleic acid, and 0.25g molybdenum disulfide (MoS) 2 ) And (3) powder. After magnetic stirring for 20min and ultrasonic treatment for 20min, the mixture is transferred to an ultrasonic cell grinder, and the system temperature is kept at 50 ℃ for accumulated ultrasonic treatment for 10h. After the completion of the pulverization, the mixture was centrifuged at 5000rpm for 10min, and the resulting supernatant was washed twice with DMF and was then subjected to rotary evaporation with deionized water (H 2 O) the original solvent DMF was replaced twice and the dispersion was recorded as 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) is added. Simultaneously adding 10g of sodium chloride/potassium chloride (NaCI/KCI) as mixed molten salt (controlling the mass ratio of Na salt to K salt to be 9:11), mixing and grinding for 30min by using a mortar, pouring into a 50ml crucible with a cover, spreading the mixed powder in the crucible, then placing into a muffle furnace for 120min to rise to 550 ℃ (the temperature rising rate is 5 ℃/min), reacting for 180min at constant temperature, 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, and then filtered and repeated three times. Drying in a 50 ℃ oven, grinding and sieving to obtain dark yellow powder which is marked as a product II.
1g of product II was weighed into a beaker with 500ml of deionized water added, magnetically stirred for 20min, and then sonicated for 10h with an ultrasonic cell disruptor to maintain the system temperature at 50 ℃. After the completion of the pulverization, the mixture was centrifuged at 5000rpm for 10 minutes, the upper dispersion was collected by rotary evaporation, and the lower solid was dried and pulverized, and the obtained sample was designated as product III.
0.5g of product III and 2.5ml of product I are weighed and placed in a 100ml polytetrafluoroethylene lining reaction kettle, and after 52.5ml of deionized water is supplemented, magnetic stirring is carried out for 30min. The reaction kettle is put into a constant temperature oven at 140 ℃ to react for 12 hours and then is naturally cooled. Subsequently, the mixed liquid in the reaction vessel was subjected to solid-liquid separation using a centrifuge to obtain a lower precipitate. Washing the solid precipitate with deionized water for several times, and drying the solid precipitate for 12 hours in a 50 ℃ oven, wherein the obtained product is the target product.
Example 5
0.25g polyvinylpyrrolidone (PVP) was dissolved in 50ml N, N-Dimethylformamide (DMF) containing 0.25g oleic acid, and 0.25g molybdenum disulfide (MoS) 2 ) And (3) powder. After magnetic stirring for 20min and ultrasonic treatment for 20min, the mixture is transferred to an ultrasonic cell grinder, and the system temperature is kept at 50 ℃ for accumulated ultrasonic treatment for 10h. After the completion of the pulverization, the mixture was centrifuged at 5000rpm for 10min, and the resulting supernatant was washed twice with DMF and was then subjected to rotary evaporation with deionized water (H 2 O) the original solvent DMF was replaced twice and the dispersion was recorded as 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) is added. Simultaneously adding 10g of sodium chloride/potassium chloride (NaCI/KCI) as mixed molten salt (controlling the mass ratio of Na salt to K salt to be 9:11), mixing and grinding for 30min by using a mortar, pouring into a 50ml crucible with a cover, spreading the mixed powder in the crucible, then placing into a muffle furnace for 120min to rise to 550 ℃ (the temperature rising rate is 5 ℃/min), reacting for 180min at constant temperature, 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, and then filtered and repeated three times. Drying in a 50 ℃ oven, grinding and sieving to obtain dark yellow powder which is marked as a product II.
1g of product II was weighed into a beaker with 500ml of deionized water added, magnetically stirred for 20min, and then sonicated for 10h with an ultrasonic cell disruptor to maintain the system temperature at 50 ℃. After the completion of the pulverization, the mixture was centrifuged at 5000rpm for 10 minutes, the upper dispersion was collected by rotary evaporation, and the lower solid was dried and pulverized, and the obtained sample was designated as product III.
0.5g of product III and 10ml of product I are weighed and placed in a 100ml polytetrafluoroethylene lining reaction kettle, 45ml of deionized water is added, and magnetic stirring is carried out for 30min. The reaction kettle is put into a constant temperature oven at 140 ℃ to react for 12 hours and then is naturally cooled. Subsequently, the mixed liquid in the reaction vessel was subjected to solid-liquid separation using a centrifuge to obtain a lower precipitate. Washing the solid precipitate with deionized water for several times, and drying the solid precipitate for 12 hours in a 50 ℃ oven, wherein the obtained product is the target product.
Example 6
0.25g polyvinylpyrrolidone (PVP) was dissolved in 50ml N, N-Dimethylformamide (DMF) containing 0.25g oleic acid, and 0.25g molybdenum disulfide (MoS) 2 ) And (3) powder. After magnetic stirring for 20min and ultrasonic treatment for 20min, the mixture is transferred to an ultrasonic cell grinder, and the system temperature is kept at 50 ℃ for accumulated ultrasonic treatment for 10h. After the completion of the pulverization, the mixture was centrifuged at 5000rpm for 10min, and the resulting supernatant was washed twice with DMF and was then subjected to rotary evaporation with deionized water (H 2 O) the original solvent DMF was replaced twice and the dispersion was recorded as 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) is added. Simultaneously adding 10g of sodium chloride/potassium chloride (NaCI/KCI) as mixed molten salt (controlling the mass ratio of Na salt to K salt to be 9:11), mixing and grinding for 30min by using a mortar, pouring into a 50ml crucible with a cover, spreading the mixed powder in the crucible, then placing into a muffle furnace for 120min to rise to 550 ℃ (the rising rate of 3 ℃/min), reacting for 200min at constant temperature, 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, and then filtered and repeated three times. Drying in a 50 ℃ oven, grinding and sieving to obtain dark yellow powder which is marked as a product II.
1g of product II was weighed into a beaker with 500ml of deionized water added, magnetically stirred for 20min, and then sonicated for 10h with an ultrasonic cell disruptor to maintain the system temperature at 50 ℃. After the completion of the pulverization, the mixture was centrifuged at 5000rpm for 10 minutes, the upper dispersion was collected by rotary evaporation, and the lower solid was dried and pulverized, and the obtained sample was designated as product III.
0.5g of product III and 10ml of product I are weighed and placed in a 100ml polytetrafluoroethylene lining reaction kettle, 45ml of deionized water is added, and magnetic stirring is carried out for 30min. The reaction kettle is put into a constant temperature oven at 130 ℃ for reaction for 13 hours and then naturally cooled. Subsequently, the mixed liquid in the reaction vessel was subjected to solid-liquid separation using a centrifuge to obtain a lower precipitate. Washing the solid precipitate with deionized water for several times, and drying the solid precipitate for 12 hours in a 50 ℃ oven, wherein the obtained product is the target product.
Example 7
0.25g polyvinylpyrrolidone (PVP) was dissolved in 50ml N, N-Dimethylformamide (DMF) containing 0.25g oleic acid, and 0.25g molybdenum disulfide (MoS) 2 ) And (3) powder. After magnetic stirring for 20min and ultrasonic treatment for 20min, the mixture is transferred to an ultrasonic cell grinder, and the system temperature is kept at 50 ℃ for accumulated ultrasonic treatment for 10h. After the completion of the pulverization, the mixture was centrifuged at 5000rpm for 10min, and the resulting supernatant was washed twice with DMF and was then subjected to rotary evaporation with deionized water (H 2 O) the original solvent DMF was replaced twice and the dispersion was recorded as 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) is added. Simultaneously adding 10g of sodium chloride/potassium chloride (NaCI/KCI) as mixed molten salt (controlling the mass ratio of Na salt to K salt to be 9:11), mixing and grinding for 30min by using a mortar, pouring into a 50ml crucible with a cover, spreading the mixed powder in the crucible, then placing into a muffle furnace for 120min to rise to 550 ℃ (the rising rate of 6 ℃/min), reacting for 150min at constant temperature, 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, and then filtered and repeated three times. Drying in a 50 ℃ oven, grinding and sieving to obtain dark yellow powder which is marked as a product II.
1g of product II was weighed into a beaker with 500ml of deionized water added, magnetically stirred for 20min, and then sonicated for 10h with an ultrasonic cell disruptor to maintain the system temperature at 50 ℃. After the completion of the pulverization, the mixture was centrifuged at 5000rpm for 10 minutes, the upper dispersion was collected by rotary evaporation, and the lower solid was dried and pulverized, and the obtained sample was designated as product III.
0.5g of product III and 10ml of product I are weighed and placed in a 100ml polytetrafluoroethylene lining reaction kettle, 45ml of deionized water is added, and magnetic stirring is carried out for 30min. The reaction kettle is put into a constant temperature oven at 150 ℃ to react for 11 hours and then is naturally cooled. Subsequently, the mixed liquid in the reaction vessel was subjected to solid-liquid separation using a centrifuge to obtain a lower precipitate. Washing the solid precipitate with deionized water for several times, and drying the solid precipitate for 12 hours in a 50 ℃ oven, wherein the obtained product is the target product.
To characterize the morphology of the graphite-phase carbon nitride-based photocatalytic composite material, a field emission Scanning Electron Microscope (SEM) test was performed on the target product of example 2, and the results are shown in fig. 1. FIG. 1 SEM image (2 μm) of a graphite-phase carbon nitride-based photocatalytic composite material obtained in example 2
From the figure, the sample morphology appears to be aggregated and holes appear, which illustrates a few MoS layers 2 With lamellar g-C 3 N 4 Bonding occurs gradually. The morphology still keeps g-C 3 N 4 Typical layered structures.
To verify the crystal structure characteristics of the graphite-phase carbon nitride-based photocatalytic composite material, an X-ray powder diffraction (XRD) test was performed on the target product in example 2, 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 graph, the graphite phase carbon nitride-based photocatalytic composite material has peaks and pure g-C at about 27.5 degrees and 13.3 degrees 3 N 4 Similar Bragg diffraction peaks, which indicate that the crystal structure is not due to MoS 2 The addition of the nanolayer is destroyed. In contrast, by comparing the (002) diffraction peak at 27.5 °, it was found that the half-width of the composite material was slightly narrowed and the peak position was shifted to the left, and that the crystallinity was improved instead means MoS 2 With g-C 3 N 4 The sheet faces are fairly tightly bonded and the expansion of the interlayer spacing occurs due to the few MoS layers 2 Enter into g-C 3 N 4 Interlayer, indicating successful recombination of the two semiconductors. In addition, it can be observed that the composite material shows an original few-layer MoS at 39.5 °, 44.5 ° and 58.3 ° 2 Weak diffraction peaks of (103), (104) and (110) planes, confirm MoS 2 Is a successful introduction of (a).
Degradation of organic dyes is the most important index reflecting 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 was added to 50ml of 20mg/l rhodamine B (RhB) solution, stirred for 30 minutes under dark conditions using magnetic stirring to reach adsorption-desorption equilibrium, then illuminated with a 300W xenon lamp under stirring, 1ml of the supernatant was sampled every interval of time, and the concentration change of rhodamine B was measured under an ultraviolet-visible spectrophotometer. The maximum absorption intensity was measured at 553nm and plotted to obtain a degradation curve, the results of which are shown in FIG. 3. FIG. 3 degradation RhB Properties of the graphite-phase carbon nitride-based photocatalytic composite Material obtained in example 2
From the graph, the degradation rate of the composite material is obviously improved, and approximately 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 heterojunction.
The performance of the target product was evaluated by testing the degradation effect of formaldehyde. The specific test process is as follows:
uniformly placing 0.1g of prepared photocatalytic sample into a culture dish, placing the culture dish into the bottom of a 500ml cylinder gas reactor, sealing the upper part by using light-transmitting quartz glass, covering the upper part by using tinfoil paper to prevent light transmission, simultaneously connecting a side wall interface of the gas reactor with an infrared sound spectrum gas detector (Innova 1512), and starting to monitor formaldehyde and CO in the gas reactor in real time 2 、H 2 Concentration of gaseous components such as O. Before the reaction starts, 100ppm of formaldehyde gas is injected from the side wall interface, after the formaldehyde in the reactor is stable and reaches adsorption-desorption balance, the tinfoil paper is taken off, the 300W xenon lamp is adopted for illumination, the photocatalytic reaction starts, and the detection interval of the gas detector is set to be 10 minutes. The results are shown in FIG. 4. FIG. 4 Formaldehyde degradation Properties of the graphite-phase carbon nitride-based photocatalytic composite Material obtained in example 2
From the graph, the degradation efficiency of the composite material reaches 77.6% after 2h illumination, which shows that electron migration generated by coupling of heterojunction interfaces is very effective for separating carriers, thereby generating more active h + Takes part in the oxidation reaction.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Finally, it should be noted that: the above embodiments are only for illustrating the technical aspects of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those of ordinary skill in the art that: modifications and equivalents may be made to the specific embodiments of the invention without departing from the spirit and scope of the invention, which is intended to be covered by the claims.
Claims (6)
1. The preparation method of the graphite-phase carbon nitride-based photocatalytic composite material is characterized by comprising the following steps of:
dissolving polyvinylpyrrolidone into N, N-dimethylformamide containing oleic acid, and adding molybdenum disulfide powder; stirring, ultrasonic pulverizing, centrifuging, and washing the supernatant to obtain water-dispersed MoS 2 A nanosheet dispersion;
mixing melamine powder, thioacetamide and sodium chloride/potassium chloride, and performing thermal polycondensation reaction to obtain a dark yellow product, namely the S-doped g-C prepared by molten salt 3 N 4 ；
S doping g-C 3 N 4 Adding water, ultrasonic pulverizing, centrifuging, collecting upper dispersion, rotary evaporating, collecting lower solid, drying, and grinding to obtain few modified g-C 3 N 4 A powder;
taking few layers of modified g-C 3 N 4 Powder and MoS 2 Mixing the nano-sheet dispersion liquid, preparing a mixed liquid, performing hydrothermal treatment on the mixed liquid, performing solid-liquid separation on the mixed liquid after full reaction to obtain a lower layer precipitate, and obtaining the graphite-phase carbon nitride-based photocatalytic composite material MoS 2 /g-C 3 N 4 ；
Wherein, the mass ratio of polyvinylpyrrolidone, oleic acid and molybdenum disulfide powder is 1:1:1, a step of;
the mass ratio of sodium chloride to potassium chloride in the sodium chloride/potassium chloride is 9:11;
the conditions of the thermal polycondensation reaction are as follows:
heating to 550 ℃ within 120min, heating at a speed of 4-6 ℃/min, and reacting at a constant temperature of 550 ℃ for 150-200 min;
the hydrothermal condition is 130-150 ℃, and the reaction is carried out for 10-13 hours and then natural cooling is carried out.
2. The method for preparing a graphite-phase carbon nitride-based photocatalytic composite material according to claim 1, wherein the addition amount of the thioacetamide is not more than 20wt% of the total mass of the melamine powder and the thioacetamide.
3. The method for preparing the graphite-phase carbon nitride-based photocatalytic composite material according to claim 1, wherein,
the less-layer modified g-C 3 N 4 Powder and MoS 2 The solid-to-liquid ratio of the nano-sheet dispersion liquid is 1g/5-20ml.
4. The method for preparing a graphite-phase carbon nitride-based photocatalytic composite material according to claim 1, wherein the ultrasonic cell pulverizer is adopted for both ultrasonic pulverization, the system temperature is kept at 50 ℃ during the treatment, and the accumulated ultrasonic waves are 10h;
the rotational speed of the centrifugation is 5000rpm for both times, and the centrifugation is 10min.
5. A graphite-phase carbon nitride-based photocatalytic composite material, characterized by being produced by the method according to any one of claims 1 to 4.
6. Use of the graphite-phase carbon nitride-based photocatalytic composite material prepared by the method according to any one of claims 1 to 4 for treating formaldehyde pollution.
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