CN113828308A - Ag2WO4/WO3/g-C3N4Heterojunction composite photocatalytic material and preparation method thereof - Google Patents
Ag2WO4/WO3/g-C3N4Heterojunction composite photocatalytic material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 67
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 14
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with tungsten
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Abstract
The invention discloses Ag2WO4/WO3/g‑C3N4A heterojunction composite photocatalytic material and a preparation method thereof. The method obtains the three-dimensional network-shaped g-C by preparation3N4g-C in the form of a three-dimensional network3N4The Ag is prepared by forming nano mesopores and macropores with the particle size of more than submicron2WO4/WO3The composite nano sheet has large specific surface area and is Ag2WO4/WO3Size and g-C of composite nanosheet3N4The pore diameter of the macropore is matched, so that Ag is2WO4/WO3The composite nano sheets can enter g-C after being dispersed by ball milling3N4The macropores of the silver-doped copper alloy are in direct contact with the silver-doped copper alloy, and Ag is added2WO4/WO3Composite nanosheets and g-C3N4Contact area of heterojunction is formed, and g-C3N4The nano mesopores are reserved after ball milling, and abundant active sites are provided for photocatalytic reaction. The composite photocatalytic material prepared by the method disclosed by the invention realizes a quick catalytic effect while ensuring high photocatalytic activity.
Description
Technical Field
The invention relates to the field of photocatalytic materials, in particular to Ag2WO4/WO3/g-C3N4A heterojunction composite photocatalytic material and a preparation method thereof.
Background
Graphitic carbon nitride (g-C)3N4) The graphene-like photocatalytic material has a graphene-like layered structure, is a novel visible light response type photocatalytic material, and is widely applied to water decomposition and photocatalytic degradation of organic pollutants due to the advantages of stability, no toxicity, no noble metal, a forbidden band width of 2.7eV, simple preparation process and the like. However, pure g-C is obtained by simple calcination pyrolysis3N4The photoproduction electron-hole pairs are easy to recombine, resulting in low photocatalytic efficiencyThe photocatalytic activity of the photocatalyst is improved, and the selection of a proper semiconductor to be coupled with the semiconductor to form a heterojunction is one of effective technologies for improving the photocatalytic performance. WO3Because the catalyst has the characteristics of no toxicity, good stability, narrow band gap, capability of utilizing visible light to carry out photocatalytic reaction and the like, the WO is3Becomes a good candidate for synthesizing semiconductor heterojunction with higher photocatalytic activity, and research shows that WO3/g-C3N4Composite photocatalyst, and pure WO3And g-C3N4Compared with the prior art, the photocatalytic activity is remarkably improved, and the photocatalytic activity is improved in g-C3N4In which WO is incorporated3Can accelerate g-C3N4The photoproduction electron transfer improves the separation rate of electrons and holes and further improves the photocatalysis efficiency. However, due to WO3The amount of incorporation should not be too high, which would lead to WO3Agglomeration causes a decrease in photocatalytic efficiency, and WO is incorporated3The suppression of the recombination of photo-generated electrons and holes is limited to some extent.
To further facilitate the separation of photogenerated electrons and holes, patent document No. 202010142859.1 discloses a WO3/Ag/g-C3N4Method for synthesizing three-phase photocatalytic material, which is layered g-C3N4、WO3The nano-rods and the nano-silver particles are used as structural reference substances, the nano-noble metal Ag particles are introduced as a cocatalyst, a three-phase composite system is constructed, the absorption of the composite on visible light is enhanced by utilizing the surface plasma resonance of the noble metal Ag, the separation of photo-generated electrons and holes is promoted, the utilization efficiency of light energy is improved, and the effect of improving the photocatalytic activity is achieved.
In view of the above-mentioned related art, the inventors consider WO3/Ag/g-C3N4The three-phase photocatalytic material contributes to the enhancement of the photocatalytic activity, however, due to WO3Is a nano rod, is easy to be mutually interlaced and intertwined, and is not beneficial to WO3Fully dispersed with g-C3N4WO in direct contact to form heterojunction and intertwined therewith3Is not favorable for the reactants to fully contact with the photocatalytic material for photocatalytic reaction, resulting in WO3/Ag/g-C3N4Three-phase photocatalysisThe photocatalytic reaction rate of the material is not high.
Disclosure of Invention
In order to improve the photocatalytic reaction rate while ensuring good photocatalytic activity, the present application provides an Ag alloy2WO4/WO3/g-C3N4A heterojunction composite photocatalytic material and a preparation method thereof.
In a first aspect, the present invention provides an Ag2WO4/WO3/g-C3N4The preparation method of the heterojunction composite photocatalytic material is realized by adopting the following technical scheme:
ag2WO4/WO3/g-C3N4The preparation method of the heterojunction composite photocatalytic material is characterized by comprising the following steps:
(1) g-C obtained by pyrolysis of melamine3N4Pretreating, adding deionized water, stirring uniformly, adding concentrated hydrochloric acid, reacting at 140-180 ℃ for 0.5-4 h, cooling, washing and drying to obtain three-dimensional network-shaped g-C3N4g-C in the form of a three-dimensional network3N4The nanometer mesopore and the macropore with the submicron or more are formed in the material;
(2) dissolving sodium tungstate in deionized water, adding lactic acid, then dropwise adding hydrochloric acid, adjusting the pH to 1-2, adding silver nitrate, reacting at 160-200 ℃ for 18-24 h, cooling, washing and drying to obtain Ag2WO4/WO3Composite nanosheets;
(3) subjecting the three-dimensional network-shaped g-C prepared in the step (1)3N4And Ag prepared in step (2)2WO4/WO3Ball-milling and mixing the composite nanosheets for 8-12h to prepare the Ag2WO4/WO3/g-C3N4A heterojunction composite photocatalytic material.
Optionally, in the step (1), the temperature of melamine is raised to 500-550 ℃, the melamine is calcined and pyrolyzed for 2-4 hours, and the melamine is ground to obtain powder g-C3N4。
Optionally, g-C obtained by pyrolysis in step (1)3N4With deionized water,The concentrated hydrochloric acid is added in a ratio of (1-2g) to (20-25 ml) to (5-10 ml).
Optionally, the three-dimensional network g-C prepared in the step (1)3N4The aperture of the nanometer mesoporous is 5-50 nanometers, and the aperture of the macropore above the submicron is 0.8-2 microns.
Optionally, in the step (2), the reaction raw materials are weighed according to a molar ratio of Ag to W of 1:1 to 1: 5.
Optionally, Ag obtained in step (2)2WO4/WO3The size of the composite nano sheet is 400-600 nanometers, and the thickness of the composite nano sheet is 10-20 nanometers.
Optionally, the mass ratio in the step (3) is (Ag)2WO4/WO3):g-C3N4Weighing the reaction raw materials according to the ratio of 1: 5-1: 10.
Optionally, in the step (2), the reaction raw materials are weighed according to a molar ratio of Ag to W being 1 to 1, and in the step (3), the reaction raw materials are weighed according to a mass ratio of (Ag)2WO4/WO3):g-C3N4The reaction materials were weighed at 1: 10.
Optionally, ball-milling in the step (3) is performed with a ball-material ratio of 10-12: 1, grinding aid is added in the ball milling, the ratio of the total weight of the ball-milling materials to the amount of the grinding aid is (1-2g) - (4-6ml), and after ball milling, Ag is added2WO4/WO3The composite nano sheet is filled in the three-dimensional network-shaped g-C3N4And g-C in three-dimensional network form in macropores with submicron or more3N4The nano mesopores are remained.
In a second aspect, the present application provides an Ag2WO4/WO3/g-C3N4The heterojunction composite photocatalytic material is prepared by the preparation method.
In summary, the present application includes at least one of the following beneficial technical effects:
1. the Ag provided by the invention2WO4/WO3/g-C3N4Preparation method of heterojunction composite photocatalytic material and g-C obtained by pyrolysis3N4The three-dimensional network-shaped g-C is prepared by pretreatment3N4In the form of a three-dimensional network g-C3N4Nano mesopores and macropores with submicron or more are formed in the Ag-Ag alloy, so that the prepared Ag2WO4/WO3The composite nano sheets can enter macropores of a three-dimensional network to be neutralized with g-C after being fully dispersed by ball milling3N4Forming a direct contact heterojunction and further increasing Ag2WO4/WO3Composite nanosheets and g-C3N4The contact area of the nano mesoporous silica gel improves the speed of the photocatalytic reaction, and the nano mesoporous silica gel is reserved after ball milling, so that abundant active sites are provided for the photocatalytic reaction, and the speed of the photocatalytic reaction is further improved.
2. The Ag provided by the invention2WO4/WO3/g-C3N4The preparation method of the heterojunction composite photocatalytic material adopts a one-step chemical method to prepare Ag2WO4/WO3The composite nanosheet is simple in process, is in a three-dimensional sheet structure, is large in specific surface area, is beneficial to improving the visible light absorption rate and the photoproduction electron hole separation rate, and is Ag2WO4In situ deposition in WO3Nanosheet surface, WO3The surface of the nano sheet is smooth and flat, which is beneficial to being respectively matched with WO3And g-C3N4Contact to form a ternary heterojunction, and further improve the photocatalytic activity and the reaction rate.
3. The Ag provided by the invention2WO4/WO3/g-C3N4Preparation method of heterojunction composite photocatalytic material, and Ag is realized by ball milling process2WO4/WO3The composite nano-sheet is fully dispersed to g-C3N4In the three-dimensional network, the contact area of the heterojunction is increased, and simultaneously, the impact effect on the material generated when the ball-milling grinding medium is thrown off is utilized, so that the macroporous lamination is promoted, and the Ag content is improved2WO4/WO3Composite nanosheets and g-C3N4The contact area is simple, the process is easy to control, and the method is suitable for popularization of industrial application.
4. The Ag provided by the invention2WO4/WO3/g-C3N4Preparation of heterojunction composite photocatalytic materialMethod, three-dimensional network-like g-C3N4The aperture of the formed macropore with more than submicron is 0.8-2 microns, and Ag is2WO4/WO3The size of the composite nanosheet is 400-600 nanometers, the size is adaptive, and Ag is facilitated2WO4/WO3The composite nano-sheets are fully dispersed to the three-dimensional network-shaped g-C3N4The direct contact heterojunction is formed in the macropores above the submicron.
5. The Ag provided by the invention2WO4/WO3/g-C3N4The heterojunction composite photocatalytic material has high catalytic reaction rate while ensuring high photocatalytic activity, and the Ag prepared by the method2WO4/WO3/g-C3N4The heterojunction composite photocatalytic material is prepared by adding 0.1g of composite photocatalytic material into a solution containing 100mL of 10mg/L rhodamine B, and irradiating for 30min, wherein the degradation rate can reach 84.75-96.23%, and more preferably can reach 93.77-96.23%.
Drawings
FIG. 1 shows g-C after pretreatment in step (1) of example 13N4An X-ray diffraction pattern of the sample;
FIG. 2 shows g-C after pretreatment in step (1) of example 13N4Scanning electron micrographs of the sample;
FIG. 3 shows Ag obtained in step (2) of example 12WO4/WO3An X-ray diffraction pattern of the composite sample;
FIG. 4 shows Ag obtained in step (2) of example 12WO4/WO3Scanning electron micrographs of the composite sample;
FIG. 5 shows Ag obtained in step (3) of example 12WO4/WO3/g-C3N4An X-ray diffraction pattern of the heterojunction composite photocatalyst;
FIG. 6 shows Ag obtained in step (3) of example 12WO4/WO3/g-C3N4EDS diagram of the heterojunction composite photocatalyst;
FIG. 7 shows Ag obtained in step (3) of example 12WO4/WO3/g-C3N4Scanning electron microscope images of the heterojunction composite photocatalyst;
FIG. 8 is the pyrolytic g-C produced in step (1) of example 13N4Pretreatment g-C3N4And Ag prepared in step (3)2WO4/WO3/g-C3N4Degrading a rhodamine B map by using the heterojunction composite photocatalyst;
FIG. 9 shows Ag obtained in step (3) of examples 2 and 32WO4/WO3/g-C3N4A graph of degrading rhodamine B by using the heterojunction composite photocatalyst.
Detailed Description
Graphitic carbon nitride (g-C)3N4) It is considered to be a stable non-metallic photocatalyst because of its non-toxicity, narrow forbidden band, high conduction band position and high response to visible light. Because the preparation is generally prepared by adopting a thermal condensation method, the specific surface area is relatively low, abundant surface active sites are difficult to provide, and the recombination rate of photon-generated carriers is high, which causes g-C3N4The photocatalytic activity is not high. In order to improve the photocatalytic activity, researchers have constructed a material based on g-C3N4To increase g-C3N4The separation efficiency of the photo-generated electron-hole pairs and the promotion of the transfer of the photo-generated electrons. Tungsten trioxide (WO)3) Has good photoelectric effect, mainly plays a role in compounding and doping in the field of photocatalysis, and WO is constructed3/g-C3N4Composite photocatalyst, incorporating WO3Can obviously accelerate the transfer of photo-generated electrons, effectively promote the separation of electrons and holes and improve the photocatalysis efficiency. Furthermore, researchers can accelerate charge separation on one hand and widen the visible light response range and improve the photocatalytic efficiency by introducing nano noble metal silver (Ag) for modification on the other hand. However, the related art (application No. 202010142859.1) produced g-C by calcination pyrolysis3N4Nano thin sheet, WO prepared by reaction of sodium tungstate and sodium chloride3Is in the shape of a nano-rod prepared by mixing g-C3N4Nanoplatelets and WO3The nano rods are respectively dispersed intoAfter two different solvents are added, the two dispersion systems are continuously stirred for 24 hours and then sintered for 2 hours at 400 ℃ to obtain WO3/g-C3N4Composite material, and WO3/g-C3N4Adding the composite photocatalyst into silver nitrate solution, irradiating with xenon lamp, stirring for 2 hr, oven drying, and sintering at 400 deg.C for 2 hr to obtain WO3/Ag/g-C3N4A three-phase photocatalytic material. Due to WO3The nano-rods are easy to be interlaced and intertwined in the stirring process, which is not beneficial to WO3Nanorods with g-C3N4The contact and the reaction of the reactant and the photocatalytic material lead to longer time for degrading organic pollutants, complex preparation process, long reaction period, high energy consumption and being not beneficial to energy conservation and environmental protection because of needing to be sintered at high temperature for many times.
The inventor finds that g-C prepared by pyrolyzing melamine through long-term experimental research3N4Carrying out a pretreatment of g-C3N4Adding the mixture into deionized water, stirring the mixture evenly, adding concentrated hydrochloric acid, reacting the mixture for 0.5 to 4 hours at the temperature of between 140 and 180 ℃, cooling, washing and drying the reaction product to obtain the three-dimensional network-shaped g-C3N4g-C in the form of a three-dimensional network3N4The nanometer mesopore and the macropore with the submicron or more are formed in the material; the aperture of the nanometer mesoporous is 5-50 nanometers, and the aperture of the macropore above the submicron is 0.8-2 microns. Meanwhile, adding lactic acid into a sodium tungstate solution, then dropwise adding a hydrochloric acid solution, adjusting the pH to 1-2, reacting at 160-200 ℃ for 18-24 h, cooling, washing and drying to obtain the Ag2WO4/WO3The composite nanosheet is simple in process, does not need to be sintered at high temperature, and is Ag2WO4In situ deposition in WO3Nanosheet surface, uniform distribution, WO3The surface of the nano sheet is smooth, and the three-dimensional nano sheet has the advantage of large specific surface area compared with a two-dimensional nano rod, so that organic pollutants are fully contacted with the photocatalyst, and the photocatalytic activity and the reaction rate are improved. The obtained Ag2WO4/WO3The size of the composite nano sheet is 400-600 nanometers, the thickness is 10-20 nanometers, and Ag is used2WO4/WO3Size and three-dimensional network g-C of composite nanosheet3N4Pore size adaptation of medium macropore, making Ag2WO4/WO3The composite nano sheet is easy to disperse to three-dimensional network g-C3N4In the macropores, Ag is added2WO4/WO3Composite nanosheets and g-C3N4The contact area of the heterojunction is formed. Finally, the Ag is processed by ball milling2WO4/WO3g-C with composite nano-sheet dispersed into three-dimensional network3N4The three-dimensional network g-C ensures high photocatalytic reaction activity and improves the photocatalytic reaction rate at the same time3N4The nano mesopores can be reserved after ball milling, rich active sites are provided for photocatalytic reaction, and the photocatalytic reaction rate is further improved. In addition, due to the characteristics of the ball milling process, the ball milling medium generates throwing-off type movement, and is beneficial to promoting the large-hole pressing of a three-dimensional network and promoting Ag in the process of impacting materials2WO4/WO3Composite nanosheets and g-C3N4In direct contact. The invention is obtained on the basis of the method.
Specifically, in the step (1), the temperature of melamine is raised to 500-550 ℃, the melamine is calcined and pyrolyzed for 2-4 hours, and the melamine is ground to obtain powder g-C3N4g-C obtained by pyrolysis3N4Pyrolyzing g-C during pretreatment3N4The ratio of the deionized water to the concentrated hydrochloric acid is (1-2g), (20-25 ml) and (5-10 ml). By adopting the raw materials in the proportion for pretreatment reaction, the three-dimensional network-shaped g-C can be prepared3N4And controlling the three-dimensional network g-C prepared in the step (1)3N4The aperture of the nanometer mesoporous is 5-50 nanometers, and the aperture of the macropore above the submicron is 0.8-2 microns. In the step (2), the reaction raw materials are weighed according to the molar ratio of Ag to W being 1: 1-1: 5, and the reaction is carried out according to the ratio, so that the Ag can be obtained through control2WO4/WO3The composite nanosheet is large in specific surface area, 400-600 nanometers in size, 10-20 nanometers in thickness and three-dimensional network-shaped g-C3N4Is largePore adaptation is beneficial to the composite nanosheet entering g-C3N4In the macropores of (1), Ag after reaction2WO4In situ deposition in WO3The surface of the nano sheet and the surface of the composite nano sheet are kept flat and smooth, which is beneficial to Ag2WO4/WO3Composite nanosheets and g-C3N4Fully contacting and increasing the contact area. In the step (3), the mass ratio is calculated according to (Ag)2WO4/WO3):g-C3N4Weighing the reaction raw materials according to the ratio of 1: 5-1: 10 to obtain Ag2WO4/WO3The composite nano sheet can be fully dispersed into g-C3N4In the macropores of (a). Preferably, the raw materials for the reaction are weighed in a molar ratio of Ag to W of 1 to 1 in step (2), and in a mass ratio of (Ag) in step (3)2WO4/WO3):g-C3N4The reaction raw materials are weighed in a ratio of 1:10, and the catalytic activity and the photocatalytic reaction rate of the photocatalyst are further improved. Ball-milling in the step (3) with a ball-material ratio of 10-12: 1, adding a grinding aid such as absolute ethyl alcohol in a ball milling manner, wherein the ratio of the total weight of ball-milling materials to the using amount of the grinding aid is (1-2g) - (4-6ml), and performing ball milling, and then adding Ag2WO4/WO3The composite nano sheet is filled in the three-dimensional network-shaped g-C3N4In the macropores above the submicron to avoid Ag2WO4/WO3Agglomerated composite nanosheets and three-dimensionally networked g-C3N4The nano mesopores are remained.
The present invention will be described in further detail with reference to examples.
Example 1
Ag2WO4/WO3/g-C3N4The preparation method of the heterojunction composite photocatalytic material comprises the following steps:
(1) weighing 20g of melamine, adding the melamine into a crucible with a cover, putting the crucible into a tube furnace, heating to 550 ℃ at the heating rate of 5 ℃/min, calcining and pyrolyzing for 4h, and grinding to obtain a powder material g-C3N4. Grinding to obtain powder material g-C3N4Pretreating, weighing 1g of g-C3N4Adding into 20mlAdding 10ml of concentrated hydrochloric acid (36-38 wt%) into deionized water, stirring for 15min, transferring the mixed solution into a 50ml reaction kettle, placing the reaction kettle in a forced air drying oven, reacting for 1h at 180 ℃, cooling, washing with deionized water, and drying to obtain pretreated g-C3N4And (3) sampling. FIG. 1 shows g-C obtained by the pretreatment in step (1)3N4XRD pattern of sample, as shown in FIG. 1, g-C3N4The sample was still g-C3N4Single phase, no other impurities are present. FIG. 2 shows pretreatment g-C in step (1)3N4SEM image of sample, from FIG. 2, g-C can be seen3N4g-C in the form of a three-dimensional network3N4The mesoporous silica material is provided with nano mesopores and macropores above submicron, the aperture of the nano mesopores is 5-50 nanometers, and the aperture of the macropores above submicron is 0.8-2 micrometers.
(2) Weighing 1g of NaWO4·2H2O into 50ml of deionized water, stirred for 15min, 1ml of lactic acid was added dropwise thereto, then 3mol/L hydrochloric acid was added dropwise thereto until the pH of the solution became 2, and then 0.1g of AgNO was added thereto3(in terms of molar ratio, Ag: W is 1:5), continuously stirring for 20min, transferring the mixed solution into a 100ml reaction kettle, placing the reaction kettle into a forced air drying box, reacting for 24h at 180 ℃, cooling, washing with deionized water, and drying to obtain Ag2WO4/WO3Compounding the sample. FIG. 3 is Ag2WO4/WO3XRD pattern of the composite sample, Ag can be seen from FIG. 32WO4/WO3The composite sample comprises Ag2WO4And WO3. FIG. 4 shows Ag2WO4/WO3SEM image of composite sample, from FIG. 4, Ag can be seen2WO4/WO3The composite sample is in the form of nano-sheet, Ag2WO4/WO3The size of the composite nano sheet is 400-600 nanometers, the thickness is 10-20 nanometers, and Ag is2WO4Formed in situ in WO3Nanosheet surface, and Ag2WO4/WO3The surface of the composite nano sheet is smooth.
(3) Ag prepared in the step (2)2WO4/WO3Sample, g-C obtained by pretreatment in step (1)3N4Adding the mixture into a ball milling tank according to the mass ratio of 1:5, wherein the total weight of the added materials is 1.2g, and then adding 6ml of absolute ethyl alcohol as a grinding aid for ball milling for 12 hours, wherein the ball-to-material ratio is 10: 1. Washing and drying with absolute ethyl alcohol to obtain Ag2WO4/WO3/g-C3N4A heterojunction composite photocatalyst. FIG. 5 shows Ag2WO4/WO3/g-C3N4XRD pattern of the heterojunction composite photocatalyst, it can be seen from FIG. 5 that the sample comprises Ag2WO4、WO3And g-C3N4And (4) phase(s). FIG. 6 shows Ag2WO4/WO3/g-C3N4EDS picture of the heterojunction composite photocatalyst shows that Ag, C, N, O and W elements are detected and no other impurities exist in the EDS picture. FIG. 7 shows Ag2WO4/WO3/g-C3N4SEM image of the heterojunction composite photocatalyst, and Ag can be seen from FIG. 72WO4/WO3g-C with nanosheet filled in three-dimensional network3N4In the macropores of (2) with g-C3N4Direct contact to form a heterojunction, and a three-dimensional network g-C3N4The nanometer mesopores are reserved, and abundant photocatalytic reaction active sites are provided.
0.1g of each of the pyrolytic g-C prepared in step (1) of this example3N4Pretreatment g-C3N4And (3) preparing to obtain Ag2WO4/WO3/g-C3N4The heterojunction composite photocatalyst is added into rhodamine B solutions of 100ml and 10mg/L respectively, after adsorption, desorption and equilibrium are carried out in a dark room for 30 minutes, sampling is carried out at intervals of 10 minutes under simulated visible light irradiation of a xenon lamp (with the power of 300W), concentration change is analyzed by utilizing an ultraviolet-visible light spectrophotometer and combining a standard curve, and the measured curve for degrading rhodamine B is shown in figure 8, as can be seen from figure 8, the Ag prepared in the embodiment is used for degrading rhodamine B2WO4/WO3/g-C3N4The degradation rate of the heterojunction composite photocatalyst can reach 93.77 percent after being illuminated for 30min, which is far higher than that of the heterojunction composite photocatalystPyrolytic g-C prepared in step (1)3N4And pretreatment g-C3N4. In addition, the obtained Ag prepared in this example2WO4/WO3/g-C3N4The photocatalytic reaction rate of the heterojunction composite photocatalyst is obviously faster than that of the best embodiment in the related art (application number 202010142859.1), and the best embodiment in the related art is 15WO3/3Ag/g-C3N4After the composite photocatalyst is continuously illuminated for 30min, the degradation rate is about 57%, the reaction rate is obviously lower than that of the embodiment, and the degradation rate of the composite photocatalyst in the related technology can reach 96.8% by illumination for 100 min.
Example 2
Ag2WO4/WO3/g-C3N4The preparation method of the heterojunction composite photocatalytic material comprises the following steps:
(1) weighing 20g of melamine, adding the melamine into a crucible with a cover, putting the crucible into a tube furnace, heating to 550 ℃ at the heating rate of 5 ℃/min, calcining and pyrolyzing for 4h, and grinding to obtain a powder material g-C3N4. Grinding to obtain powder material g-C3N4Pretreating, weighing 1g of g-C3N4Adding the mixture into 20ml of deionized water, adding 10ml of concentrated hydrochloric acid (36-38 wt%), stirring for 15min, transferring the mixed solution into a 50ml reaction kettle, placing the reaction kettle in a forced air drying oven, reacting for 1h at 180 ℃, cooling, washing with deionized water, and drying to obtain pretreated g-C3N4And (3) sampling.
(2) Weighing 1g of NaWO4·2H2O into 50ml of deionized water, stirred for 15min, 1ml of lactic acid was added dropwise thereto, followed by 3mol/L hydrochloric acid until the pH of the solution became 2, and then 0.52g of AgNO was added thereto3(in terms of molar ratio, Ag: W is 1:1), continuously stirring for 20min, transferring the mixed solution into a 100ml reaction kettle, placing the reaction kettle in a forced air drying box, reacting for 24h at 180 ℃, cooling, washing and drying to obtain Ag2WO4/WO3Compounding the sample. Detection of Ag2WO4/WO3In XRD pattern obtained from composite sampleIt can be seen that Ag2WO4/WO3The composite sample comprises Ag2WO4And WO3. Detection of Ag2WO4/WO3As can be seen in the SEM images obtained from the composite samples, Ag2WO4/WO3The composite sample is in a nano-flake shape, the size of the nano-sheet is 400-600 nanometers, the thickness of the nano-sheet is 10-20 nanometers, and Ag is2WO4Formed in situ in WO3The surface of the nano sheet is smooth.
(3) Ag prepared in the step (2)2WO4/WO3Sample, pretreatment g-C prepared in step (1)3N4Adding the mixture into a ball milling tank according to the mass ratio of 1:5, wherein the total weight of the added materials is 1.2g, and then adding 6ml of absolute ethyl alcohol as a grinding aid for ball milling for 12 hours, wherein the ball-to-material ratio is 10: 1. Washing and drying the ball-milled product by absolute ethyl alcohol to obtain Ag2WO4/WO3/g-C3N4A heterojunction composite photocatalyst.
0.1g of Ag obtained in step (3) of this example was collected2WO4/WO3/g-C3N4A heterojunction composite photocatalyst is added into 100ml of 10mg/L rhodamine B solution, sampling is carried out every 10min under the simulated visible light irradiation of a xenon lamp, the concentration change of the rhodamine B solution is analyzed by utilizing an ultraviolet-visible spectrophotometer and combining a standard curve, the measured rhodamine B degradation curve is shown in figure 9, and as can be seen from figure 9, the Ag prepared in the embodiment is shown in the figure 92WO4/WO3/g-C3N4The degradation rate of the heterojunction composite photocatalyst can reach 84.75 percent after being illuminated for 30 min.
Example 3
Ag2WO4/WO3/g-C3N4The preparation method of the heterojunction composite photocatalytic material comprises the following steps:
(1) weighing 20g of melamine, adding the melamine into a crucible with a cover, putting the crucible into a tube furnace, heating to 550 ℃ at the heating rate of 5 ℃/min, calcining and pyrolyzing for 4h, and grinding to obtain a powder material g-C3N4. Grinding to obtain powder material g-C3N4Pretreating, weighing 1g of g-C3N4Adding the mixture into 20ml of deionized water, adding 10ml of concentrated hydrochloric acid (36-38 wt%), stirring for 15min, transferring the mixed solution into a 50ml reaction kettle, placing the reaction kettle in a forced air drying oven, reacting for 1h at 180 ℃, cooling, washing and drying to obtain pretreated g-C3N4。
(2) Weighing 1g of NaWO4·2H2O into 50ml of deionized water, stirred for 15min, 1ml of lactic acid was added dropwise thereto, followed by 3mol/L hydrochloric acid until the pH of the solution became 2, and then 0.52g of AgNO was added thereto3(in terms of molar ratio, Ag: W is 1:1), continuously stirring for 20min, transferring the mixed solution into a 100ml reaction kettle, placing the reaction kettle in a forced air drying box, reacting for 24h at 180 ℃, cooling, washing and drying to obtain Ag2WO4/WO3Compounding the sample.
(3) Ag prepared in the step (2)2WO4/WO3Sample, pretreatment g-C prepared in step (1)3N4Adding the mixture into a ball milling tank according to the mass ratio of 1:10, wherein the total weight of the added materials is 1.2g, and then adding 6ml of absolute ethyl alcohol as a grinding aid for ball milling for 12 hours, wherein the ball-to-material ratio is 10: 1. Washing and drying the ball-milled product by absolute ethyl alcohol to obtain Ag2WO4/WO3/g-C3N4A heterojunction composite photocatalyst. Detecting the obtained Ag2WO4/WO3/g-C3N4The XRD spectrum of the heterojunction composite photocatalyst can show that the sample contains Ag2WO4、WO3And g-C3N4And (4) phase(s). Detecting the obtained Ag2WO4/WO3/g-C3N4An EDS diagram analysis sample of the heterojunction composite photocatalyst contains Ag, C, N, O and W elements and has no other impurities. From Ag2WO4/WO3/g-C3N4Ag is seen in SEM picture of heterojunction composite photocatalyst2WO4/WO3The nano sheet is filled in the three-dimensional network g-C3N4In the macropores of (2) with g-C3N4Direct contact to form a heterojunction, and a three-dimensional network g-C3N4The nano mesopores in the composite material are reserved and used as active sites of photocatalytic reaction.
0.1g of Ag prepared in step (3) of this example was collected2WO4/WO3/g-C3N4A heterojunction composite photocatalyst is added into 100ml of 10mg/L rhodamine B solution, sampling is carried out every 10min under the simulated visible light irradiation of a xenon lamp, the concentration change of the rhodamine B solution is analyzed by utilizing an ultraviolet-visible spectrophotometer and combining a standard curve, the measured rhodamine B degradation curve is shown in figure 9, and as can be seen from figure 9, the Ag prepared in the embodiment is shown in the figure 92WO4/WO3/g-C3N4The degradation rate of the heterojunction composite photocatalyst can reach 96.23 percent after being illuminated for 30 min.
Comparative example 1
The difference from example 1 is that in step (1) pyrolysis of g-C is omitted3N4The pretreatment step, the remaining method steps are the same as example 1, and Ag is obtained2WO4/WO3/g-C3N4A heterojunction composite photocatalyst. The degradation rate of rhodamine B is tested under the same test conditions as in example 1, and the Ag prepared in the comparative example is obtained through the test2WO4/WO3/g-C3N4After the heterojunction composite photocatalyst is illuminated for 30min, the degradation rate is 80.13%.
Comparative example 2
The difference from the example 1 is that the ball milling time in the ball milling process of the step (3) is 6h, and the rest method steps are the same as the example 1 to prepare the Ag2WO4/WO3/g-C3N4A heterojunction composite photocatalyst. The degradation rate of rhodamine B is tested under the same test conditions as in example 1, and the Ag prepared in the comparative example is obtained through the test2WO4/WO3/g-C3N4After the heterojunction composite photocatalyst is illuminated for 30min, the degradation rate is 77.35%.
The above embodiments are preferred embodiments of the present application, and the protection scope of the present application is not limited by the above embodiments, so: all equivalent changes in the mechanism, shape and principle of the present application shall be covered by the protection scope of the present application.
Claims (10)
1. Ag2WO4/WO3/g-C3N4The preparation method of the heterojunction composite photocatalytic material is characterized by comprising the following steps:
(1) g-C obtained by pyrolysis of melamine3N4Pretreating, adding deionized water, stirring uniformly, adding concentrated hydrochloric acid, reacting at 140-180 ℃ for 0.5-4 h, cooling, washing and drying to obtain three-dimensional network-shaped g-C3N4g-C in the form of a three-dimensional network3N4The nanometer mesopore and the macropore with the submicron or more are formed in the material;
(2) dissolving sodium tungstate in deionized water, adding lactic acid, then dropwise adding hydrochloric acid, adjusting the pH to 1-2, adding silver nitrate, reacting at 160-200 ℃ for 18-24 h, cooling, washing and drying to obtain Ag2WO4/WO3Composite nanosheets;
(3) subjecting the three-dimensional network-shaped g-C prepared in the step (1)3N4And Ag prepared in step (2)2WO4/WO3Ball-milling and mixing the composite nanosheets for 8-12h to prepare the Ag2WO4/WO3/g-C3N4A heterojunction composite photocatalytic material.
2. Ag according to claim 12WO4/WO3/g-C3N4The preparation method of the heterojunction composite photocatalytic material is characterized in that in the step (1), the temperature of melamine is raised to 500-550 ℃, the melamine is calcined and pyrolyzed for 2-4 hours, and the melamine is ground to obtain powder g-C3N4。
3. Ag according to claim 12WO4/WO3/g-C3N4The preparation method of the heterojunction composite photocatalytic material is characterized in that g-C prepared by pyrolysis in the step (1)3N4The ratio of the deionized water to the concentrated hydrochloric acid is (1-2g), (20-25 ml) and (5-10 ml).
4. Ag according to any one of claims 1 to 32WO4/WO3/g-C3N4The preparation method of the heterojunction composite photocatalytic material is characterized in that the three-dimensional network g-C prepared in the step (1)3N4The aperture of the nanometer mesoporous is 5-50 nanometers, and the aperture of the macropore above the submicron is 0.8-2 microns.
5. Ag according to claim 12WO4/WO3/g-C3N4The preparation method of the heterojunction composite photocatalytic material is characterized in that in the step (2), the reaction raw materials are weighed according to the molar ratio of Ag to W which is 1: 1-1: 5.
6. Ag according to claim 1 or 52WO4/WO3/g-C3N4The preparation method of the heterojunction composite photocatalytic material is characterized in that the Ag obtained in the step (2)2WO4/WO3The size of the composite nano sheet is 400-600 nanometers, and the thickness of the composite nano sheet is 10-20 nanometers.
7. Ag according to claim 12WO4/WO3/g-C3N4The preparation method of the heterojunction composite photocatalytic material is characterized in that in the step (3), the weight ratio is calculated according to (Ag)2WO4/WO3):g-C3N4Weighing the reaction raw materials according to the ratio of 1: 5-1: 10.
8. Ag according to claim 12WO4/WO3/g-C3N4The preparation method of the heterojunction composite photocatalytic material is characterized in that the reaction raw materials are weighed according to the molar ratio of Ag to W of 1 to 1 in the step (2), and the reaction raw materials are weighed according to the mass ratio of (Ag) in the step (3)2WO4/WO3):g-C3N4The reaction materials were weighed at 1: 10.
9. Ag according to claim 1 or 72WO4/WO3/g-C3N4The preparation method of the heterojunction composite photocatalytic material is characterized in that ball-milling in the step (3) is performed at a ball-material ratio of 10-12: 1, grinding aid is added in the ball milling, the ratio of the total weight of the ball-milling materials to the using amount of the grinding aid is (1-2g) - (4-6ml), and Ag is obtained after ball milling2WO4/WO3The composite nano sheet is filled in the three-dimensional network-shaped g-C3N4And g-C in three-dimensional network form in macropores with submicron or more3N4The nano mesopores are remained.
10. Ag2WO4/WO3/g-C3N4A heterojunction composite photocatalytic material made of Ag as claimed in any one of claims 1 to 92WO4/WO3/g-C3N4The preparation method of the heterojunction composite photocatalytic material is obtained.
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