CN113828308B - Ag (silver) alloy 2 WO 4 /WO 3 /g-C 3 N 4 Heterojunction composite photocatalytic material and preparation method thereof - Google Patents

Ag (silver) alloy 2 WO 4 /WO 3 /g-C 3 N 4 Heterojunction composite photocatalytic material and preparation method thereof Download PDF

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CN113828308B
CN113828308B CN202111311703.2A CN202111311703A CN113828308B CN 113828308 B CN113828308 B CN 113828308B CN 202111311703 A CN202111311703 A CN 202111311703A CN 113828308 B CN113828308 B CN 113828308B
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孙艳
赵倩茹
刘思南
陈双洋
任炳华
王欢
阳康
徐世荣
余梦帆
杨勇
杨姗姗
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Chengdu University
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Abstract

The invention discloses an Ag 2 WO 4 /WO 3 /g‑C 3 N 4 Heterojunction composite photocatalytic material and a preparation method thereof. The method prepares the three-dimensional network g-C 3 N 4 Three-dimensional network g-C 3 N 4 Wherein nano mesopores and macropores above submicron are formed in the silver oxide, and the prepared Ag 2 WO 4 /WO 3 The composite nano-sheet has large specific surface area and Ag 2 WO 4 /WO 3 Size and g-C of composite nanoplatelets 3 N 4 Is adapted to the macropore pore diameter of Ag 2 WO 4 /WO 3 The composite nano-sheet can enter g-C after being dispersed by ball milling 3 N 4 Is in direct contact with the large pores of (a) to increase Ag 2 WO 4 /WO 3 Composite nanosheets and g-C 3 N 4 Forming a contact area of heterojunction g-C 3 N 4 The nano mesoporous is reserved after ball milling, and rich active sites are provided for photocatalysis reaction. The composite photocatalytic material prepared by the invention ensures high photocatalytic activity and realizes the effect of rapid catalysis.

Description

Ag (silver) alloy 2 WO 4 /WO 3 /g-C 3 N 4 Heterojunction composite photocatalytic material and preparation method thereof
Technical Field
The invention relates to the field of photocatalytic materials, in particular to Ag 2 WO 4 /WO 3 /g-C 3 N 4 Heterojunction composite photocatalytic material and a preparation method thereof.
Background
Graphite carbon nitride (g-C) 3 N 4 ) The material has a graphene-like layered structure, is a novel visible light response type photocatalysis material, and is widely applied to water decomposition and photocatalysis 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 pyrolysis 3 N 4 The photo-generated electron-hole pair is easy to be combined, so that the photo-catalytic efficiency is low, and in order to improve the photo-catalytic activity, the selection of a proper semiconductor to be coupled with the photo-generated electron-hole pair to form a heterojunction is one of effective technologies for improving the photo-catalytic performance. WO (WO) 3 The WO is made by the characteristics of innocuity, good stability, narrow band gap, and being capable of utilizing visible light to carry out photocatalysis reaction 3 Becomes a good candidate for synthesizing semiconductor heterojunction with higher photocatalytic activity, and research shows that WO 3 /g-C 3 N 4 Composite photocatalyst and pure WO 3 And g-C 3 N 4 Compared with the prior art, the photocatalytic activity is obviously improved, and the photocatalytic activity is improved in g-C 3 N 4 In incorporation of WO 3 Can accelerate g-C 3 N 4 The photo-generated electrons are transferred, so that the separation rate of electrons and holes is improved, and the photocatalysis efficiency is further improved. However, due to WO 3 The incorporation amount should not be too high, otherwise WO is caused 3 Agglomeration causes a decrease in photocatalytic efficiency, and thus incorporation into WO 3 Suppressing recombination of photogenerated electrons and holes is somewhat limited.
To further promote the separation of photogenerated electrons and holes, the patent document of application number 202010142859.1 discloses a WO 3 /Ag/g-C 3 N 4 Method for synthesizing three-phase photocatalytic material in layered g-C form 3 N 4 、WO 3 The nanorods and the nano silver particles are used as structural reference substances, nano noble metal Ag particles are introduced as cocatalysts, a three-phase composite system is constructed, the absorption of visible light by the surface plasmon resonance enhancement compound of the noble metal Ag is utilized, 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.
For the above related art, the inventors consider WO 3 /Ag/g-C 3 N 4 Three-phase photocatalytic materials help to increase photocatalytic activity, however, due to WO 3 Is a nano rod, is easy to interweave and twine, and is unfavorable for WO 3 Fully disperse and g-C 3 N 4 Direct contact to form heterojunction while interweaving and wrapping WO 3 Adverse to the adequate contact of reactants with photocatalytic material to effect photocatalytic reaction, resulting in WO 3 /Ag/g-C 3 N 4 The photocatalytic reaction rate of the three-phase photocatalytic 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 2 WO 4 /WO 3 /g-C 3 N 4 Heterojunction composite photocatalytic material and a preparation method thereof.
In a first aspect, the present invention provides an Ag 2 WO 4 /WO 3 /g-C 3 N 4 The preparation method of the heterojunction composite photocatalytic material is realized by adopting the following technical scheme:
ag (silver) alloy 2 WO 4 /WO 3 /g-C 3 N 4 The preparation method of the heterojunction composite photocatalytic material is characterized by comprising the following steps of:
(1) g-C obtained by pyrolysis of melamine 3 N 4 Pretreating, 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 g-C 3 N 4 G of three-dimensional network shape-C 3 N 4 The middle part is formed with nano mesoporous and macropores above submicron;
(2) Dissolving sodium tungstate in deionized water, adding lactic acid, then dropwise adding hydrochloric acid, regulating the pH value to be 1-2, adding silver nitrate into the solution, reacting for 18-24 hours at 160-200 ℃, cooling, washing and drying to obtain Ag 2 WO 4 /WO 3 Composite nanosheets;
(3) The three-dimensional network g-C prepared in the step (1) is subjected to 3 N 4 And Ag obtained in the step (2) 2 WO 4 /WO 3 Ball milling and mixing the composite nano-sheets for 8-12 hours to prepare Ag 2 WO 4 /WO 3 /g-C 3 N 4 Heterojunction composite photocatalytic material.
Optionally, the melamine in the step (1) is heated to 500-550 ℃, calcined and pyrolyzed for 2-4 hours, and ground to obtain powder g-C 3 N 4 。
Optionally, the g-C obtained by pyrolysis in step (1) 3 N 4 The adding ratio of the aqueous solution to deionized water and concentrated hydrochloric acid is (1-2 g) (20-25 ml) (5-10 ml).
Optionally, the three-dimensional network g-C obtained in step (1) 3 N 4 The aperture of the nanometer mesoporous is 5-50 nanometers, and the aperture of the macroporous above submicron is 0.8-2 microns.
Optionally, in the step (2), the reaction raw materials are weighed according to the molar ratio of Ag to W=1:1-1:5.
Optionally, ag obtained in step (2) 2 WO 4 /WO 3 The size of the composite nano-sheet is 400-600 nanometers, and the thickness is 10-20 nanometers.
Optionally, in step (3), the metal oxide is added in a mass ratio of (Ag 2 WO 4 /WO 3 ):g-C 3 N 4 The reaction raw materials are weighed in a ratio of (1:5) - (1:10).
Optionally, in the step (2), the reaction raw materials are weighed according to the molar ratio of Ag: w=1:1, and in the step (3), the reaction raw materials are weighed according to the weight ratio of (Ag 2 WO 4 /WO 3 ):g-C 3 N 4 The reaction starting materials were weighed =1:10.
Optionally, ball-to-material ratio of ball milling in step (3)Grinding aid is added in a ratio of 10-12:1, the ratio of the total weight of ball milling materials to the consumption of the grinding aid is (1-2 g) (4-6 ml), and Ag is added after ball milling 2 WO 4 /WO 3 The composite nano-sheet is filled in the three-dimensional network g-C 3 N 4 In the macropores above submicron, and in a three-dimensional network-like g-C 3 N 4 The nano mesoporous of the (2) is reserved.
In a second aspect, the present application provides an Ag 2 WO 4 /WO 3 /g-C 3 N 4 The 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. ag provided by the invention 2 WO 4 /WO 3 /g-C 3 N 4 Preparation method of heterojunction composite photocatalytic material and g-C obtained by pyrolysis 3 N 4 The three-dimensional network g-C is prepared through pretreatment 3 N 4 In three-dimensional network g-C 3 N 4 Wherein nano mesopores and macropores above submicron are formed in the silver oxide, so that the prepared Ag 2 WO 4 /WO 3 The composite nano-sheet can be fully dispersed by ball milling and then enter into macropores of a three-dimensional network to be mixed with g-C 3 N 4 Forming a direct contact heterojunction to further increase Ag 2 WO 4 /WO 3 Composite nanosheets and g-C 3 N 4 The contact area of the nano mesoporous material is increased, the speed of the photocatalytic reaction is increased, and the nano mesoporous material is reserved after ball milling, so that rich active sites are provided for the photocatalytic reaction, and the speed of the photocatalytic reaction is increased.
2. Ag provided by the invention 2 WO 4 /WO 3 /g-C 3 N 4 Preparation method of heterojunction composite photocatalytic material adopts one-step chemical method to prepare Ag 2 WO 4 /WO 3 The composite nano sheet has simple process, is of a three-dimensional sheet structure, has large specific surface area, is favorable for improving the visible light absorptivity and the photo-generated electron hole separation rate, and is Ag 2 WO 4 In situ deposition in WO 3 Nanosheet surface，WO 3 The nano-sheet has smooth and flat surface, which is beneficial to being respectively matched with WO 3 And g-C 3 N 4 And the contact forms a ternary heterojunction, so that the photocatalytic activity and the reaction rate are further improved.
3. Ag provided by the invention 2 WO 4 /WO 3 /g-C 3 N 4 Preparation method of heterojunction composite photocatalytic material and ball milling process for realizing Ag 2 WO 4 /WO 3 The composite nano-sheet is fully dispersed into g-C 3 N 4 In the three-dimensional network of (2), the contact area of the heterojunction is increased, and meanwhile, the impact effect on materials generated when ball milling grinding media are thrown off is utilized, so that the macro-pore lamination is promoted, and the Ag is improved 2 WO 4 /WO 3 Composite nanoplatelets and g-C 3 N 4 The contact area of the metal alloy is simple in process, easy to control and suitable for popularization of industrial application.
4. Ag provided by the invention 2 WO 4 /WO 3 /g-C 3 N 4 Preparation method of heterojunction composite photocatalytic material and three-dimensional network-shaped g-C 3 N 4 The pore diameter of the macropores above submicron is 0.8-2 microns, ag 2 WO 4 /WO 3 The size of the composite nano-sheet is 400-600 nanometers, and the size is adaptive, which is beneficial to Ag 2 WO 4 /WO 3 The composite nano-sheets are fully dispersed into three-dimensional network g-C 3 N 4 Forming a direct contact heterojunction in the macropores above submicron.
5. Ag provided by the invention 2 WO 4 /WO 3 /g-C 3 N 4 The heterojunction composite photocatalytic material has high catalytic reaction rate while ensuring high photocatalytic activity, and Ag prepared by using the method 2 WO 4 /WO 3 /g-C 3 N 4 The heterojunction composite photocatalytic material is prepared by adding 0.1g of the composite photocatalytic material into a rhodamine B solution containing 100mL and 10mg/L, and illuminating for 30min, wherein the degradation rate can reach 84.75% -96.23%, and more preferably can reach 93.77% -96.23%.
Drawings
FIG. 1 is the g-C after pretreatment in step (1) of example 1 3 N 4 X-ray diffraction pattern of the sample;
FIG. 2 is the g-C after pretreatment in step (1) of example 1 3 N 4 Scanning electron microscope images of the samples;
FIG. 3 shows the Ag obtained in step (2) of example 1 2 WO 4 /WO 3 An X-ray diffraction pattern of the composite sample;
FIG. 4 shows the Ag obtained in step (2) of example 1 2 WO 4 /WO 3 Scanning electron microscope images of the composite samples;
FIG. 5 shows the Ag obtained in step (3) of example 1 2 WO 4 /WO 3 /g-C 3 N 4 An X-ray diffraction pattern of the heterojunction composite photocatalyst;
FIG. 6 shows the Ag obtained in step (3) of example 1 2 WO 4 /WO 3 /g-C 3 N 4 EDS diagram of heterojunction composite photocatalyst;
FIG. 7 shows the Ag obtained in step (3) of example 1 2 WO 4 /WO 3 /g-C 3 N 4 Scanning electron microscope pictures of heterojunction composite photocatalysts;
FIG. 8 is a pyrolysis g-C obtained in the step (1) of example 1 3 N 4 Pretreatment of g-C 3 N 4 And Ag prepared in the step (3) 2 WO 4 /WO 3 /g-C 3 N 4 Degrading rhodamine B graph by using a heterojunction composite photocatalyst;
FIG. 9 shows the Ag obtained in step (3) of examples 2 and 3 2 WO 4 /WO 3 /g-C 3 N 4 Graph of heterojunction composite photocatalyst degradation rhodamine B.
Detailed Description
Graphite carbon nitride (g-C) 3 N 4 ) It is considered a stable nonmetallic photocatalyst due to its non-toxicity, narrow forbidden band, high conduction band position and high response to visible light. Because the material is generally prepared by a thermal condensation method, the specific surface area is relatively low, abundant surface active sites are difficult to provide, and the recombination rate of photo-generated carriers is high, so that g-C is caused 3 N 4 The photocatalytic activity is not high. To increase photocatalytic activity, researchers have been led toOver-construction based on g-C 3 N 4 To increase g-C 3 N 4 And promotes the transfer of photogenerated electrons. Tungsten trioxide (WO) 3 ) Has good photoelectric effect, and has the functions of compounding and doping in the photocatalysis field, and the method constructs WO 3 /g-C 3 N 4 Composite photocatalyst incorporating WO 3 The transfer of photo-generated electrons can be obviously accelerated, the separation of electrons and holes is effectively promoted, and the photocatalysis efficiency is improved. Furthermore, researchers can accelerate charge separation on one hand and can widen visible light response range and improve photocatalysis efficiency by introducing nano noble metal silver (Ag) modification and unique surface plasmon resonance effect on the other hand. However, the related art (application No. 202010142859.1) produced g-C by calcination pyrolysis 3 N 4 WO (WO) prepared by reacting nano-flake, sodium tungstate and sodium chloride 3 In the form of nano rod by mixing g-C 3 N 4 Nanoflakes and WO 3 Dispersing the nano rods into two different solvents respectively, stirring the two dispersion systems for 24 hours, and sintering at 400 ℃ for 2 hours to obtain WO 3 /g-C 3 N 4 Composite material, WO 3 /g-C 3 N 4 Adding a silver nitrate solution into the composite photocatalyst, irradiating with a xenon lamp, continuously stirring for 2h, drying, and sintering at 400 ℃ for 2h to obtain WO 3 /Ag/g-C 3 N 4 Three-phase photocatalytic material. Due to WO 3 The nano rod is easy to interweave and twine in the stirring process, which is unfavorable for WO 3 Nanorods and g-C 3 N 4 The contact of the organic pollutant and the reaction of the reactant and the photocatalytic material, which results in long time for degrading the organic pollutant, complex preparation process, long reaction period, high-temperature sintering for many times, high energy consumption and unfavorable energy conservation and environmental protection.
The inventors have found through long-term experimental studies that g-C is prepared by pyrolysis of melamine 3 N 4 Pretreatment is carried out, g-C 3 N 4 Adding into deionized water, stirring, adding concentrated hydrochloric acid, reacting at 140-180deg.C for 0.5-4 hr, cooling, washing and drying to obtain three-dimensional netCollateral g-C 3 N 4 Three-dimensional network g-C 3 N 4 The middle part is formed with nano mesoporous and macropores above submicron; the aperture of the nanometer mesoporous is 5-50 nanometers, and the aperture of the macroporous above submicron is 0.8-2 microns. Meanwhile, adding lactic acid into sodium tungstate solution, then dripping hydrochloric acid solution, regulating the PH to 1-2, reacting for 18-24 hours at 160-200 ℃, cooling, washing and drying to obtain Ag 2 WO 4 /WO 3 The composite nano sheet has simple process, does not need high-temperature sintering, and is Ag 2 WO 4 In situ deposition in WO 3 Nanosheets surface, uniform distribution, WO 3 The nano-sheet has a flat surface, and the three-dimensional nano-sheet has the advantage of large specific surface area compared with the two-dimensional nano-rod, so that the organic pollutants are fully contacted with the photocatalyst, and the photocatalytic activity and the reaction rate are improved. The prepared Ag 2 WO 4 /WO 3 The size of the composite nano-sheet is 400-600 nanometers, the thickness is 10-20 nanometers, and the Ag is the material 2 WO 4 /WO 3 Size of composite nano-sheet and three-dimensional network g-C 3 N 4 Is adapted to the macropore pore diameter of the Ag, so that Ag 2 WO 4 /WO 3 The composite nano-sheet is easy to disperse into three-dimensional network g-C 3 N 4 In the macropores of (a), ag is added 2 WO 4 /WO 3 Composite nanosheets and g-C 3 N 4 The contact area of the heterojunction is formed. Finally, ag is processed by ball milling process 2 WO 4 /WO 3 The composite nano-sheets are dispersed into three-dimensional network g-C 3 N 4 In the macropores above submicron, the high photocatalytic reaction activity is ensured, the photocatalytic reaction rate is improved, and the three-dimensional network g-C is formed 3 N 4 The nano mesoporous of the catalyst can be reserved after ball milling, so that 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, ball milling media perform throwing movement, and in the process of impacting materials, the three-dimensional network macroporous lamination is facilitated, and Ag is facilitated 2 WO 4 /WO 3 Composite nanosheets and g-C 3 N 4 Direct contact. The invention is thatObtained on the basis of the above.
Specifically, in the step (1), melamine is heated to 500-550 ℃, calcined and pyrolyzed for 2-4 hours, and ground to obtain powder g-C 3 N 4 Pyrolyzing the obtained g-C 3 N 4 During the pretreatment, pyrolysis of g-C 3 N 4 The adding ratio of the aqueous solution to deionized water and concentrated hydrochloric acid is (1-2 g) (20-25 ml) (5-10 ml). The raw materials with the proportion are adopted for pretreatment reaction, so that the three-dimensional network-shaped g-C can be prepared 3 N 4 And controlling the three-dimensional network g-C obtained in the step (1) 3 N 4 The aperture of the nanometer mesoporous is 5-50 nanometers, and the aperture of the macroporous above 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=1:1-1:5, and the reaction is carried out according to the proportion, so that Ag can be controlled and obtained 2 WO 4 /WO 3 Composite nano sheet with specific surface area, size of 400-600 nm, thickness of 10-20 nm and three-dimensional network g-C 3 N 4 Is beneficial to the composite nano sheet to enter g-C 3 N 4 In the macropores of (1), ag after reaction 2 WO 4 In situ deposition in WO 3 The surface of the nano sheet is kept smooth and flat, which is favorable for Ag 2 WO 4 /WO 3 Composite nanosheets and g-C 3 N 4 And the contact is sufficient, so that the contact area is increased. In the step (3), the composition is prepared according to the mass ratio of (Ag 2 WO 4 /WO 3 ):g-C 3 N 4 The reaction raw materials are weighed in a ratio of (1:5) - (1:10), so that Ag is obtained 2 WO 4 /WO 3 The composite nano-sheet can be fully dispersed into g-C 3 N 4 Is formed in the large hole of the steel plate. Preferably, the reaction raw materials are weighed in the molar ratio of Ag to W=1:1 in the step (2), and the reaction raw materials are weighed in the mass ratio of Ag in the step (3) 2 WO 4 /WO 3 ):g-C 3 N 4 The raw materials are weighed in the ratio of (1:10), so that the catalytic activity and the photocatalytic reaction rate of the photocatalyst are further improved. Ball material ratio of ball milling in the step (3) is 10-12:1, grinding aid such as absolute ethyl alcohol is added in ball milling, the ratio of total weight of ball milling material to consumption of grinding aid is (1-2 g) (4-6 ml), and Ag is added after ball milling 2 WO 4 /WO 3 The composite nano-sheet is filled in the three-dimensional network g-C 3 N 4 In the macropores above submicron, avoid Ag 2 WO 4 /WO 3 Composite nanoplatelets agglomerate and are three-dimensional network-like g-C 3 N 4 The nano mesoporous of the (2) is reserved.
The present invention will be described in further detail with reference to examples.
Example 1
Ag (silver) alloy 2 WO 4 /WO 3 /g-C 3 N 4 The preparation method of the heterojunction composite photocatalytic material comprises the following steps:
(1) Weighing 20g of melamine, adding into a crucible with a cover, placing the crucible into a tube furnace, heating to 550 ℃ at a heating rate of 5 ℃/min, calcining and pyrolyzing for 4 hours, and grinding to obtain a powder material g-C 3 N 4 . Grinding to obtain powder material g-C 3 N 4 Pretreating, weighing 1g of g-C 3 N 4 Adding into 20ml deionized water, adding 10ml concentrated hydrochloric acid (36-38wt%) into the solution, stirring for 15min, transferring the mixed solution into 50ml reaction kettle, placing into a forced air drying oven, making reaction at 180 deg.C for 1 hr, cooling, washing with deionized water, drying to obtain pretreated g-C 3 N 4 And (3) a sample. FIG. 1 shows the g-C obtained by the pretreatment in step (1) 3 N 4 XRD patterns of the samples, g-C, are shown in FIG. 1 3 N 4 The sample was still g-C 3 N 4 Single phase, no other impurities are present. FIG. 2 shows the pretreatment of g-C in step (1) 3 N 4 SEM image of the sample, g-C can be seen from FIG. 2 3 N 4 Three-dimensional network g-C 3 N 4 The nanometer mesoporous and the macropores with the diameter of more than submicron are formed, the aperture of the nanometer mesoporous is 5-50 nanometers, and the aperture of the macropores with the diameter of more than submicron is 0.8-2 microns.
(2) Weigh 1g NaWO 4 ·2H 2 O was added to 50ml of deionized water, stirred for 15 minutes, 1ml of lactic acid was added dropwise thereto, followed by dropwise addition of 3mol/L hydrochloric acid thereto until the pH of the solution became 2, followed by addition of 0.1g of AgNO thereto 3 (in moles)Ratio of Ag to W=1:5), continuously stirring for 20min, transferring the mixed solution into a 100ml reaction kettle, placing into a blast drying box for reaction at 180 ℃ for 24h, cooling, washing with deionized water, and drying to obtain Ag 2 WO 4 /WO 3 And (5) compounding the sample. FIG. 3 is Ag 2 WO 4 /WO 3 XRD patterns of the composite samples, as can be seen from FIG. 3, ag 2 WO 4 /WO 3 The composite sample comprises Ag 2 WO 4 And WO 3 . FIG. 4 is Ag 2 WO 4 /WO 3 SEM image of composite sample, ag can be seen from FIG. 4 2 WO 4 /WO 3 The composite sample is nano flake-shaped, ag 2 WO 4 /WO 3 The size of the composite nano-sheet is 400-600 nanometers, the thickness is 10-20 nanometers, and Ag 2 WO 4 In situ formation in WO 3 Nano-sheet surface, and Ag 2 WO 4 /WO 3 The composite nano-sheet has a flat surface.
(3) Ag obtained in step (2) 2 WO 4 /WO 3 Sample, g-C obtained by pretreatment in step (1) 3 N 4 According to the mass ratio, adding the materials into a ball milling tank in a 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 material ratio is 10:1. Washing with absolute ethanol, drying to obtain Ag 2 WO 4 /WO 3 /g-C 3 N 4 Heterojunction composite photocatalyst. FIG. 5 is Ag 2 WO 4 /WO 3 /g-C 3 N 4 The XRD pattern of the heterojunction composite photocatalyst, from FIG. 5, can be seen that the sample includes Ag 2 WO 4 、WO 3 And g-C 3 N 4 And (3) phase (C). FIG. 6 is Ag 2 WO 4 /WO 3 /g-C 3 N 4 The EDS diagram of the heterojunction composite photocatalyst shows that Ag, C, N, O and W elements are detected in the EDS diagram, and no other impurities exist. FIG. 7 is Ag 2 WO 4 /WO 3 /g-C 3 N 4 SEM image of heterojunction composite photocatalyst, ag can be seen from FIG. 7 2 WO 4 /WO 3 The nano-sheets are filled in g-C of a three-dimensional network 3 N 4 Large pores of (2)In combination with g-C 3 N 4 Direct contact forms heterojunction, and three-dimensional network g-C 3 N 4 The nano mesoporous in the catalyst is reserved, and rich photocatalytic reaction active sites are provided.
0.1g of pyrolytic g-C obtained in the step (1) of this example was taken, respectively 3 N 4 Pretreatment of g-C 3 N 4 Ag is prepared by the step (3) 2 WO 4 /WO 3 /g-C 3 N 4 The heterojunction composite photocatalyst is added into rhodamine B solution respectively filled with 100ml and 10mg/L, after adsorption and desorption are balanced for 30 minutes in a darkroom, sampling is carried out every 10 minutes under the irradiation of simulated visible light of a xenon lamp (power 300W), the concentration change is analyzed by an ultraviolet-visible light spectrophotometer in combination with a standard curve, the measured curve of degrading rhodamine B is shown as figure 8, and as can be seen from figure 8, ag prepared by the embodiment 2 WO 4 /WO 3 /g-C 3 N 4 The degradation rate of the heterojunction composite photocatalyst can reach 93.77% after illumination for 30min, which is far higher than the pyrolysis g-C prepared in the step (1) 3 N 4 And pretreatment of g-C 3 N 4 . In addition, the Ag obtained in this example 2 WO 4 /WO 3 /g-C 3 N 4 The photocatalytic reaction rate of the heterojunction composite photocatalyst is significantly faster than that of the preferred embodiment of the related art (application No. 202010142859.1), 15WO in the preferred embodiment of the related art 3 /3Ag/g-C 3 N 4 After the composite photocatalyst is continuously irradiated 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% after being irradiated for 100 min.
Example 2
Ag (silver) alloy 2 WO 4 /WO 3 /g-C 3 N 4 The preparation method of the heterojunction composite photocatalytic material comprises the following steps:
(1) Weighing 20g of melamine, adding into a crucible with a cover, placing the crucible into a tube furnace, heating to 550 ℃ at a heating rate of 5 ℃/min, calcining and pyrolyzing for 4 hours, and grinding to obtain a powder material g-C 3 N 4 . Grinding to obtain powder material g-C 3 N 4 Pretreating, weighing 1g of g-C 3 N 4 Adding into 20ml deionized water, adding 10ml concentrated hydrochloric acid (36-38wt%) into the solution, stirring for 15min, transferring the mixed solution into 50ml reaction kettle, placing into a forced air drying oven, making reaction at 180 deg.C for 1 hr, cooling, washing with deionized water, drying to obtain pretreated g-C 3 N 4 And (3) a sample.
(2) Weigh 1g NaWO 4 ·2H 2 O was added to 50ml of deionized water, stirred for 15 minutes, 1ml of lactic acid was added dropwise thereto, followed by dropwise addition of 3mol/L hydrochloric acid thereto until the pH of the solution became 2, followed by addition of 0.52g of AgNO thereto 3 (in terms of molar ratio, ag: W=1:1), continuously stirring for 20min, transferring the mixed solution into a 100ml reaction kettle, placing into a blast drying box, reacting for 24h at 180 ℃, cooling, washing and drying to obtain Ag 2 WO 4 /WO 3 And (5) compounding the sample. Detection of Ag 2 WO 4 /WO 3 As can be seen in the XRD pattern obtained for the composite sample, ag 2 WO 4 /WO 3 The composite sample comprises Ag 2 WO 4 And WO 3 . Detection of Ag 2 WO 4 /WO 3 As can be seen from SEM images obtained from the composite samples, ag 2 WO 4 /WO 3 The composite sample is nano-sheet, the size of the nano-sheet is 400-600 nanometers, the thickness is 10-20 nanometers, and Ag 2 WO 4 In situ formation in WO 3 The surfaces of the nano sheets are flat.
(3) Ag obtained in step (2) 2 WO 4 /WO 3 Sample, pretreatment g-C prepared in step (1) 3 N 4 Adding the materials into a ball milling tank in a 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 material ratio is 10:1. Washing and drying the ball-milled material by absolute ethyl alcohol to obtain Ag 2 WO 4 /WO 3 /g-C 3 N 4 Heterojunction composite photocatalyst.
Taking 0.1g of Ag prepared in the step (3) of the embodiment 2 WO 4 /WO 3 /g-C 3 N 4 The heterojunction composite photocatalyst is added into rhodamine B solution containing 100ml and 10mg/L, sampling is carried out every 10min under the irradiation of the simulation visible light of a xenon lamp, the concentration change is analyzed by an ultraviolet-visible light spectrophotometer and by combining a standard curve, the measured curve of the degradation rhodamine B is shown as figure 9, and the Ag prepared by the embodiment can be seen from figure 9 2 WO 4 /WO 3 /g-C 3 N 4 The degradation rate of the heterojunction composite photocatalyst can reach 84.75% after illumination for 30 min.
Example 3
Ag (silver) alloy 2 WO 4 /WO 3 /g-C 3 N 4 The preparation method of the heterojunction composite photocatalytic material comprises the following steps:
(1) Weighing 20g of melamine, adding into a crucible with a cover, placing the crucible into a tube furnace, heating to 550 ℃ at a heating rate of 5 ℃/min, calcining and pyrolyzing for 4 hours, and grinding to obtain a powder material g-C 3 N 4 . Grinding to obtain powder material g-C 3 N 4 Pretreating, weighing 1g of g-C 3 N 4 Adding into 20ml deionized water, adding 10ml concentrated hydrochloric acid (36-38wt%) into the solution, stirring for 15min, transferring the mixed solution into 50ml reaction kettle, placing into a forced air drying oven, making reaction at 180 deg.C for 1 hr, cooling, washing and drying so as to obtain the pretreated g-C 3 N 4 。
(2) Weigh 1g NaWO 4 ·2H 2 O was added to 50ml of deionized water, stirred for 15 minutes, 1ml of lactic acid was added dropwise thereto, followed by dropwise addition of 3mol/L hydrochloric acid thereto until the pH of the solution became 2, followed by addition of 0.52g of AgNO thereto 3 (in terms of molar ratio, ag: W=1:1), continuously stirring for 20min, transferring the mixed solution into a 100ml reaction kettle, placing into a blast drying box, reacting for 24h at 180 ℃, cooling, washing and drying to obtain Ag 2 WO 4 /WO 3 And (5) compounding the sample.
(3) The Ag prepared in the step (2) is treated 2 WO 4 /WO 3 Sample, pretreatment g-C prepared in step (1) 3 N 4 Adding into a ball milling tank in a mass ratio of 1:10, wherein the total weight of the added materials is 1.2g, and then6ml of absolute ethyl alcohol is added as grinding aid for ball milling for 12 hours, wherein the ball-to-material ratio is 10:1. Washing and drying the ball-milled material by absolute ethyl alcohol to obtain Ag 2 WO 4 /WO 3 /g-C 3 N 4 Heterojunction composite photocatalyst. Detecting the obtained Ag 2 WO 4 /WO 3 /g-C 3 N 4 XRD pattern of heterojunction composite photocatalyst can be seen that the sample contains Ag 2 WO 4 、WO 3 And g-C 3 N 4 And (3) phase (C). Detecting the obtained Ag 2 WO 4 /WO 3 /g-C 3 N 4 The EDS diagram analysis sample of the heterojunction composite photocatalyst contains Ag, C, N, O and W elements, and has no other impurities. From Ag 2 WO 4 /WO 3 /g-C 3 N 4 Ag is seen in SEM image of heterojunction composite photocatalyst 2 WO 4 /WO 3 The nano-sheets are filled in a three-dimensional network g-C 3 N 4 Is combined with g-C in the macropores of (2) 3 N 4 Direct contact forms heterojunction, and three-dimensional network g-C 3 N 4 The nano mesoporous in the nano-porous material is reserved and used as an active site of a photocatalysis reaction.
Taking 0.1g of Ag prepared in the step (3) of the embodiment 2 WO 4 /WO 3 /g-C 3 N 4 The heterojunction composite photocatalyst is added into rhodamine B solution containing 100ml and 10mg/L, sampling is carried out every 10min under the irradiation of the simulation visible light of a xenon lamp, the concentration change is analyzed by an ultraviolet-visible light spectrophotometer and by combining a standard curve, the measured curve of the degradation rhodamine B is shown as figure 9, and the Ag prepared by the embodiment can be seen from figure 9 2 WO 4 /WO 3 /g-C 3 N 4 The degradation rate of the heterojunction composite photocatalyst can reach 96.23% after illumination for 30 min.
Comparative example 1
The difference from example 1 is that the pyrolysis of g-C is omitted in step (1) 3 N 4 The pretreatment step was performed, and the other steps were the same as in example 1 to obtain Ag 2 WO 4 /WO 3 /g-C 3 N 4 Heterojunction composite photocatalyst. The same test strip as in example 1 was usedThe piece was subjected to rhodamine B degradation rate test to obtain Ag prepared in this comparative example 2 WO 4 /WO 3 /g-C 3 N 4 The degradation rate of the heterojunction composite photocatalyst is 80.13% after 30min of illumination.
Comparative example 2
The difference from example 1 is that the ball milling time in the ball milling process of step (3) is 6 hours, and the rest method steps are the same as those of example 1, and Ag is prepared 2 WO 4 /WO 3 /g-C 3 N 4 Heterojunction composite photocatalyst. The degradation rate of rhodamine B was measured under the same measuring conditions as those of example 1 to obtain Ag obtained in this comparative example 2 WO 4 /WO 3 /g-C 3 N 4 The degradation rate of the heterojunction composite photocatalyst is 77.35% after 30min of illumination.
The foregoing are all preferred embodiments of the present application, and are not intended to limit the scope of the present application in any way, therefore: all equivalent changes of the mechanism, shape and principle of the present application should be covered in the protection scope of the present application.

Claims (7)

1. Ag (silver) alloy 2 WO 4 /WO 3 /g-C 3 N 4 The preparation method of the heterojunction composite photocatalytic material is characterized by comprising the following steps of:
(1) g-C obtained by pyrolysis of melamine 3 N 4 Pretreating, adding deionized water, uniformly stirring, adding concentrated hydrochloric acid, reacting at 140-180 ℃ for 0.5-4 h, cooling, washing and drying to obtain three-dimensional network g-C 3 N 4 Three-dimensional network g-C 3 N 4 The middle part is formed with nano mesoporous and macropores above submicron; the pore diameter of the nanometer mesopores is 5-50 nanometers, and the pore diameter of macropores above submicron is 0.8-2 microns;
(2) Dissolving sodium tungstate in deionized water, adding lactic acid, then dropwise adding hydrochloric acid, adjusting the pH to 1-2, adding silver nitrate into the solution, reacting for 18-24 hours at 160-200 ℃, cooling, washing and drying to obtain Ag 2 WO 4 /WO 3 Composite nanosheets; ag (silver) 2 WO 4 /WO 3 The size of the composite nano sheet is 400-600 nanometers, and the thickness is 10-20 nanometers;
(3) The three-dimensional network g-C prepared in the step (1) is subjected to 3 N 4 And Ag obtained in the step (2) 2 WO 4 /WO 3 Ball milling and mixing the composite nano-sheets for 8-12 hours, wherein the ball material ratio is 10-12:1, grinding aid is added in ball milling, the ratio of the total weight of ball milling materials to the consumption of the grinding aid is (1-2 g) (4-6 mL), and Ag is prepared 2 WO 4 /WO 3 /g-C 3 N 4 Heterojunction composite photocatalytic material; after ball milling, ag 2 WO 4 /WO 3 The composite nano-sheet is filled in the three-dimensional network g-C 3 N 4 In the macropores above submicron, and in a three-dimensional network-like g-C 3 N 4 The nano mesoporous of the (2) is reserved.
2. Ag according to claim 1 2 WO 4 /WO 3 /g-C 3 N 4 The preparation method of the heterojunction composite photocatalytic material is characterized in that melamine is pyrolyzed in the step (1) to prepare g-C 3 N 4 The method comprises the following steps: heating melamine to 500-550 ℃, calcining and pyrolyzing for 2-4 hours, and grinding to obtain powder g-C 3 N 4 。
3. Ag according to claim 1 2 WO 4 /WO 3 /g-C 3 N 4 The preparation method of the heterojunction composite photocatalytic material is characterized in that the preparation method comprises the following steps of (1) preparing g-C by pyrolysis 3 N 4 The adding ratio of the aqueous solution to deionized water and concentrated hydrochloric acid is (1-2 g) (20-25 mL) (5-10 mL).
4. Ag according to claim 1 2 WO 4 /WO 3 /g-C 3 N 4 The 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=1:1-1:5.
5. Ag according to claim 1 2 WO 4 /WO 3 /g-C 3 N 4 The preparation method of the heterojunction composite photocatalytic material is characterized in that in the step (3), the material is prepared by the following steps (Ag 2 WO 4 /WO 3 ):g-C 3 N 4 The reaction raw materials are weighed in a ratio of (1:5) - (1:10).
6. Ag according to claim 1 2 WO 4 /WO 3 /g-C 3 N 4 The 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=1:1, and in the step (3), the reaction raw materials are weighed according to the mass ratio of (Ag 2 WO 4 /WO 3 ):g-C 3 N 4 The reaction starting materials were weighed =1:10.
7. Ag (silver) alloy 2 WO 4 /WO 3 /g-C 3 N 4 A heterojunction composite photocatalytic material comprising Ag as defined in any one of claims 1 to 6 2 WO 4 /WO 3 /g-C 3 N 4 The heterojunction composite photocatalytic material is prepared by a preparation method.
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