CN109759119B - Molybdenum carbide modified tubular carbon nitride photocatalytic material and preparation method and application thereof - Google Patents
Molybdenum carbide modified tubular carbon nitride photocatalytic material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a molybdenum carbide modified tubular carbon nitride photocatalytic material and a preparation method and application thereof. The preparation method comprises the following steps: suspending tubular carbon nitride in methanol to obtain a suspension; and dispersing molybdenum carbide in the suspension, fully stirring and drying to obtain the molybdenum carbide modified tubular carbon nitride photocatalytic material. The molybdenum carbide modified tubular carbon nitride photocatalytic material improves the energy band structure of carbon nitride, and forms a molybdenum carbide/carbon nitride heterojunction, so that the effective separation of a photoproduction electron-hole pair is realized, the utilization efficiency of the photoproduction electron-hole is increased, the photocatalytic degradation effect is promoted, and the molybdenum carbide modified tubular carbon nitride photocatalytic material can be applied to the degradation of antibiotics or dyes in wastewater.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a molybdenum carbide modified tubular carbon nitride photocatalytic material and a preparation method and application thereof.
Background
In recent years, as the problems of energy crisis and environmental pollution are becoming more prominent, the use of photocatalysts to degrade environmental pollutants has received much attention as an environmentally friendly and low-cost technology. The semiconductor photocatalysis technology shows unique advantages in the field of environmental purification application, and particularly shows the advantages of environmental friendliness, high efficiency, energy conservation, cleanness and the like in the aspect of photodegradation organic pollution. However, the development of the traditional semiconductor photocatalyst in the field of photocatalysis is restricted by the problems of low photocatalytic efficiency and low separation efficiency of photon-generated carriers. Therefore, the preparation of photocatalysts with excellent photocatalytic performance has become an important research field.
The carbon nitride is composed of two elements of carbon and nitrogen, and has the advantages of abundant element reserves, wide sources, simple and convenient synthesis method, good economy and easy obtainment. In addition, carbon nitride has good visible light response capability and high stability, so that the application of the carbon nitride in the field of visible light photocatalysis is concerned. However, the monomer carbon nitride also has the non-negligible defects, and the photocatalytic performance of the monomer carbon nitride is not obvious due to the defects of small specific surface area, high electron-hole recombination rate, low quantum efficiency, low utilization rate of visible light and the like. Therefore, the large-scale application of graphite-phase carbon nitride semiconductors in the fields of energy and environmental photocatalytic research is severely limited.
In recent years, transition metal carbide becomes a research hotspot in the field of novel inorganic catalytic materials due to the unique electronic structure and excellent catalytic performance. Molybdenum carbide (Mo)2C) Is produced by carbon atoms entering into transition metal molybdenum crystal latticeA gap-filling type compound having a metallic property. Research shows that molybdenum carbide also has an electronic structure and catalytic characteristics similar to those of noble metal electrons, the molybdenum carbide catalyst shows higher catalytic characteristics in reactions such as hydrodenitrogenation, hydrodesulfurization, alkane isomerization, water-vapor conversion and the like, and the catalytic performance of the molybdenum carbide catalyst can be comparable to that of noble metal catalysts such as platinum, iridium and the like in some reactions and is known as a platinum-like catalyst, so that the molybdenum carbide catalyst is attracting wide attention of scholars at home and abroad.
How to research an environment-friendly photocatalyst which has good degradation effect on pollutants which are difficult to degrade in the environment, such as tetracycline, rhodamine B and the like, and has excellent photocatalytic performance is a technical problem which needs to be solved urgently in the field.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a tubular carbon nitride photocatalytic material modified by molybdenum carbide and a preparation method and application thereof, wherein the tubular carbon nitride photocatalytic material modified by molybdenum carbide is modified by molybdenum carbide, the energy band structure of carbon nitride is improved, and a molybdenum carbide/carbon nitride heterojunction is formed, so that the effective separation of photogenerated electron-hole pairs is realized, the utilization efficiency of the photogenerated electron-hole pairs is increased, and the effect of photocatalytic degradation is promoted. The preparation method has the advantages of simple preparation process, easy control, easily obtained raw materials, low cost, suitability for continuous large-scale batch production, low heating temperature and convenient operation and popularization. And the molybdenum carbide modified tubular carbon nitride photocatalytic material can be applied to degrading pollutants which are difficult to degrade in water, such as dyes, antibiotics and the like, and has a good effect.
In order to solve the technical problem, the invention provides a molybdenum carbide modified tubular carbon nitride photocatalytic material which comprises molybdenum carbide and tubular carbon nitride, wherein the tubular carbon nitride is modified on the surface of the tubular carbon nitride. Further, the tubular carbon nitride is prepared by taking urea and melamine as raw materials and performing hydrothermal reaction and calcination.
Further, the mass ratio of the molybdenum carbide to the tubular carbon nitride is 1-5: 100.
As a general technical concept, the invention also provides a preparation method of the molybdenum carbide modified tubular carbon nitride photocatalytic material, which comprises the following steps:
s1, suspending tubular carbon nitride in methanol to obtain a suspension;
and S2, dispersing molybdenum carbide in the suspension, fully stirring, and drying to obtain the molybdenum carbide modified tubular carbon nitride photocatalytic material.
In the preparation method of the molybdenum carbide modified tubular carbon nitride photocatalytic material, in S1, the preparation method of the tubular carbon nitride comprises the following steps:
s1-1, carrying out hydrothermal reaction on urea and melamine serving as raw materials at 180-240 ℃ for 18-24 h to obtain a carbon nitride precursor;
and S1-2, calcining the carbon nitride precursor for 4-6 h at 400-600 ℃ in an inert atmosphere to obtain the tubular carbon nitride.
In the preparation method of the molybdenum carbide modified tubular carbon nitride photocatalytic material, in S1-1, the molar ratio of urea to melamine is 1-5: 1.
In the preparation method of the molybdenum carbide modified tubular carbon nitride photocatalytic material, in the S1-2, the calcination is carried out in a muffle furnace, and the temperature rise rate in the muffle furnace is 2.3-6 ℃/min.
In the preparation method of the molybdenum carbide modified tubular carbon nitride photocatalytic material, the preparation method of molybdenum carbide in S2 is as follows:
s2-1, dropwise adding the hydrochloric acid solution into a mixed solution containing ammonium heptamolybdate, aniline solution and deionized water to obtain a white precipitate;
s2-2, placing the white precipitate in a tube furnace, and keeping the temperature at 500-800 ℃ for 4-6 h under inert atmosphere to obtain molybdenum carbide.
Further, the preparation method of the molybdenum carbide in the step S2 is as follows:
s2-1, dropwise adding a hydrochloric acid solution into a mixed solution of ammonium heptamolybdate, an aniline solution and deionized water to obtain a white precipitate; placing the white precipitate in an oil bath at 40-100 ℃, and magnetically stirring to obtain white powder;
s2-2, putting the white powder in a tube furnace, and keeping the temperature at 500-800 ℃ for 4-6 h under inert atmosphere to obtain the molybdenum carbide.
In the preparation method of the molybdenum carbide modified tubular carbon nitride photocatalytic material, in S2-1, the concentration of the hydrochloric acid solution is 1 mol/L-4 mol/L.
In the preparation method of the molybdenum carbide modified tubular carbon nitride photocatalytic material, in the S2-1, the molar ratio of ammonium heptamolybdate to aniline is 1: 12-18 in the mixed solution containing ammonium heptamolybdate, aniline solution and deionized water.
In the preparation method of the molybdenum carbide modified tubular carbon nitride photocatalytic material, in S2-2, the temperature rise rate of the tubular furnace is 2-5 ℃/min.
As a general technical concept, the invention also provides an application of the molybdenum carbide modified tubular carbon nitride photocatalytic material in degrading antibiotics and dyes in wastewater.
The application method of the molybdenum carbide modified tubular carbon nitride photocatalytic material in degrading antibiotics and dyes in wastewater comprises the following steps:
(1) adding a molybdenum carbide modified tubular carbon nitride photocatalytic material into wastewater, and stirring in a dark place to achieve adsorption balance;
(2) the photocatalytic reaction is carried out under visible light.
The molybdenum carbide modified tubular carbon nitride photocatalytic material is applied to degrading antibiotics and dyes in wastewater, and the stirring time is 1-4 h.
The molybdenum carbide modified tubular carbon nitride photocatalytic material is applied to degrading antibiotics and dyes in wastewater, and the lambda of visible light is more than or equal to 400 nm; the time of the photocatalytic reaction is 60-240 min.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a tubular carbon nitride photocatalytic material modified by molybdenum carbide, which is modified by molybdenum carbide, improves the energy band structure of carbon nitride, and forms a molybdenum carbide/carbon nitride heterojunction, thereby realizing the effective separation of a photoproduction electron-hole pair, increasing the utilization efficiency of the photoproduction electron-hole, and promoting the effect of photocatalytic degradation. The coupling interface between the molybdenum carbide and the carbon nitride is easy to transfer and separate photogenerated charges, so that the recombination of electron holes is inhibited, a large contact area between the molybdenum carbide and the carbon nitride can provide more electron transfer channels, and electrons flow from the carbon nitride to the molybdenum carbide. On the other hand, molybdenum carbide particles with abundant catalytically active sites may consume electrons through the carbon nitride for degradation of contaminants.
(2) The invention provides a molybdenum carbide modified tubular carbon nitride photocatalytic material which has the advantages of strong visible light absorption capacity, large specific surface area, high photo-generated charge separation rate, high photocatalytic activity, stable chemical property, corrosion resistance and the like. Compared with pure carbon nitride and pure molybdenum carbide, the molybdenum carbide/carbon nitride composite photocatalyst has better photocatalytic activity.
(3) The invention provides a molybdenum carbide modified tubular carbon nitride photocatalytic material, which takes tubular carbon nitride as a carrier, wherein the tubular carbon nitride belongs to a one-dimensional nano material, compared with monomer carbon nitride with a blocky structure, the tubular carbon nitride has larger specific surface area and orientation characteristic along a certain direction, so that the tubular carbon nitride is considered as an ideal material for directional electron transmission, is a minimum dimension material for effectively transmitting electrons and light excitons, can provide a direct path for the migration of electrons, reduces a crystal boundary and leads to excellent charge transmission property.
(4) The invention provides a preparation method of various molybdenum carbide modified tubular carbon nitride photocatalytic materials, which has the advantages of simple preparation process, easy control, easy obtainment of raw materials, low cost, suitability for continuous large-scale batch production, low heating temperature and convenient operation and popularization.
(5) The invention provides application of various molybdenum carbide modified tubular carbon nitride photocatalytic materials, can realize high-efficiency degradation of antibiotics and rhodamine B, has the advantages of stable photocatalytic performance, strong corrosion resistance and high degradation efficiency, and has good practical application prospect.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
FIG. 1 is a scanning electron microscope image of the carbon nitride monomer of comparative example 1 and the carbon nitride tube of example 1 according to the present invention.
FIG. 2 is a transmission electron microscope image of the monomeric carbon nitride of comparative example 1 and the tubular carbon nitride of example 1 according to the present invention.
FIG. 3 is a graph comparing the X-ray diffraction patterns of the monomeric carbon nitride of comparative example 1 and the tubular carbon nitride of example 1 in accordance with the present invention.
FIG. 4 is a graph showing the X-ray diffraction contrast of the photocatalytic material for tubular carbon nitride, molybdenum carbide or molybdenum carbide modified in example 1 of the present invention.
FIG. 5 is a DRS comparison of monomeric carbon nitride of comparative example 1 and tubular carbon nitride of example 1 in accordance with the present invention
Fig. 6 is a time-degradation efficiency relationship diagram corresponding to when the tubular carbon nitride photocatalytic material modified by the monomer carbon nitride, the tubular carbon nitride and the molybdenum carbide degrades tetracycline wastewater in the application method of embodiment 2 of the present invention.
Fig. 7 is a cyclic experimental diagram of tetracycline degradation by the molybdenum carbide-modified tubular carbon nitride photocatalytic material in the application method of embodiment 2 of the present invention.
Fig. 8 is a time-degradation efficiency relationship diagram corresponding to when the monomer carbon nitride, tubular carbon nitride, and molybdenum carbide modified tubular carbon nitride photocatalytic material degrades rhodamine B in the application method of embodiment 3 of the present invention.
Fig. 9 is a cycle experimental diagram of degradation of rhodamine B by the molybdenum carbide modified tubular carbon nitride photocatalytic material in the application method in embodiment 3 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The materials and equipment used in the following examples are commercially available.
Comparative example 1
One photocatalyst of the present invention is unmodified monomer carbon nitride (g-C)3N4) The preparation method of the photocatalyst comprises the following steps:
putting 5g of melamine into a crucible, placing the crucible into a muffle furnace, heating the crucible to 550 ℃ at the heating rate of 2.3 ℃/min, preserving the heat at 550 ℃ for 4h, carrying out the whole process under the protection of nitrogen, taking out the melamine after natural cooling, and grinding the melamine by using a mortar to obtain a yellow powder sample, namely the monomer carbon nitride.
Example 1
The molybdenum carbide modified tubular carbon nitride (Mo) is prepared by using the molybdenum carbide modified tubular carbon nitride (Mo) as a raw material2C/TCN) photocatalytic material, the preparation method comprises the following steps:
(1) preparing tubular carbon nitride:
1.1, grinding 8.56g of urea and 6g of melamine, dissolving in 70ml of deionized water, and stirring at a constant speed for 2 hours to prepare a uniform mixed solution.
1.2, transferring the mixed solution into a 100mL high-pressure reaction kettle, preserving the temperature for 24 hours at 180 ℃, naturally cooling, washing with water and ethanol for 3 times respectively, filtering, and drying at 100 ℃ for 12 hours to obtain the carbon nitride precursor.
1.3, placing the carbon nitride precursor into a crucible, placing the crucible into a muffle furnace, heating the crucible to 550 ℃ at the heating rate of 2.3 ℃/min, preserving the heat at 550 ℃ for 4 hours, carrying out the whole process under the protection of nitrogen, taking out the carbon nitride precursor after natural cooling, and grinding the carbon nitride precursor by using a mortar to obtain a yellow powder sample, namely the tubular carbon nitride.
(2) Preparing molybdenum carbide:
2.1 taking 2mmol of ammonium heptamolybdate ((NH)4)6Mo7O24·4H2O), 36mmol aniline solution, 40mL deionized water, and 1mol/L aqueous hydrochloric acid solution was added dropwise to the solution under magnetic stirring until a white precipitate appeared (pH 4).
2.2, placing the white precipitate in an oil bath at 50 ℃, magnetically stirring for 4h, washing the precipitate with distilled water and ethanol for 3 times after the treatment at 50 ℃, drying overnight at 60 ℃, and grinding with a mortar to obtain a white powder sample.
2.3, transferring the white powder sample into a tube furnace, introducing argon, heating to 775 ℃ at the heating rate of 2 ℃/min, preserving the heat at 775 ℃ for 5h, naturally cooling, and taking out to obtain a black powder sample, namely molybdenum carbide (Mo)2C)。
(3) Preparation of molybdenum carbide-modified tubular carbon nitride (Mo)2C/TCN):
3.1, taking 1g of the tubular carbon nitride powder prepared in the step (1), adding the tubular carbon nitride powder into a beaker containing 25mL of methanol, and carrying out ultrasonic treatment for 30min to obtain a suspension.
3.2, dispersing 0.01g of molybdenum carbide prepared in the step (2) in the suspension prepared in the step 3.1, stirring at room temperature for 24h, removing residual methanol through evaporation in nitrogen flow, collecting the obtained light yellow powder, and drying in a vacuum drying oven at 60 ℃ overnight to obtain the molybdenum carbide modified tubular carbon nitride photocatalytic material (Mo)2C/TCN composite).
Experimental example 1: the monomeric carbon nitride of comparative example 1 and the tubular carbon nitride of example 1 were subjected to electron microscope scanning.
FIG. 1 is a Scanning Electron Microscope (SEM) representation of the present invention, comparative example 1, monomeric carbon nitride, and example 1, tubular carbon nitride, wherein (a) is monomeric carbon nitride and (b) is tubular carbon nitride.
FIG. 2 is a Transmission Electron Microscope (TEM) representation of the present invention, comparative example 1, monomeric carbon nitride, and example 1, tubular carbon nitride, wherein (a) is monomeric carbon nitride and (b) is hollow tubular carbon nitride.
As can be seen from fig. 1 and 2, the monomeric carbon nitride has a bulk aggregation structure, a small specific surface area and no nano-pores on the surface. However, the tubular carbon nitride has a clear hollow tubular structure and has a part of nano-pores on the surface.
Experimental example 2: the single body of comparative example 1, the tubular carbon nitride of example 1, molybdenum carbide and Mo2The C/TCN composite material is subjected to X-ray scanning.
FIG. 3 is an X-ray diffraction (XRD) pair of the monomeric carbon nitride of comparative example 1 and the tubular carbon nitride of example 1 in accordance with the present inventionAnd (4) comparing the maps. From the figure, it can be found that two distinct XRD diffraction peaks ascribed to graphite-phase carbon nitride (100) and (002) crystal planes appear at 13.1 DEG and 27.2 DEG, confirming that the product prepared is g-C3N4. Compared with monomer carbon nitride, the 27.2-degree peak of the tubular carbon nitride is widened and the strength is weakened, which shows that the crystal form is weakened, the thickness is thinned, and a hollow tubular structure is successfully formed.
FIG. 4 tubular carbon nitride, molybdenum carbide and Mo of example 12X-ray diffraction (XRD) contrast pattern of the C/TCN composite material. It can be seen from the figure that: mo2C/TCN composite material and monomer g-C3N4Two typical diffraction peaks, both at about 27.5 ° and 13.1 °, can be assigned to the (002) and (110) diffraction planes of TCN, but due to the small amount of Mo2C, hardly in Mo2Mo is found in C/TCN composite material2Diffraction peak of C. At the same time, e.g. Mo2As shown in the XRD chart of C, 8 main peaks of 34.47 °, 38.03 °, 39.52 °, 52.17 °, 61.43 °, 69.64 °, 74.80 ° and 75.55 ° were observed, respectively. Respectively correspond to Mo2Diffraction peaks of (021), (200), (102), (221), (040), (321), (223) and (142) of C proved that Mo was successfully produced2C。
Experimental example 3: the monomeric carbon nitride of comparative example 1, the tubular carbon nitride of example 1 were subjected to specific surface area, pore volume and pore diameter measurements. The specific surface area of the monomeric carbon nitride is 12.735m2Per g, pore volume 0.073cm3(ii)/g, pore size 19.676 nm; and the specific surface area of the tubular carbon nitride is 32.669m2Per g, pore volume 0.204cm3Per g, the pore diameter is 25.209 nm. From this, it is known that tubular carbon nitride has advantages of large surface area, large pore volume, large pore diameter, and the like.
Experimental example 4: DRS comparison was performed on the monomeric carbon nitride of comparative example 1, the tubular carbon nitride of example 1. Fig. 5 is a comparison graph of DRS of the monomer carbon nitride and the tubular carbon nitride according to the present invention, and it can be seen from the graph that the absorption wavelength of the monomer carbon nitride is about 470nm, and the wavelength of the hollow tubular carbon nitride photocatalytic material is widened to more than 500nm, such that the light absorption range is increased, and the light utilization rate is improved.
Example 2
An application method of the molybdenum carbide modified tubular carbon nitride photocatalytic material in the degradation of antibiotic wastewater in embodiment 1 is as follows:
weighing 0.03g of molybdenum carbide modified tubular carbon nitride photocatalytic material, adding the molybdenum carbide modified tubular carbon nitride photocatalytic material into 30mL of antibiotic wastewater with Tetracycline (TC) concentration of 20mg/L, and magnetically stirring the mixture for one hour in a dark place to achieve adsorption balance; then, a light source is turned on, and the light is irradiated under visible light (lambda is more than or equal to 400nm) to carry out photocatalytic reaction for 60min, so that the degradation of the antibiotic wastewater is completed. Within 60min of the photocatalytic reaction, 2ml of tetracycline solution is taken every 15min, the characteristic peak value of the tetracycline in the solution is measured by an ultraviolet-visible spectrophotometer, and the degradation efficiency is calculated. Meanwhile, the molybdenum carbide modified tubular carbon nitride photocatalytic material is circulated for four times according to the same application method, and the stability of the molybdenum carbide modified tubular carbon nitride photocatalytic material is inspected.
Meanwhile, the same application was performed for the monomeric carbon nitride of comparative example 1 and the tubular carbon nitride of example 1, and the degradation efficiency was calculated. The corresponding time-degradation efficiency graph of the tubular carbon nitride photocatalytic material modified by the monomer carbon nitride, the tubular carbon nitride and the molybdenum carbide for degrading the tetracycline wastewater is shown in FIG. 6. As can be seen from fig. 6: after illumination is carried out for 1h, the molybdenum carbide/carbon nitride composite photocatalytic material has the highest degradation efficiency on tetracycline, and reaches 72.96%; tubular carbon nitride is inferior, and the degradation efficiency of the monomer carbon nitride to tetracycline is only 30.12%.
Fig. 7 is a cyclic experimental diagram of tetracycline degradation by the molybdenum carbide-modified tubular carbon nitride photocatalytic material, and it can be seen from the cyclic experimental diagram that the tetracycline degradation effect is good after the molybdenum carbide-modified tubular carbon nitride photocatalytic material is recycled for four times.
Example 3
An application method of the molybdenum carbide modified tubular carbon nitride photocatalytic material in degradation of dye wastewater in embodiment 1 is as follows:
weighing 0.03g of molybdenum carbide modified tubular carbon nitride photocatalytic material, adding the molybdenum carbide modified tubular carbon nitride photocatalytic material into 30mL of dye wastewater with rhodamine B (RhB) concentration of 20mg/L, and magnetically stirring the mixture for one hour in a dark place to achieve adsorption balance; then, a light source is turned on, and the light is irradiated under visible light (lambda is more than or equal to 400nm) to carry out photocatalytic reaction for 60min, thus finishing the degradation of the dye wastewater. Within 60min of the photocatalytic reaction, 2ml of rhodamine B solution is taken every 15min, the characteristic peak value of the rhodamine B in the solution is measured by an ultraviolet-visible spectrophotometer, and the degradation efficiency is calculated. Meanwhile, the molybdenum carbide modified tubular carbon nitride photocatalytic material is circulated for four times according to the same application method, and the stability of the molybdenum carbide modified tubular carbon nitride photocatalytic material is inspected.
Meanwhile, the same application was performed for the monomeric carbon nitride of comparative example 1 and the tubular carbon nitride of example 1, and the degradation efficiency was calculated. The graph of the corresponding time-degradation efficiency relationship when the tubular carbon nitride photocatalytic material modified by the monomer carbon nitride, the tubular carbon nitride and the molybdenum carbide degrades the dye is shown in fig. 8. As can be seen from fig. 8: the molybdenum carbide modified tubular carbon nitride photocatalytic material has extremely high degradation capability on rhodamine B, and after 15min of illumination, the degradation efficiency reaches 84.88%; tubular carbon nitride is inferior, and the degradation efficiency of monomer carbon nitride on rhodamine B is only 62.34%.
Fig. 9 is a circular experimental diagram of degradation of rhodamine B by the molybdenum carbide modified tubular carbon nitride photocatalytic material, and it can be known from the circular experimental diagram that the degradation effect of the molybdenum carbide modified tubular carbon nitride photocatalytic material on rhodamine B is good after the tubular carbon nitride photocatalytic material is circularly used for four times.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or equivalent modifications, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.
Claims (9)
1. The tubular carbon nitride photocatalytic material modified by molybdenum carbide is characterized by comprising molybdenum carbide and tubular carbon nitride, wherein the molybdenum carbide is modified on the surface of the tubular carbon nitride; the mass ratio of the molybdenum carbide to the tubular carbon nitride is 1-5: 100; the preparation method of the tubular carbon nitride comprises the following steps:
(a) urea and melamine are used as raw materials, and the raw materials are subjected to hydrothermal reaction at 180-240 ℃ for 18-24 h to obtain a carbon nitride precursor; the molar ratio of the urea to the melamine is 1-5: 1;
(b) calcining the carbon nitride precursor for 4-6 h at 400-600 ℃ in an inert atmosphere to obtain tubular carbon nitride; the calcination is carried out in a muffle furnace, and the temperature rise rate in the muffle furnace is 2.3-6 ℃/min.
2. The preparation method of the molybdenum carbide modified tubular carbon nitride photocatalytic material according to claim 1, characterized by comprising the following steps:
s1, suspending tubular carbon nitride in methanol to obtain a suspension;
and S2, dispersing molybdenum carbide in the suspension, fully stirring, and drying to obtain the molybdenum carbide modified tubular carbon nitride photocatalytic material.
3. The method for preparing the molybdenum carbide-modified tubular carbon nitride photocatalytic material according to claim 2, wherein the method for preparing the tubular carbon nitride in S1 comprises:
s1-1, carrying out hydrothermal reaction on urea and melamine serving as raw materials at 180-240 ℃ for 18-24 h to obtain a carbon nitride precursor;
and S1-2, calcining the carbon nitride precursor for 4-6 h at 400-600 ℃ in an inert atmosphere to obtain the tubular carbon nitride.
4. The method for preparing the molybdenum carbide modified tubular carbon nitride photocatalytic material according to claim 3, wherein the molybdenum carbide modified tubular carbon nitride photocatalytic material is a molybdenum carbide-based photocatalytic material,
in the S1-1, the molar ratio of the urea to the melamine is 1-5: 1;
and/or in the S1-2, the calcination is carried out in a muffle furnace, and the temperature rise rate in the muffle furnace is 2.3-6 ℃/min.
5. The method for preparing the molybdenum carbide modified tubular carbon nitride photocatalytic material according to claim 3, wherein the method for preparing molybdenum carbide in S2 comprises the following steps:
s2-1, dropwise adding the hydrochloric acid solution into a mixed solution containing ammonium heptamolybdate, aniline solution and deionized water to obtain a white precipitate;
s2-2, placing the white precipitate in a tube furnace, and keeping the temperature at 500-800 ℃ for 4-6 h under inert atmosphere to obtain molybdenum carbide.
6. The method for preparing the molybdenum carbide modified tubular carbon nitride photocatalytic material according to claim 5, wherein the molybdenum carbide modified tubular carbon nitride photocatalytic material is a molybdenum carbide-based photocatalytic material,
in the S2-1, the concentration of the hydrochloric acid solution is 1-4 mol/L;
and/or in the S2-1, in the mixed solution containing ammonium heptamolybdate, aniline solution and deionized water, the molar ratio of ammonium heptamolybdate to aniline is 1: 12-18;
and/or in the S2-2, the temperature rise rate of the tube furnace is 2-5 ℃/min.
7. The use of the molybdenum carbide-modified tubular carbon nitride photocatalytic material according to claim 1 for degrading antibiotics and dyes in wastewater.
8. The application of the molybdenum carbide modified tubular carbon nitride photocatalytic material in degrading antibiotics and dyes in wastewater according to claim 7 is characterized in that the application method comprises the following steps:
(1) adding a molybdenum carbide modified tubular carbon nitride photocatalytic material into wastewater, and stirring in a dark place to achieve adsorption balance;
(2) the photocatalytic reaction is carried out under visible light.
9. The application of the molybdenum carbide modified tubular carbon nitride photocatalytic material in degrading antibiotics and dyes in wastewater according to claim 8, wherein the stirring time is 1-4 h; the lambda of the visible light is more than or equal to 400 nm; the time of the photocatalytic reaction is 60-240 min.
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| CN113443695B (en) * | 2021-06-30 | 2023-08-22 | 福州大学 | Molybdenum carbide auxiliary agent, preparation method thereof and application thereof in Fenton reaction degradation of organic pollutants |
| CN114733540B (en) * | 2022-03-30 | 2023-06-06 | 华南农业大学 | Nanoscale carbon-coated Mo-Mo 2 Heterogeneous nanoparticle of C and preparation method and application thereof |
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