CN114570424A - Double-modified carbon nitride and preparation method and application thereof - Google Patents
Double-modified carbon nitride and preparation method and application thereof Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
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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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Abstract
The invention provides double-modified carbon nitride and a preparation method and application thereof, wherein the preparation method of the double-modified carbon nitride comprises the following steps: (1) mixing carbon nitride in a hydrogen peroxide solution, and stirring to obtain hydroxylated carbon nitride; (2) and (2) mixing the hydroxylated carbon nitride obtained in the step (1) with a coupling agent in a solvent, reacting, and drying to obtain the double-modified carbon nitride. The double-modified carbon nitride prepared by the preparation method can obviously improve the degradation rate of the double-modified carbon nitride to dye wastewater MB, and has higher application value in dye wastewater.
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to double-modified carbon nitride and a preparation method and application thereof.
Background
With the vigorous development of social economy, energy crisis and environmental pollution become very important issues for researchers in all countries around the world. Photocatalytic technology has shown great potential in environmental remediation and new energy development. However, the existing photocatalyst has low activity, and the reason is shown in multiple aspects, such as complicated preparation process of the catalyst, high cost, low utilization rate of sunlight, weak performance of the photocatalyst and the like, which brings many limitations to the application of the photocatalytic technology. Therefore, it is necessary to develop a photocatalyst with simple preparation method, low catalyst cost, high sunlight utilization rate and strong catalytic performance.
Carbon nitride (C)3N4) The method provides a new direction for the large-scale cheap production of the photocatalyst, has the advantages of unique electronic structure, proper energy band structure, good chemical and thermal stability and the like, is simple in preparation method and low in catalyst cost, and can be obtained by directly calcining the precursor. However, direct calcination of the resulting bulk g-C3N4The specific surface area is small, the adsorption capacity to reactants is poor, the catalytic effect is influenced, and the catalytic activity is not ideal. In addition, good light absorption capability is also one aspect of improving the photocatalytic performance, and in order to improve the catalytic performance, modification needs to be carried out on the photocatalyst.
By doping with metal or non-metal component pairs g-C3N4And (4) carrying out modification. Binary or ternary composites may also be prepared. For example, CN202010245137.9 discloses a method for preparing graphite with up-conversion characteristics by two steps of solvothermal method and calcining methodA phase carbonitride/high iodine bismuth oxide heterojunction, CN202010142859.1 provides a WO3/Ag/g-C3N4A method for synthesizing a three-phase photocatalytic material. The doped or compounded material can realize effective separation of photon-generated carriers, and the utilization efficiency of light energy is improved, so that the photocatalytic performance of the material is improved. However, the modification process is usually complicated, and some metal components need to be introduced, which causes the material cost to rise.
Structural regulation is also a modification method. The purpose is to increase C3N4Specific surface area, thereby improving the adsorption performance and the photocatalytic performance. For example, preparation of C with high specific surface area by template method3N4. Wherein the specific surface of the material prepared by the soft template method is not too high, or the carbon-nitrogen ratio of the prepared material is too large to deviate from the ideal value. Although the hard template method can prepare C with large specific surface area3N4However, the preparation process is complicated.
The silane coupling agent is a common modifier, is commonly used for treating inorganic fillers such as silicon dioxide, carbon black and the like, plays the roles of an active agent, a coupling agent, a cross-linking agent and a reinforcing agent in polymers such as rubber, silicon rubber and the like, is used as a metal surface antirust agent for treating the surface of metal, and effectively improves the corrosion resistance and the oxidation resistance of the surface of the metal and increases the adhesion of the metal and high polymer materials such as resin and the like. However, there are few reports of studies on the use of silane coupling agents for modification of photocatalysts, and among these reports, silane coupling agents play a major role as binders. For example, tiamulin and the like adopt silane coupling agent WD-50 to modify TiO2The expanded graphite composite material adopts silane coupling agent as adhesive and utilizes a sol-gel method to prepare TiO2(P25) is supported on expanded graphite, and the photocatalytic efficiency is higher than that of P25 at low supporting amount. There are also reports of modifications of certain components in composites, for example CN201710569142.3 discloses a highly visible active ATP/g-C3N4Preparation of-Ag composites in which the silane coupling agent propyl trimethoxysilane was used. The main application of using silane coupling agent gamma-methacryloxypropyltrimethoxysilane to modify single photocatalyst component is in TiO2And ZnO.
CN111437868A discloses a preparation method of a sugarcoated gourd-shaped attapulgite/carbon nitride composite material and application thereof in light nitrogen fixation. Firstly, preparing graphite-phase carbon nitride by using a nitrogen-rich precursor; then, modifying the attapulgite by using a silane coupling agent; preparing the candied gourd-shaped attapulgite/carbon nitride composite material (ATP/g-C) by using graphite phase carbon nitride and the modified attapulgite as raw materials3N4). The attapulgite/carbon nitride composite material is used for photocatalytic nitrogen fixation, and can achieve excellent photocatalytic nitrogen fixation effect.
CN110655843A discloses a C3N4A method for preparing a photocatalytic self-polishing resin-based composite coating material. Firstly, the method comprises the following steps: using silane coupling agent KH-570 to C3N4Modifying to obtain a product a; II, secondly: the product a, fluorine-containing acrylate monomer, acrylic monomer and acrylate monomer are polymerized by free radical solution to prepare C3N4Carrying out photocatalysis self-polishing on the resin mixture to obtain a product b; thirdly, the method comprises the following steps: and performing ultrasonic dispersion treatment on the product b to obtain the composite coating material. Compared with the conventional self-polishing coating, the fluorine-containing side chain and the hydrolysis functional group can jointly adjust the hydrolysis speed of the resin matrix, so that the problem of short service life of the photocatalytic self-polishing coating is solved; compared with the conventional C3N4The coating is a hydrophobic phase formed in the resin, so that the problem that the photocatalyst is lost along with the resin which is removed by polishing is solved; the hole structure of the hydrolyzed resin enables the photocatalyst in the resin to contact with the outside to form free radicals with antifouling activity, and the photocatalytic efficiency of the coating is improved.
Therefore, in view of the above disadvantages, it is desirable to provide a novel modified carbon nitride, which improves the photocatalytic degradation purification capability.
Disclosure of Invention
The invention aims to solve the technical problems that the existing modified carbon nitride has poor photocatalytic degradation capability and poor catalytic effect, and aims at overcoming the defects in the prior art, the invention provides double-modified carbon nitride and a preparation method and application thereof so as to achieve the purpose of improving the photocatalytic degradation performance of the carbon nitride.
In order to solve the above technical problems, in a first aspect, the present invention provides a method for preparing double-modified carbon nitride, comprising: the preparation method comprises the following steps:
(1) mixing carbon nitride in a hydrogen peroxide solution, and stirring to obtain hydroxylated carbon nitride;
(2) and (2) mixing the hydroxylated carbon nitride obtained in the step (1) with a coupling agent in a solvent, reacting, and drying to obtain the double-modified carbon nitride.
The method modifies the surface of the carbon nitride without complex steps, an internal doping or compounding process and a method for improving the specific surface area, but adopts hydroxylation and coupling agent to modify the carbon nitride, so that the surface hydroxyl is easy to capture cavities to generate hydroxyl radicals, namely, the local space charge separation of the carbon nitride is obviously promoted, the generated hydroxyl radicals promote the photocatalytic degradation of methylene blue, and the modification of the coupling agent can improve the dispersibility of catalyst particles in a reaction system, promote the contact of reactants and a catalyst, further obviously improve the degradation rate of reaction substrates, and is a very effective modification strategy for the degradation rate of the Methylene Blue (MB) in dye wastewater.
The preparation method of the carbon nitride in the step (1) comprises the following steps: and calcining the melamine to obtain the carbon nitride.
Preferably, the calcination temperature is 500 to 600 ℃, for example, 500 ℃, 520 ℃, 550 ℃, 560 ℃, 580 ℃, or 600 ℃.
Preferably, the calcination time is 2-4 h, for example, 2h, 2.5h, 3h, 3.5h or 4 h.
Preferably, the ratio of the carbon nitride to the hydrogen peroxide solution in step (1): 50mL of hydrogen peroxide solution per 0.5g of carbon nitride was used.
Preferably, the mass concentration of the hydrogen peroxide solution is 0.1-30%. The hydrogen peroxide solution used in the present invention has a relatively wide mass concentration range, and any concentration can be used as long as it is suitable for the carbon nitride hydroxylation reaction.
The coupling agent in the step (2) is a silane coupling agent or a siloxane coupling agent.
In the present invention, the siloxane coupling agent may be Hexamethyldisiloxane (HMDSO) or the like.
Preferably, the coupling agent is a silane coupling agent.
According to the invention, after the hydroxylated carbon nitride is treated by adopting the silane coupling agent or the siloxane coupling agent, partial hydroxyl on the surface of the carbon nitride is subjected to condensation reaction with the silane coupling agent, so that the coupling agent is grafted on the surface of the carbon nitride, the grafted surface of the carbon nitride can promote the reaction with a reaction substrate, and the catalytic degradation effect of the carbon nitride is improved.
Preferably, the silane coupling agent is any one of aminopropyltrimethoxysilane (KH-792), vinyltrimethoxysilane (YDH-171), gamma-methacryloxypropyltrimethoxysilane (KH-570) or gamma-chloropropylmethyldiethoxysilane (YDH-701).
At present, the silane coupling agents are applied to the modification of carbon nitride, and the effect is excellent.
Preferably, the silane coupling agent is gamma-chloropropylmethyldiethoxysilane.
In the invention, the most preferable silane coupling agent is gamma-chloropropyl methyl diethoxy silane (YDH-701), and because of the grafting reaction of the coupling agent and hydroxylated carbon nitride, the number of hydroxyl groups on the surface of the grafted double-modified carbon nitride and the number of groups of the coupling agent reach the optimal balance, the synergistic effect of promoting the separation of photogenerated electron holes and the dispersion of particles is fully exerted, and the effect of promoting the catalytic degradation is achieved.
Preferably, the mass ratio of the hydroxylated carbon nitride to the coupling agent in the step (2) is 1 (0.4-4), and may be, for example, 1:0.4, 1:1, 1:2, 1:3, 1:4, or the like.
Preferably, the mass ratio of the hydroxyl carbon nitride to the coupling agent is 1: 1.
Preferably, the solvent in the step (2) is any one of toluene, benzene, cyclohexane or n-hexane. In the present invention, toluene is generally preferably used as the solvent.
Preferably, the drying temperature in step (2) is 50 to 120 ℃, for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃ and the like.
Preferably, the drying time in the step (2) is 10-15 h, for example, 10h, 11h, 12h, 13h, 14h or 15h, etc.
In a second aspect, the present invention provides a double-modified carbon nitride prepared by the preparation method of the first aspect.
In a third aspect, the invention provides the use of the double-modified carbon nitride as described in the first aspect in photocatalytic degradation of methylene blue in dye wastewater.
When the double-modified carbon nitride provided by the invention is applied to catalytic degradation in dye wastewater MB, the degradation rate of catalytic MB can reach more than 50% in light reaction for 15min, the degradation rate in two hours can reach more than 90%, and the highest degradation rate can reach 97.7%.
The technical scheme of the invention has the following beneficial effects:
the method modifies the surface of the carbon nitride without complex steps, an internal doping or compounding process is omitted, modification is not performed by a method for improving the specific surface area, hydroxylation and a coupling agent are adopted for carrying out double modification on the carbon nitride, so that surface hydroxyl is easy to capture cavities to generate hydroxyl radicals, namely, the local space charge separation of the carbon nitride is obviously promoted, the generated hydroxyl radicals promote the photocatalytic degradation of methylene blue, the modification of the coupling agent can improve the dispersibility of catalyst particles in a reaction system, promote the contact of reactants and a catalyst, further obviously improve the degradation rate of reaction substrates, and is a very effective modification strategy for the degradation rate of dye wastewater MB.
When the double-modified carbon nitride provided by the invention is applied to catalytic degradation in dye wastewater MB, the degradation rate of catalytic MB can generally reach more than 50% after being subjected to light reaction for 15min, the degradation rate of two hours can reach more than 90%, the highest degradation rate can reach 97.7%, and the double-modified carbon nitride has high catalytic degradation efficiency for substances such as methylene blue and the like.
Drawings
Fig. 1 is a graph of MB degradation rate provided by an embodiment of the present invention.
FIG. 2 is an XRD (X-ray diffraction) characterization diagram of carbon nitride, hydroxylated carbon nitride and YDH-701 hydroxylated double-modified carbon nitride provided by the invention.
FIG. 3A is a scanning electron micrograph of carbon nitride according to the present invention.
FIG. 3B is a scanning electron micrograph of hydroxylated carbon nitride provided by the invention.
FIG. 3C is a scanning electron microscope image of YDH-701 hydroxylated double-modified carbon nitride provided by the invention.
Fig. 4A is a contact angle test chart of carbon nitride provided by the present invention.
FIG. 4B is a contact angle test chart of hydroxylated carbon nitride provided by the invention.
FIG. 4C is a contact angle test chart of YDH-701 hydroxylation double-modified carbon nitride provided by the invention.
In the SEM image, the scale is 2 μm.
Detailed Description
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, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
(1) The preparation of the carbon nitride and the application of the carbon nitride in the photocatalytic degradation of the dye wastewater MB are disclosed.
Weighing 10g of melamine solid by using an electronic balance, placing the melamine solid in a crucible, placing the crucible in a muffle furnace, setting the program to be 2.3 ℃/min, heating the melamine solid from 20 ℃ to 550 ℃, and keeping the melamine solid at 550 ℃ for 3h until the reaction is finished.
C is to be3N4In the photocatalytic degradation process of the dye wastewater MB, for a 10mg/L MB aqueous solution, the degradation rates of the MB are respectively 36.9%, 51.8%, 62.2% and 70.6% after the MB is subjected to light reaction for 15min, 30min and 60min, and 120 min.
(2) Preparation of hydroxylated carbon nitride and testing of MB degradation rate.
0.5g of C are weighed3N450mL of 20% hydrogen peroxide solution was added and stirred in a thermostatic water bath at 25 ℃ for various times in a heating stirrer. And (5) performing suction filtration, putting the mixture into an oven for 24 hours, scraping, grinding, weighing and bottling.
Hydroxylating C3N4In the photocatalytic degradation process of the dye wastewater MB, the degradation rates of MB of 10mg/L are respectively 52.3%, 75.9%, 85.2% and 86.8% for light reaction for 15min, 30min, 60min and 120 min.
In the following examples, the hydroxylated carbon nitrides used were all those prepared as described above. The silane coupling agents used in the examples of the present invention can be purchased from commercially available sources.
Example 1
This example prepares a KH-792 modified hydroxylated carbon nitride by the following procedure
Accurately weigh 0.1g of hydroxylated C3N4A three-neck flask is added with 50mL of toluene solvent, ultrasonic dispersion is carried out for 10min at room temperature, then 0.1mL of KH-792 is added, and the mixture is stirred and refluxed for reaction at 80 ℃ for 8 h. After the reaction is finished and the temperature is reduced to room temperature, filtering, washing twice by toluene and absolute ethyl alcohol respectively, placing at 100 ℃ and drying for 12h in vacuum to obtain the KH-792 modified hydroxylated C3N4A pale yellow powder.
Example 2
This example prepares YDH-171-modified hydroxylated carbon nitride by the following procedure
Accurately weigh 0.1g of hydroxylated C3N4Adding 50mL of toluene solvent into a three-neck flask, ultrasonically dispersing for 10min at room temperature, adding 0.1mL of YDH-171, and carrying out stirring reflux reaction at 80 ℃ for 8 h. After the reaction is finished and the temperature is reduced to the room temperature, filtering, washing twice by toluene and absolute ethyl alcohol respectively, and placing at 100 ℃ for vacuum drying for 12h to obtain YDH-171 modified hydroxylated C3N4A pale yellow powder.
Example 3
This example prepares an HMDSO modified hydroxylated carbon nitride by the following procedure
Accurately weigh 0.1g of hydroxylated C3N4Adding 50mL of toluene solvent into a three-neck flask, carrying out ultrasonic dispersion for 10min at room temperature, adding 0.1mL of HMDSO, and carrying out stirring reflux reaction at 80 ℃ for 8 h. After the reaction is finished and the temperature is reduced to the room temperature, filtering, washing twice by toluene and absolute ethyl alcohol respectively, and placing at 100 ℃ for vacuum drying for 12h to obtain the HMDSO modified hydroxylated C3N4A pale yellow powder.
Example 4
This example prepares YDH-701-modified hydroxylated carbon nitride by the following procedure
Accurately weigh 0.1g of hydroxylated C3N4Adding 50mL of toluene solvent into a three-neck flask, carrying out ultrasonic dispersion for 10min at room temperature, adding 0.1mL of silane coupling agent YDH-701, stirring at different oil bath temperatures set at different times, and carrying out reflux reaction. After the reaction is finished and the temperature is reduced to the room temperature, filtering, washing twice by toluene and absolute ethyl alcohol respectively, and placing at 100 ℃ for vacuum drying for 12h to obtain YDH-701 modified hydroxylated C3N4A pale yellow powder.
Example 5
This example prepares a KH-570 modified hydroxylated carbon nitride by the following procedure
Accurately weigh 0.1g of hydroxylated C3N4Adding 50mL of toluene solvent into a three-neck flask, ultrasonically dispersing for 10min at room temperature, adding 0.1mL of silane coupling agent KH-570, stirring at different oil bath temperatures set at different times, and carrying out reflux reaction. After the reaction is finished and the temperature is reduced to the room temperature, filtering, respectively washing twice by toluene and absolute ethyl alcohol, placing at 100 ℃ and drying in vacuum for 12h to obtain the KH-570 modified hydroxylated C3N4A pale yellow powder.
The double-modified carbon nitride obtained in the above examples 1 to 5 was subjected to a catalytic degradation performance test, specifically, the method was: in the process of using the double-modified carbon nitride for photocatalytic degradation of the dye wastewater MB, for a 10mg/L MB aqueous solution, the degradation rates of MB of 15min, 30min, 60min and 120min of light reaction are respectively tested, and the specifically obtained degradation rate data are shown in the following table 1:
TABLE 1
The degradation rate and the catalytic degradation time of carbon nitride, hydroxylated carbon nitride and the di-modified carbon nitride prepared in examples 1 to 5 for MB were plotted, as shown in FIG. 1 (all curves in FIG. 1 represent curves for hydroxylated and silane coupling agent di-modified carbon nitride).
As can be seen from the data obtained in table 1 and fig. 1, the degradation rate of the hydroxylated modified carbon nitride for catalyzing MB degradation is higher than that of the carbon nitride; and the degradation rate of the catalytic MB is further improved by the silane coupling agent and the hydroxylated double-modified carbon nitride.
As can be seen from the comparison of the data in the embodiments 1 to 5, the initial catalytic effect of the double-modified carbon nitride is not necessarily improved obviously after about 15min, but the catalytic effect is improved obviously after the catalytic time is prolonged, and the catalytic effect of the double-modified carbon nitride is better after about 120 min. The product with the best catalytic effect is YDH-701 hydroxylated double-modified carbon nitride, and the degradation rate of MB catalytic degradation in 2h can reach 97.7%.
Further, for carbon nitride (C)3N4) The hydroxylated carbon nitride and the YDH-701 hydroxylated double-modified carbon nitride are subjected to performance characterization, and the performance characterization specifically comprises X-ray diffraction, a scanning electron microscope and contact angle testing. The characterization results are shown in fig. 2, fig. 3A, fig. 3B, fig. 3C, fig. 4A, fig. 4B, and fig. 4C, respectively.
As can be seen from FIG. 2, compared with unmodified carbon nitride, the crystal form main structures of the carbon hydroxynitride and the carbon hydroxynitride modified by YDH-701 are kept unchanged, but the characteristic peak intensities are sequentially increased. This indicates that the surface modification does not affect the bulk structure of the catalyst, but has some effect on crystallinity and crystallite size.
FIG. 3A, FIG. 3B and the drawings3C comparison shows that C is modified by surface hydroxyl3N4The structure is relatively loose, the specific surface area is increased, and small particles are coated on the surface of the hydroxylated carbon nitride after the YDH-701 is modified, which is caused by the surface modification of the coupling agent.
As can be seen from the comparison of FIG. 4A, FIG. 4B and FIG. 4C, the contact angles of carbon nitride and hydroxyl carbon nitride are both 0, which indicates that both are hydrophilic materials, while the contact angle of carbon nitride after YDH-701 modification is 24.3 degrees, which indicates that the hydrophobicity is improved, and which also indicates that the coupling agent is successfully grafted on the surface of carbon nitride.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of double-modified carbon nitride is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) mixing carbon nitride in a hydrogen peroxide solution, and stirring to obtain hydroxylated carbon nitride;
(2) and (2) mixing the hydroxylated carbon nitride obtained in the step (1) with a coupling agent in a solvent, reacting, and drying to obtain the double-modified carbon nitride.
2. The production method according to claim 1, characterized in that: the preparation method of the carbon nitride in the step (1) comprises the following steps: calcining melamine to obtain the carbon nitride;
preferably, the calcining temperature is 500-600 ℃;
preferably, the calcination time is 2-4 h.
3. The method of claim 1, wherein: the ratio of the carbon nitride to the hydrogen peroxide solution in the step (1) is as follows: 50mL of hydrogen peroxide solution per 0.5g of carbon nitride;
preferably, the mass concentration of the hydrogen peroxide solution is 0.1-30%.
4. The method of claim 1, wherein: the coupling agent in the step (2) is a silane coupling agent or a siloxane coupling agent.
5. The method of claim 4, wherein: the coupling agent is a silane coupling agent;
preferably, the silane coupling agent is any one of aminopropyltrimethoxysilane, vinyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane or gamma-chloropropylmethyldiethoxysilane.
6. The method of claim 5, wherein: the silane coupling agent is gamma-chloropropyl methyl diethoxy silane.
7. The method of claim 1, wherein: the mass ratio of the hydroxylated carbon nitride to the coupling agent in the step (2) is 1 (0.4-4);
preferably, the mass ratio of the hydroxyl carbon nitride to the coupling agent is 1: 1.
8. The method of claim 1, wherein: in the step (2), the solvent is any one of toluene, benzene, cyclohexane or n-hexane;
preferably, the drying temperature in the step (2) is 50-120 ℃;
preferably, the drying time in the step (2) is 10-15 h.
9. The doubly modified carbon nitride produced by the production method according to any one of claims 1 to 8.
10. Use of the di-modified carbon nitride according to claim 9 in the photocatalytic degradation of methylene blue from dye waste water.
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