CN110252334B - Doped nano manganese dioxide composite material, preparation method and application thereof - Google Patents
Doped nano manganese dioxide composite material, preparation method and application thereof Download PDFInfo
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 33
- 230000001699 photocatalysis Effects 0.000 claims abstract description 14
- 239000011572 manganese Substances 0.000 claims abstract description 13
- 238000005303 weighing Methods 0.000 claims abstract description 13
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- 238000010525 oxidative degradation reaction Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 11
- 230000015556 catabolic process Effects 0.000 claims description 9
- 238000006731 degradation reaction Methods 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 238000009775 high-speed stirring Methods 0.000 claims description 3
- 230000000149 penetrating effect Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 238000002835 absorbance Methods 0.000 description 19
- 239000011941 photocatalyst Substances 0.000 description 10
- 239000011148 porous material Substances 0.000 description 9
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- 238000001471 micro-filtration Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 6
- 238000004043 dyeing Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 206010047700 Vomiting Diseases 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 208000035475 disorder Diseases 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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Abstract
The invention belongs to a doped nano manganese dioxide composite material, and discloses an Fe doped composite nano photocatalytic material and application thereof in photocatalytic oxidative degradation of methylene blue. Adopts a one-step synthesis technology according to a certain Mn 7+ ：Mn 4+ Molar ratio of (2) and certain Fe: weighing potassium permanganate and MnSO according to the mass ratio of Mn 4 ·H 2 O and Fe 2 (SO 4 ) 3 And deionized water is used for preparing the above-mentioned materials into solutions respectively, the prepared solutions are added according to a certain sequence by utilizing oxidation-reduction method to make reaction so as to produce precipitate, and the precipitate is undergone the process of centrifugal washing and drying so as to obtain the invented clustered ellipsoidal Fe-doped nano manganese dioxide catalyst. The catalyst shows excellent catalytic activity in photocatalytic oxidative degradation of methylene blue.
Description
Technical field:
the invention belongs to the field of nano material preparation technology and sewage treatment, and particularly relates to an Fe-doped nano photocatalyst and application thereof in photocatalytic oxidation degradation of methylene blue.
The background technology is as follows:
along with the improvement of life quality, the demands of people for dyes such as dress making and tanning are gradually increased, and the printing and dyeing industry becomes the industry of gradually burning and exploding at present, but the generated printing and dyeing wastewater is discharged into a water environment in a large amount without effective treatment, so that serious harm is caused to ecological environment and human health. Among the various dyes, methylene blue is a typical dye which is used in a large amount for dyeing and coloring various articles, and ingestion of methylene blue causes serious damage to eyes of human and animals and may cause adverse symptoms of nerve disorders, nausea and vomiting, and the like, which are harmful to human health. Therefore, it is of great importance to degrade methylene blue in printing and dyeing wastewater to convert it into harmless substances.
At present, the treatment method of printing and dyeing wastewater at home and abroad mainly comprises a physical adsorption method, a microbial decomposition method and a chemical oxidation method. The physical adsorption method mainly adopts active carbon which is a material with strong adsorptivity, and although the treatment method has low energy consumption and obvious effect in a short period, the adsorption product is easy to desorb and secondary pollution is easy to cause; the microbial decomposition method mainly relies on the metabolic activity of microorganisms to decompose pollutants, and has the advantages of low speed, incomplete decomposition and even potential pollution sources; the photocatalytic oxidation in the chemical oxidation method is a clean and effective treatment method, but the treatment effect is limited by the catalyst. Therefore, the modification of the conventional photocatalyst and the development of a novel photocatalyst are necessary.
The invention comprises the following steps:
the invention aims to provide a preparation method of a novel composite photocatalyst, which is applied to photocatalytic oxidation degradation of methylene blue, and has the advantages of simple preparation method and high catalytic degradation efficiency.
According to the invention, fe is doped into nano manganese dioxide by using an oxidation-reduction method, so that the novel composite nano photocatalyst with excellent photocatalytic performance is obtained.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a doped nano manganese dioxide composite material is Fe doped nano manganese dioxide; the Fe doping amount of the Fe doped nano manganese dioxide is 5 percent, the Fe doped nano manganese dioxide is a cluster nano elliptic porous structure, the pore size is 3.427nm, and the specific surface area is 250.163m 2 Per mg, pore volume of 0.284cc/gThe surface of the nano ellipsoid is provided with a fine fiber rod-shaped penetrating structure, the length of the fine fiber rod-shaped structure is 1-2 mu m, the nano ellipsoids are connected with each other through fiber rods, and the surface of the nano ellipsoid is in a hollow laminar shape.
The preparation method of the novel composite photocatalyst comprises the following steps:
(1) According to Mn 7+ ∶Mn 4+ The molar ratio of the reaction is 2:3, and a certain amount of potassium permanganate and MnSO are weighed 4 ·H 2 O, weighing potassium permanganate and MnSO with deionized water 4 ·H 2 O is prepared into a solution; weighing a certain amount of Fe according to the mass ratio of Fe to Mn of 5% 2 (SO 4 ) 3 And the weighed Fe was dissolved in deionized water 2 (SO 4 ) 3 Is prepared into a solution.
(2) Placing the potassium permanganate solution prepared in the step (1) on a magnetic stirrer, heating, stirring and dissolving;
(3) Dropwise adding the Fe prepared in the step (1) into the potassium permanganate solution in the step (2) under the condition of high-speed stirring 2 (SO 4 ) 3 After the solution is added, the rotating speed of the magnetic stirrer is increased;
(4) Dropwise adding the MnSO prepared in the step (1) into the reaction solution in the step (3) under the condition of intense stirring 4 ·H 2 After the O solution is added, stirring vigorously for 2 hours in a boiling state until a precipitate is generated;
(5) Naturally cooling the solution obtained in the step (4) at room temperature, and centrifuging after cooling to obtain a precipitate;
(6) Repeatedly washing the precipitate in the step (5) with deionized water, and then drying at a constant temperature of 80 ℃ for 12 hours to obtain the Fe-doped nano manganese dioxide composite material.
The invention also provides an application of the doped nano manganese dioxide composite material in photocatalytic oxidation degradation of methylene blue. The method comprises the following specific steps: and (3) adding the Fe-doped nano manganese dioxide composite material into methylene blue solution, placing the reaction solution under the condition of ultraviolet light and stirring with magnetic force, and reacting for 3 hours to finish the oxidative degradation of the methylene blue.
Wherein the added mass of the Fe-doped nano manganese dioxide composite material is 10 mg-90 mg.
Preferably, the mass of the Fe-doped nano manganese dioxide composite material is 20mg.
Further, the volume of the methylene blue solution is 120ml, and the concentration is 10mg/L.
Further, the pH of the reaction solution is 3.0 to 11.0.
Further, the temperature of the reaction solution is 25 ℃ to 65 ℃.
Further, the magnetic stirring rotating speed is 300r/min.
Compared with the prior art, the preparation and application of the Fe-doped nano manganese dioxide photocatalyst have the following advantages:
the Fe-doped nano manganese dioxide is adopted to prepare the novel composite photocatalytic material, so that the preparation process is simple, and the catalytic degradation efficiency is high. The photocatalyst is utilized to degrade methylene blue, so that the reaction time is effectively shortened while the degradation efficiency is improved, the influence of pH and reaction temperature on the methylene blue removal rate is reduced, the use of acid-base reagents is reduced, the pH adjustment link can be omitted, and the operation cost is reduced.
Description of the drawings:
fig. 1: an electron microscope scan of the Fe-doped nano manganese oxide composite material prepared in example 1.
Fig. 2: an electron microscope scan of the Fe-doped nano manganese oxide composite material prepared in example 1.
Fig. 3: an electron microscope scan of the Fe-doped nano manganese oxide composite material prepared in example 1.
Fig. 4: an electron microscope scan of the Fe-doped nano manganese oxide composite material prepared in example 1.
The specific embodiment is as follows:
unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. The test reagents used in the following examples are all conventional biochemical reagents unless otherwise specified, and the test methods are all conventional methods unless otherwise specified.
The invention and its application will now be described in detail with reference to examples
Example 1
According to Mn 7+ ∶Mn 4+ The molar ratio of the reaction is 2:3, and a certain amount of potassium permanganate solution and MnSO are weighed 4 ·H 2 O is prepared into solution in deionized water, and a certain amount of Fe is weighed according to the mass ratio of Fe to Mn of 5 percent 2 (SO 4 ) 3 And is dissolved in deionized water to prepare a solution. Heating, stirring and dissolving potassium permanganate on a magnetic stirrer, and then dropwise adding Fe into the solution under high-speed stirring 2 (SO 4 ) 3 After the solution is added dropwise, the rotation speed of a magnetic stirrer is increased, and MnSO is added dropwise under the conditions of intense stirring and heating 4 ·H 2 And (3) after the O solution is added dropwise, stirring vigorously for hours in a boiling state to generate a precipitate, naturally cooling and centrifuging at room temperature, repeatedly washing with deionized water, and drying at a constant temperature of 80 ℃ for 12 hours to obtain the Fe-doped nano manganese dioxide.
Example 2
Measuring a certain amount of 10mg/L methylene blue sample, filtering with a microfiltration membrane with a pore diameter of 0.45 μm, and measuring initial absorbance A at 664.0nm 0 = 1.858. Weighing 120ml of the same 10mg/L methylene blue solution into a 250ml quartz beaker, adjusting the pH value to 9, weighing 20mg of prepared Fe-doped nano manganese dioxide, adding the Fe-doped nano manganese dioxide into the weighed methylene blue solution, magnetically stirring the mixture at the temperature of 25 ℃ and 300r/min, taking 5ml of reaction solution every 20min under the irradiation condition of an ultraviolet lamp, filtering the reaction solution by a microfiltration membrane with the pore diameter of 0.45 mu m, and measuring the absorbance A at the wavelength of 664.0nm, wherein the absorbance A is expressed as eta= (A) according to a formula 0 -A)/A 0 The removal rate was calculated by x 100% (where n is the removal rate). After 20min of reaction, the absorbance a=0.189 of the reaction solution was measured, and the removal rate was calculated to be 89.9%; after 3 hours of reaction, the absorbance a=0.027 of the reaction solution was measured, and the removal rate was calculated to be 98.5%.
Example 3
Measuring a certain amount of 10mg/L methylene blue sample, filtering with a microfiltration membrane with a pore diameter of 0.45 μm, and measuring initial absorbance A at 664.0nm 0 = 1.760. Weighing 120ml of the same 10mg/L methylene blue solution into a 250ml quartz beaker, adjusting the pH value to 9, weighing 30mg of prepared Fe-doped nano manganese dioxide, adding the Fe-doped nano manganese dioxide into the weighed methylene blue solution, magnetically stirring the mixture at the temperature of 25 ℃ and 300r/min, taking 5ml of reaction solution every 20min under the irradiation condition of an ultraviolet lamp, filtering the reaction solution by a microfiltration membrane with the pore diameter of 0.45 mu m, and measuring the absorbance A at the wavelength of 664.0nm, wherein the absorbance A is expressed as eta= (A) according to a formula 0 -A)/A 0 The removal rate was calculated by x 100% (where η is the removal rate). After 20min of reaction, the absorbance a=0.108 of the reaction solution was measured, and the removal rate was calculated to be 93.9%; after 3 hours of reaction, the absorbance a=0.025 of the reaction solution was measured, and the removal rate was calculated to be 98.6%.
Example 4
Measuring a certain amount of 10mg/L methylene blue sample, filtering with a microfiltration membrane with a pore diameter of 0.45 μm, and measuring initial absorbance A at 664.0nm 0 =1.814. Weighing 120ml of the same 10mg/L methylene blue solution into a 250ml quartz beaker, adjusting the pH value to 7, weighing 20mg of prepared Fe-doped nano manganese dioxide, adding the Fe-doped nano manganese dioxide into the weighed methylene blue solution, magnetically stirring the mixture at the temperature of 25 ℃ and 300r/min, taking 5ml of reaction solution every 20min under the irradiation condition of an ultraviolet lamp, filtering the reaction solution by a microfiltration membrane with the pore diameter of 0.45 mu m, and measuring the absorbance A at the wavelength of 664.0nm, wherein the absorbance A is expressed as eta= (A) according to a formula 0 -A)/A 0 The removal rate was calculated by x 100% (where n is the removal rate). After 20min of reaction, the absorbance a=0.077 of the reaction solution was measured, and the removal rate was calculated to be 95.8%; after 3 hours of reaction, the absorbance a=0.013 of the reaction solution was measured, and the removal rate was calculated to be 99.3%.
Example 5
After a certain amount of 10mg/L of methylene blue sample was measured and filtered with a microfiltration membrane having a pore size of 0.45 μm, the initial absorbance a0=1.860 was measured at a wavelength of 664.0 nm. Weighing 120ml of the same 10mg/L methylene blue solution in a 250ml quartz beaker, adjusting the PH value to 9, weighing 20mg of prepared Fe doped nano dioxygenManganese is dissolved and added into a measured methylene blue solution, 5ml of reaction solution is taken every 20min under the condition of magnetic stirring at 35 ℃ and 300r/min and ultraviolet lamp irradiation, and after the reaction solution is filtered by a microfiltration membrane with the aperture of 0.45 mu m, the absorbance A is measured at the wavelength of 664.0nm, and according to the formula eta= (A) 0 -A)/A 0 The removal rate was calculated by x 100% (where η is the removal rate). After 20min of reaction, the absorbance a=0.117 of the reaction solution was measured, and the removal rate was calculated to be 93.7%; after 3 hours of reaction, the absorbance a=0.008 of the reaction solution was measured, and the removal rate was calculated to be 99.6%.
As can be seen from examples 1-5, the preparation process of the novel composite photocatalytic material prepared by adopting Fe-doped nano manganese dioxide is simple, and the catalytic degradation efficiency is high. Meanwhile, the removal rate of the photocatalyst for degradation treatment of methylene blue under the same conditions can reach more than 89% after 20min of reaction, and the removal rate of the photocatalyst for 3h of reaction can exceed 90%, so that the reaction time is effectively shortened, the influence of pH and reaction temperature on the removal rate of the methylene blue is reduced, the use of acid-base reagents is reduced, the pH adjustment link can be omitted, and the running cost is reduced.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (4)
1. The application of the Fe-doped nano manganese dioxide composite material in photocatalytic oxidation degradation of methylene blue is characterized in that the composite material is Fe-doped nano manganese dioxide; the Fe-doped nano manganese dioxide composite material is a cluster nano ellipsoid, the surface of the Fe-doped nano manganese dioxide composite material is provided with a fine fiber rod-shaped penetrating structure, the cluster nano ellipsoids are connected through fiber rods, and the surface of the nano ellipsoid is in a hollow layered shape.
2. The use of the Fe-doped nano manganese dioxide composite material according to claim 1 for photocatalytic oxidative degradation of methylene blue, wherein the mass ratio of Fe to Mn is 5%.
3. Use of the Fe-doped nano manganese dioxide composite material according to any one of claims 1-2 for photocatalytic oxidative degradation of methylene blue, characterized in that the preparation method of the composite material comprises the following steps:
(1) According to Mn 7+ ∶Mn 2+ The molar ratio of the reaction is 2:3, and a certain amount of potassium permanganate and MnSO are weighed 4 ·H 2 O, weighing potassium permanganate and MnSO with deionized water 4 ·H 2 O is prepared into a solution; weighing a certain amount of Fe according to the mass ratio of Fe to Mn of 5% 2 (SO 4 ) 3 The weighed Fe was treated with deionized water 2 (SO 4 ) 3 Preparing into a solution;
(2) Placing the potassium permanganate solution prepared in the step (1) on a magnetic stirrer, heating, stirring and dissolving;
(3) Dropwise adding the Fe prepared in the step (1) into the potassium permanganate solution prepared in the step (2) under the condition of high-speed stirring 2 (SO 4 ) 3 After the solution is added, the rotating speed of the magnetic stirrer is increased;
(4) Dropwise adding the MnSO configured in the step (1) into the reaction solution in the step (3) 4 ·H 2 The solution O is vigorously stirred for 2 hours in a boiling state until the solution O is completely dripped, and a precipitate is generated;
(5) Naturally cooling the reaction solution obtained in the step (4) at room temperature, and centrifuging after cooling to obtain a precipitate;
(6) Repeatedly washing the precipitate in the step (5) with deionized water, and then drying at a constant temperature of 80 ℃ for 12 hours to obtain the Fe-doped nano manganese dioxide composite material.
4. The use of the Fe-doped nano manganese dioxide composite material according to any one of claims 1-2 for photocatalytic oxidative degradation of methylene blue, characterized by the specific steps of: 10 mg-90 mg of Fe doped nano manganese dioxide composite material is added into 120mL of 10mg/L methylene blue solution, the reaction solution is placed under ultraviolet irradiation and magnetically stirred with 300r/min, the reaction pH is 3.0-11.0, the reaction temperature is 25-65 ℃, and the oxidative degradation of the methylene blue can be completed after 3 hours of reaction.
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| CN113426455B (en) * | 2021-06-22 | 2023-10-27 | 扬州工业职业技术学院 | Fenton-like catalyst with manganese dioxide clusters loaded with iron and preparation method thereof |
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