CN107456963B - Manganese dioxide nanoflower and silicon oxide nanofiber composite catalyst and preparation method thereof - Google Patents
Manganese dioxide nanoflower and silicon oxide nanofiber composite catalyst and preparation method 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 92
- 239000002121 nanofiber Substances 0.000 title claims abstract description 68
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 239000002057 nanoflower Substances 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims description 29
- 238000002360 preparation method Methods 0.000 title abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 9
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000011068 loading method Methods 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 abstract 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract 1
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 239000011572 manganese Substances 0.000 abstract 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 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 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical group [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229960003742 phenol Drugs 0.000 description 1
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B01J35/615—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The invention discloses a catalyst compounded by manganese dioxide nanoflowers and silicon oxide nanofibers and a preparation method thereof, wherein the content of the manganese dioxide nanoflowers in the catalyst is 30-60 wt%, and the preparation method comprises the following steps: the method comprises the steps of taking silicon oxide nanofibers as a carrier, taking potassium permanganate as a manganese source, taking persulfate as an oxidant, generating manganese oxide nanoflowers through a low-temperature hydrothermal reaction, and loading the manganese oxide nanoflowers on the surfaces of the silicon oxide nanofibers to form a catalyst compounded by the manganese dioxide nanoflowers and the silicon oxide nanofibers. The catalyst compounded by the manganese dioxide nanoflowers and the silicon oxide nanofibers has the outstanding advantages of good dispersibility in water, easiness in fixed forming, strong adsorption capacity, high catalytic activity and the like. The preparation method has the advantages of short process flow, simple operation, high production efficiency, low energy consumption, low requirement on equipment and easy realization of industrial production.
Description
Technical Field
The invention belongs to the technical field of preparation of environment-friendly functional materials, nano materials and catalytic materials, and particularly relates to a novel composite heterogeneous Fenton catalyst and a preparation method thereof.
Background
With the acceleration of the industrialization process, the sources, types and discharge amount of organic wastewater are increasing continuously. Many organic waste water has high toxicity, which poses great threat to ecological environment and human survival, and people pay attention to how to degrade the organic waste water. Based on sulfate radical (SO) in comparison with the conventional Fenton catalytic method4 ●-) The advanced catalytic oxidation technology has the advantages of wide working pH range, strong catalytic performance, no by-product, high efficiency, convenient medicament transportation and storage and the like, and is receiving more and more extensive attention and attention. The catalyst performance is determined by the catalytic oxygenOne of the keys of the good and bad effect of the cosmetics. Among the catalysts, the manganese dioxide catalyst has the remarkable advantages of low price, wide source, good chemical stability, environmental friendliness, high catalytic activity and the like, and has excellent application prospect.
In the prior art, manganese dioxide with nanometer-scale size is generally prepared to obtain larger specific surface area, thereby achieving stronger catalytic activity. However, nano manganese dioxide is easy to agglomerate in the synthesis process to form hard aggregates, so that the catalytic performance of the nano manganese dioxide is greatly reduced; in addition, in the actual use process, the nano manganese dioxide cannot be effectively recycled due to the excessively fine particle size, and the requirement of industrial production is difficult to meet. The development of structurally stable nano manganese dioxide, which is immobilized on a suitable carrier, is an effective method for solving the above-mentioned drawbacks, and has become one of the important directions of current research. For example, a paper published in the Journal of Hazardous Materials reports that the catalytic performance is enhanced by loading flaky nano manganese dioxide on graphene (DOI: 10.1016/j.jhazmat.2015.08.031); a paper published in the foreign journal of Industrial & Engineering Chemistry Research reports that the catalytic degradation effect of organic matters is improved by loading flaky nano manganese dioxide on diatomite (DOI: 10.1021/ie 5002229); and so on. In the prior report, the micron-size carrier is selected more, and the surface area for manganese dioxide growth load is limited; and the appearance of the carrier is mostly granular and flaky, and fibrous and nano fibrous carriers are not seen yet. In addition, the reported morphologies of the nano manganese dioxide are mainly simple morphologies such as granular, flaky, rod-shaped and fibrous shapes, and other complex morphologies are rare. For nanomaterials, morphology has a large impact on performance.
Therefore, in order to solve the existing problems, a new and novel carrier needs to be developed as a carrier of manganese dioxide, and a novel nano manganese dioxide structure and morphology are designed and combined to prepare a novel composite catalyst, so as to overcome the limitations and existing defects of the prior art and further improve the performance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, adopts silicon oxide nano-fibers which have nano-sizes and are easy to form as carriers, and loads nano flower-shaped manganese dioxide with good structural stability and large specific surface area on the surfaces of the silicon oxide nano-fibers to form a manganese dioxide nano-flower and silicon oxide nano-fiber composite catalyst with high catalytic activity and high practicability, thereby obtaining greater application value.
In the manganese dioxide nanoflower and silicon oxide nanofiber composite catalyst, the crystal structure of the manganese dioxide nanoflower is-MnO2Uniformly distributed on the surface of the silicon oxide nano fiber and presenting a highly dispersed characteristic. The preparation method of the composite catalyst is simple, high in production efficiency, mild in reaction condition, low in cost, simple in equipment and few in medicament types, and is beneficial to large-scale industrial preparation.
The manganese dioxide nanoflower and silicon oxide nanofiber composite catalyst comprises 30-60 wt% of manganese dioxide nanoflowers and 70-40 wt% of silicon oxide nanofibers.
Preferably, the diameter of the silicon oxide nanofiber in the catalyst is 20 nm-100 nm, the length of the silicon oxide nanofiber is more than 1 μm, and the length-diameter ratio of the silicon oxide nanofiber is more than 20.
Preferably, the diameter of the manganese dioxide nanoflower in the catalyst is 100-200 nm.
The invention further provides a preparation method of the catalyst compounded by the manganese dioxide nanoflower and the silicon oxide nanofiber, which comprises the following steps:
(1) completely dispersing the silicon oxide nano-fibers in water in a mechanically strong stirring manner until a uniform primary suspension is formed;
(2) adding potassium permanganate and persulfate into the primary suspension, and continuously stirring to completely dissolve the potassium permanganate and the persulfate to form uniform secondary suspension;
(3) putting the secondary suspension into a high-pressure reaction kettle, and carrying out hydrothermal reaction for a certain time;
(4) and (4) naturally cooling the secondary suspension reacted in the high-pressure reaction kettle in the step (3) to room temperature, performing solid-liquid separation, washing the obtained product for several times with water, and drying to constant weight to obtain the manganese dioxide nanoflower and silicon oxide nanofiber composite catalyst.
Preferably, the concentration of the silicon oxide nano-fibers in the primary suspension in the step (1) is 3 g/L to 6 g/L.
Preferably, the mass ratio of the potassium permanganate in the secondary suspension to the silicon oxide nanofibers in the step (2) is controlled to be 11: 14-11: 4.
Preferably, the persulfate in the secondary suspension in the step (2) is one of sodium persulfate, potassium persulfate and ammonium persulfate.
More preferably, the concentration of the persulfate is 10 mmol/L-20 mmol/L.
Preferably, the temperature of the hydrothermal reaction in the step (3) is 85-100 ℃, and the reaction time is 4-5 hours.
Preferably, the drying temperature in step (4) is 80 ℃.
Compared with the prior art, the invention has the following remarkable advantages and beneficial effects:
(1) the catalyst carrier used in the invention is silicon oxide nano-fiber with the diameter of less than 100 nm, and compared with the traditional micron-sized carrier, the catalyst carrier can provide larger specific surface area for the growth of the catalyst, simultaneously inhibits the agglomeration of the loaded catalyst to the maximum extent, and obviously improves the dispersibility, thereby greatly increasing the exposed catalytic active surface and effectively improving the adsorption performance and catalytic activity of the catalyst. (2) The carrier of the invention is amorphous silicon dioxide, which has no toxicity, strong thermal stability and chemical stability and can be widely applied to actual wastewater treatment. Meanwhile, the surface of the silicon oxide nano fiber has rich hydroxyl groups, high chemical activity and strong hydrophilicity, has excellent organic matter adsorption performance and excellent dispersibility in water, can effectively strengthen the dispersion of the nano manganese dioxide in water, and improves the practical application performance of the nano manganese dioxide. (3) The manganese dioxide catalyst is in a nanometer flower shape, and has a larger specific surface area and a richer hierarchical structure compared with the traditional rod-shaped and flaky manganese dioxide catalysts, so that more excellent catalytic activity is shown. (4) The one-dimensional nanofiber morphology of the silicon oxide nanofiber in the composite material is completely reserved, and compared with the traditional granular, spherical, flaky and columnar composite catalyst, the one-dimensional nanofiber morphology of the silicon oxide nanofiber can be prepared into a film, a filter screen and the like for fixation, and the one-dimensional nanofiber morphology of the silicon oxide nanofiber has better practicability. (5) The preparation method of the composite material is simple, only two medicaments of potassium permanganate and persulfate are needed, and the two medicaments are common medicaments in industrial production. Tap water can be used as a reaction medium, so that the production cost is greatly reduced, and water after the synthesis reaction can be recycled. The composite material is synthesized at a low temperature (85-100 ℃), and the reaction temperature is controlled within a certain temperature range without accurate temperature control. Compared with the traditional hydrothermal synthesis process, the method has the advantages that the reaction temperature is greatly reduced, and the requirements on reaction equipment are also greatly reduced.
The composite material catalyst prepared by the invention is composed of silicon oxide nano-fibers and manganese dioxide nano-flowers growing on the surfaces of the fibers and having high dispersibility, the overall appearance is a tightly combined morphology structure of the nano-fibers and the nano-flowers, and the specific surface area of the composite material catalyst can reach 300 m2More than g, strong adsorbability to organic pollutants and easy dispersion in water. Therefore, the manganese dioxide nanoflower and silicon oxide nanofiber composite catalyst prepared by the method provided by the invention can be widely applied to the field of Fenton-like catalytic degradation of organic wastewater.
The preparation method of the manganese dioxide nanoflower and silicon oxide nanofiber composite catalyst provided by the invention is simple, the production process flow is simple, the energy consumption is low, the equipment investment is small, the raw materials are cheap and easy to obtain, and the large-scale industrial production is easy to realize.
Drawings
FIG. 1: an X-ray diffraction (XRD) pattern of the manganese dioxide nanoflower and silicon oxide nanofiber composite catalyst;
FIG. 2: a Transmission Electron Microscope (TEM) image of the manganese dioxide nanoflower and silicon oxide nanofiber composite catalyst;
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments. It is to be understood that the specific embodiments described herein are merely illustrative of the invention, further illustrating the features and advantages of the invention, and are not to be taken as limiting the invention.
Example 1
Weighing 4g of silicon oxide nanofibers (the diameter of the nanofibers is 30-60 nm, the length of the nanofibers is 5-20 microns), and completely dispersing the nanofibers in 1L of water under the condition of vigorous stirring to form a uniform primary suspension. 7.40 g of potassium permanganate and 3.20 g of sodium persulfate (sodium persulfate concentration of 13.4 mmol/L) were weighed out and added to the above-mentioned primary suspension with stirring, and stirred for 10 min to completely dissolve them to obtain a secondary suspension. The secondary suspension was transferred to an autoclave and subjected to hydrothermal reaction at 90 ℃ for 4 hours. After the reaction is finished, the reaction mixture is naturally cooled to room temperature. And (3) carrying out solid-liquid separation on the suspension after the hydrothermal reaction, washing the separated solid product for 3 times by using water, and drying the product in a drying oven at the temperature of 80 ℃ to constant weight so as to obtain the final manganese dioxide nanoflower and silicon oxide nanofiber composite catalyst. The results of X-ray diffraction (XRD) analysis of the composite material are shown in FIG. 1, and the photograph of the transmission electron microscope is shown in FIG. 2. The analysis result shows that: manganese dioxide nanoflower (crystal form-MnO) with diameter of about 100-200 nm2) The silicon oxide nano-fibers are distributed on the surface of the amorphous silicon oxide nano-fibers in a dispersed state, the one-dimensional nano-fiber morphology of the silicon oxide nano-fibers is completely reserved, and the silicon oxide nano-fibers can be made into films, filter screens and the like for fixation, so that the silicon oxide nano-fibers have better practicability; the manganese dioxide is in a nanometer flower shape, has a larger specific surface area and a richer hierarchical structure, and therefore shows more excellent catalytic activity.
Example 2
Weighing 5g of silicon oxide nanofibers (the diameter of the nanofibers is 20-50 nm, the length of the nanofibers is 3-10 microns), and completely dispersing the nanofibers in 1L of water under the condition of vigorous stirring to form uniform primary suspension. 4.3 g of potassium permanganate and 2.70g of potassium persulfate (potassium persulfate concentration of 10 mmol/L) were weighed out and added to the above-mentioned primary suspension with stirring, and stirred for 10 min continuously to completely dissolve them to obtain a secondary suspension. The secondary suspension was transferred to an autoclave and subjected to hydrothermal reaction at 95 ℃ for 4.5 hours. After the reaction is finished, the reaction mixture is naturally cooled to room temperature. And (3) carrying out solid-liquid separation on the suspension after the hydrothermal reaction, washing the separated solid product for 3 times by using water, and drying the product in a drying oven at the temperature of 80 ℃ to constant weight so as to obtain the final manganese dioxide nanoflower and silicon oxide nanofiber composite catalyst.
Example 3
Weighing 5g of silicon oxide nanofibers (the diameter of the nanofibers is 40-100 nm, and the length of the nanofibers is 10-20 microns), and completely dispersing the silicon oxide nanofibers in 1L of water under the condition of vigorous stirring to form uniform primary suspension. 6.90 g of potassium permanganate and 3.80 g of ammonium persulfate (the concentration of the ammonium persulfate is 16.7 mmol/L) are weighed and added into the primary suspension under the condition of stirring, and the primary suspension is stirred continuously for 10 min to be completely dissolved to obtain a secondary suspension. The secondary suspension was transferred to a high-pressure reactor and subjected to hydrothermal reaction at 85 ℃ for 5 hours. After the reaction is finished, the reaction mixture is naturally cooled to room temperature. And (3) carrying out solid-liquid separation on the suspension after the hydrothermal reaction, washing the separated solid product for 3 times by using water, and drying the product in a drying oven at the temperature of 80 ℃ to constant weight so as to obtain the final manganese dioxide nanoflower and silicon oxide nanofiber composite catalyst.
Example 4
Weighing 6g of silicon oxide nanofibers (the diameter of the nanofibers is 20-80 nm, the length of the nanofibers is 3-15 microns), and completely dispersing the silicon oxide nanofibers in 1L of water under the condition of vigorous stirring to form uniform primary suspension. 14.66 g of potassium permanganate and 4.76 g of sodium persulfate (sodium persulfate concentration of 20 mmol/L) were weighed out and added to the above-mentioned primary suspension with stirring, and stirred for 10 min to completely dissolve them to give a secondary suspension. The secondary suspension was transferred to an autoclave and subjected to hydrothermal reaction at 100 ℃ for 5 hours. After the reaction is finished, the reaction mixture is naturally cooled to room temperature. And (3) carrying out solid-liquid separation on the suspension after the hydrothermal reaction, washing the separated solid product for 3 times by using water, and drying the product in a drying oven at the temperature of 80 ℃ to constant weight so as to obtain the final manganese dioxide nanoflower and silicon oxide nanofiber composite catalyst.
The first table shows the detection results of the products obtained in the examples and the degradation effect on organic pollutants. (note: in the catalytic process, potassium hydrogen persulfate is used as an oxidant with the dosage of 10 mmol/L; organic pollution common in the industries of phenol, bisphenol A, rhodamine B, methylene blue and the like is used as a target reactant for degradation, the initial concentration of the organic pollution is 20 mg/L; the concentration of the manganese dioxide nanoflower and the silicon oxide nanofiber composite catalyst in a reaction solution is 0.1 g/L, and the reaction time is 60 min).
From the table I, it can be known that the manganese dioxide nanoflower and silicon oxide nanofiber composite material has a high degradation rate on organic pollutants, so that the organic pollutants are effectively degraded within 60min of reaction time, and the composite material belongs to a high-efficiency Fenton-like catalyst.
While there have been shown and described what are at present considered the fundamental principles and essential features of the invention and its advantages, it will be understood by those skilled in the art that the invention is not limited by the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (1)
1. A method for preparing a manganese dioxide nanoflower and silicon oxide nanofiber composite catalyst comprises the following steps:
weighing 6g of silicon oxide nanofibers with the diameter of 20-80 nm and the length of 3-15 microns, and completely dispersing the silicon oxide nanofibers in 1L of water under the condition of vigorous stirring to form uniform primary suspension; weighing 14.66 g of potassium permanganate and 4.76 g of sodium persulfate, wherein the concentration of the sodium persulfate is 20 mmol/L, adding the potassium permanganate and the sodium persulfate into the primary suspension under the condition of stirring, and continuously stirring for 10 min to completely dissolve the potassium permanganate and the sodium persulfate to obtain secondary suspension; transferring the secondary suspension into a high-pressure reaction kettle, carrying out hydrothermal reaction for 5 hours at the temperature of 100 ℃, and naturally cooling to room temperature after the reaction is finished; and (3) carrying out solid-liquid separation on the suspension after the hydrothermal reaction, washing the separated solid product for 3 times by using water, and drying the product in a drying oven at the temperature of 80 ℃ to constant weight so as to obtain the final manganese dioxide nanoflower and silicon oxide nanofiber composite catalyst.
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