CN113083303A - Carbon-coated alpha-Fe2O3Material, preparation method and application thereof - Google Patents
Carbon-coated alpha-Fe2O3Material, preparation method and application thereof Download PDFInfo
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- CN113083303A CN113083303A CN201911340601.6A CN201911340601A CN113083303A CN 113083303 A CN113083303 A CN 113083303A CN 201911340601 A CN201911340601 A CN 201911340601A CN 113083303 A CN113083303 A CN 113083303A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 39
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 27
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 24
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910003145 α-Fe2O3 Inorganic materials 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 238000004108 freeze drying Methods 0.000 claims abstract description 13
- 239000012153 distilled water Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 9
- 239000003403 water pollutant Substances 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 2
- 229910000859 α-Fe Inorganic materials 0.000 abstract description 20
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 239000012028 Fenton's reagent Substances 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 150000007522 mineralic acids Chemical class 0.000 abstract description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 118
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 27
- 239000002086 nanomaterial Substances 0.000 description 26
- 230000035484 reaction time Effects 0.000 description 18
- 239000002114 nanocomposite Substances 0.000 description 10
- 230000001590 oxidative effect Effects 0.000 description 9
- 229910001868 water Inorganic materials 0.000 description 9
- 238000007710 freezing Methods 0.000 description 8
- 230000008014 freezing Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 231100000049 endocrine disruptor Toxicity 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- 238000005491 wire drawing 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
- 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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- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- 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
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- 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
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- 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
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- 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
- C02F2305/10—Photocatalysts
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Abstract
The invention discloses a carbon-coated alpha-Fe2O3The material and the preparation method and the application thereof, wherein the preparation method of the material comprises the following steps: adding melamine and ferric nitrate into distilled water, dissolving the melamine, adjusting the pH value of a reaction system by using inorganic acid, hydrolyzing the melamine in situ to generate cyanuric acid, and then self-assembling the melamine and the cyanuric acid to form a template; then a precursor structure with a loose structure is obtained by adopting a freeze-drying mode, and finally the alpha-Fe coated with carbon is obtained by calcining in a muffle furnace2O3. The experimental method is simple, low in cost and capable of being synthesized on a large scale. Compared with the classical Fenton reagent, the material is very stable and recyclable, and has the advantages of pH: 2-7 can effectively oxidize pollutants and more effectively utilize H2O2And does not cause secondary pollution.
Description
Technical Field
The invention relates to carbon-coated alpha-Fe2O3The material, in particular to a carbon-coated alpha-Fe prepared by a template and used for photo-Fenton oxidation of various water pollutants2O3A method of making a material.
Background
In the world, with the increase of population, the development of economy and the promotion of industrial process, more and more novel pollutants appear, including substances such as medicines, pesticides, chlorophenols and endocrine disruptors, and the substances enter a water body, are accumulated and enriched continuously, cause serious pollution to a water environment, and finally harm the life health of human beings through food chains layer by layer. However, some studies have shown that the organic pollutants and their metabolites are not only toxic but also mostly persistent and intractable, and are difficult to be effectively removed by conventional water treatment technologies such as physical and chemical means or biodegradation. Therefore, the treatment technology of the organic pollutants difficult to biodegrade becomes a research hotspot in the fields of environmental science and technology.
Classical Fenton which mainly generates strong oxidizing free radicals utilizes hydroxyl free radicals (. OH) to attack organic pollutants, so that organic molecules are gradually degraded into small molecular substances such as carbon dioxide, water, inorganic salt and the like, and the aim of efficiently removing toxic and harmful organic pollutants is fulfilled. However, the classical Fenton reaction has strict requirements on the pH value, is easy to generate iron mud to cause secondary pollution, and utilizes H2O2Is inefficient, resulting in excessive costs. In order to solve the problems, the invention develops a carbon-coated alpha-Fe prepared by a template method2O3. The semiconductor catalyst is used for absorbing visible light, so that the effects of cyclic utilization and no secondary pollution are achieved, the pH value response range is widened, pollutants are oxidized more quickly and effectively, and 99.0 percent of nitrobenzene solvent can be oxidized by illumination for 90minLiquid (100mg/L) and total mineralization (TOC measurement) 97%.
Disclosure of Invention
The invention aims to synthesize alpha-Fe with high-efficiency optical Fenton performance2O3The method solves the problems of low utilization rate of hydrogen peroxide in the classical Fenton reaction and secondary pollution caused by iron salt generated in the reaction process. The invention provides a template method for preparing carbon-coated alpha-Fe for oxidizing various water pollutants by using photo-Fenton2O3The method of (1): adding melamine and different iron salts into distilled water, dissolving the melamine, adjusting the pH value of a reaction system by using inorganic acid, hydrolyzing the melamine in situ to generate cyanuric acid, and then self-assembling the melamine and the cyanuric acid to form a template; then a precursor structure with a loose structure is obtained by adopting a freeze-drying mode, and finally the alpha-Fe coated with carbon is obtained by calcining in a muffle furnace2O3. The experimental method is simple, low in cost and capable of being synthesized on a large scale. Compared with the classical Fenton reagent, the material is very stable and recyclable, and has the advantages of pH: 2-7 can effectively oxidize pollutants and more effectively utilize H2O2And does not cause secondary pollution.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
carbon-coated alpha-Fe2O3The preparation method of the material comprises the following steps:
1) adding melamine and ferric nitrate into distilled water, and uniformly mixing;
2) detecting the pH value of the solution obtained in the step 1), and then adding strong acid to adjust the pH value to 1-3;
3) placing the solution after the pH value is adjusted in the step 2) at room temperature until white flocculent precipitate appears;
4) freeze-drying the white flocculent precipitate obtained in the step 3) to obtain a precursor;
5) calcining the precursor obtained in the step 4) in a muffle furnace to obtain carbon-coated alpha-Fe2O3A material.
Further, the step 1) is specifically as follows: under the condition of stirring at the temperature of 30-80 ℃, adding a certain amount of ferric nitrate into distilled water, stirring for 15-90min, adding a certain amount of melamine, and continuing to stir for 15-90 min.
Further, the molar concentration ratio of the melamine to the ferric nitrate in the step 1) is 1: 0.2 to 1.
Further, the molar concentration ratio of the melamine to the ferric nitrate in the step 1) is 1: 0.2.
further, the strong acid in the step 2) is concentrated nitric acid or concentrated hydrochloric acid.
Further, the standing time in the step 3) is 15-90 min.
Further, the freeze-drying process in the step 4) is as follows: placing in a refrigerator, standing at-25 deg.C for 4-24 hr; and placing the mixture in a freeze dryer, wherein the temperature is-50 ℃, the pressure is 35-50 MPa, and the freeze-drying time is 24-48h, so as to obtain the precursor.
Further, the calcining condition in the step 5) is that the temperature is increased to 500-800 ℃ in the air atmosphere, the temperature is kept for 2-4h, and finally the mixture is naturally cooled to the room temperature.
Carbon-coated alpha-Fe2O3Material of carbon-coated alpha-Fe as described above2O3The material is prepared by a preparation method.
The carbon-coated alpha-Fe2O3The material is applied to the oxidation of various water pollutants by using light Fenton.
The invention has the following beneficial effects: the method is innovative in that the method is used for preparing alpha-Fe2O3In the process, the melamine is creatively added, a supermolecule precursor with a certain shape is obtained through the hydrolysis of the melamine and strong acid, the function of a template in the prior art is achieved, and the alpha-Fe with excellent light Fenton performance can be further prepared through pyrolysis2O3Because most of the templates have high cost, the invention selects the self-generated template technology with low cost, can save a large amount of cost and provides an effective foundation for industrialized mass production.
Compared with the prior art, the method has simple and convenient process and operationAnd moreover, the used materials are common and low in price, and the method is favorable for further realizing the advantage of industrial production. Preparation of the resulting carbon-coated alpha-Fe2O3Under the irradiation of simulated sunlight, the tube is subjected to light Fenton oxidation of nitrobenzene, 99.0% of nitrobenzene is oxidized in 90min, and the tube has very good light Fenton oxidation performance. Carbon-coated alpha-Fe prepared by the method of the invention2O3The hierarchical structure with the hollow tubular structure leads to more reactive sites, is more beneficial to the reaction and has the advantages of stable structure and cyclic utilization.
The invention discloses a carbon-coated alpha-Fe prepared by a template method2O3The semiconductor catalyst is used for absorbing visible light, so that the effects of cyclic utilization and no secondary pollution can be achieved, and the pH value response range is widened.
Drawings
FIG. 1 is a scanning electron microscope image of the supramolecular precursor obtained in example 1;
FIG. 2 is the carbon-coated α -Fe obtained in example 12O3XRD pattern of the nanomaterial;
FIG. 3 shows carbon-coated α -Fe obtained in example 12O3Scanning electron microscope images of the nanomaterials;
FIG. 4 shows carbon-coated α -Fe obtained in example 12O3Transmission electron microscope photo of the nano material;
FIG. 5 shows carbon-coated α -Fe obtained in example 12O3When the pH value of the nano material is 3.55, the residual nitrobenzene quantity of the nitrobenzene oxidized by the light Fenton and the reaction time of the light Fenton are in a relational graph;
FIG. 6 shows carbon-coated α -Fe obtained in example 22O3When the pH value of the nano material is 3.55, the residual nitrobenzene quantity of the nitrobenzene oxidized by the light Fenton and the reaction time of the light Fenton are in a relational graph;
FIG. 7 shows carbon-coated α -Fe obtained in example 32O3When the pH value of the nano material is 3.55, the residual nitrobenzene quantity of the nitrobenzene oxidized by the light Fenton and the reaction time of the light Fenton are in a relational graph;
FIG. 8 shows the carbon-coated α -Fe2O3When the pH value of the nano material is 3.55, the residual nitrobenzene quantity of the nitrobenzene oxidized by the light Fenton and the reaction time of the light Fenton are in a relational graph;
FIG. 9 shows carbon-coated α -Fe obtained in example 12O3When the pH value of the nano material is 2.55, the residual nitrobenzene quantity of the nitrobenzene oxidized by the light Fenton and the reaction time of the light Fenton are in a relational graph;
FIG. 10 shows carbon-coated α -Fe obtained in example 12O3When the pH value of the nano material is 4.55, the residual nitrobenzene quantity of the nitrobenzene oxidized by the light Fenton and the reaction time of the light Fenton are in a relational graph;
FIG. 11 shows carbon-coated α -Fe obtained in example 12O3When the pH value of the nano material is 6.55, the residual nitrobenzene quantity of the nitrobenzene oxidized by the light Fenton and the reaction time of the light Fenton are in a relational graph;
FIG. 12 shows carbon-coated α -Fe obtained in example 12O3When the nano material is repeatedly recycled, the residual nitrobenzene quantity of the nitrobenzene oxidized by the light Fenton and the reaction time of the light Fenton are in a relational graph;
FIG. 13 shows carbon-coated α -Fe obtained in example 12O3The graph of the relationship between the residual total organic carbon amount of the nano material photo-Fenton oxidized nitrobenzene and the photo-Fenton reaction time;
FIG. 14 shows carbon-coated α -Fe obtained in example 12O3Free Fe in solution after the nano material is subjected to the reaction of oxidizing nitrobenzene by light Fenton2+The concentration of (c).
Detailed Description
The present invention will be described in further detail with reference to the following detailed description and accompanying drawings. It should be emphasized that the following description is merely exemplary in nature and is not intended to limit the scope of the invention or its application.
In the embodiment, the carbon-coated alpha-Fe for oxidizing various water pollutants by using photo-Fenton is prepared by using a template method2O3The method comprises the following steps:
1) under the condition of stirring at the temperature of 30-80 ℃, adding a certain amount of ferric nitrate into distilled water, stirring for 15-90min, adding a certain amount of melamine, and continuously stirring for 15-90min to obtain a white transparent solution; the molar ratio of melamine to ferric nitrate is 1: (0.2 to 1);
2) checking the pH value of the white transparent solution obtained in the step 1) by using a pH meter, and then adding strong acid (concentrated nitric acid or concentrated hydrochloric acid) to adjust the pH value to 1-3;
3) placing the solution after the pH value is adjusted in the step 2) at room temperature for 15-90min, and generating white flocculent precipitate.
4) Placing the white flocculent precipitate obtained in the step 3) into a refrigerator at (-25 ℃) for 4-24h, wherein the drying process comprises the following steps: placing the mixture in a freeze dryer, wherein the temperature reaches-50 ℃, the pressure is 35-50 MPa, and the freeze-drying time is 24-48h, so as to obtain a precursor;
5) taking out the precursor obtained in the step 4), putting the precursor into a crucible, and then putting the crucible into a muffle furnace for calcining; the calcining condition is that the temperature is raised to 500-800 ℃ under the air atmosphere, the temperature is kept for 2-4h, and finally the mixture is naturally cooled to the room temperature.
The following implementation examples are adopted to verify the beneficial effects of the invention:
example 1:
the template method of the embodiment is used for preparing carbon-coated alpha-Fe for oxidizing various water pollutants by using photo-Fenton2O3The method comprises the following steps:
0.0808g of ferric nitrate is added into a beaker filled with 100mL of distilled water, stirred in a water bath at 80 ℃ for 30min, and then 1.26g of melamine is added into the solution, and the solution is continuously and rapidly stirred for 30 min; adjusting the pH value of the obtained colorless transparent solution to 1 by using concentrated nitric acid or concentrated hydrochloric acid; taking out the beaker, placing the beaker at room temperature, naturally cooling for 60min, and precipitating white floccule with the reduction of temperature to obtain a precursor; transferring the precursor into a refrigerator for freezing at (-25 ℃), taking out the precursor after freezing for 12h, putting the precursor into a freeze dryer for freeze drying for 24h under the conditions of-50 ℃ and 50MPa to obtain a dried loose yellow-white precursor, and scanning an electron microscope (as shown in figure 1), wherein the precursor is in a rod-like shape; and finally, putting the precursor into a crucible, transferring the crucible into a muffle furnace for calcination, wherein the calcination condition is that the temperature is raised to 600 ℃ under the air atmosphere, and the temperature is kept for 2 hours.
Carbon coated alpha-Fe obtained in this example2O3The XRD pattern of the nanomaterial is shown in FIG. 2, and the carbon-coated alpha-Fe obtained in this example2O3Scanning surface electron microscope images of the nanomaterials are shown in FIG. 3, the carbon-coated α -Fe obtained in this example2O3The transmission electron micrograph of the nanomaterial is shown in fig. 4, and the sample is in a wiredrawing tubular structure, which is caused by using a supramolecular precursor as a template.
The carbon-coated α -Fe obtained in this example2O3The graph of the relationship between the residual nitrobenzene quantity of the nano-material photo-Fenton oxidized nitrobenzene and the photo-Fenton reaction time is shown in FIG. 5, and the graph shows that carbon-coated alpha-Fe2O3The nano composite material (dosage is 0.1g/L) is 5mM H2O299.0% nitrobenzene was completely oxidized in the presence of AM1.5 light for 90min (nitrobenzene solution concentration 100mg/L, pH 3.55).
Example 2:
the template method of the embodiment is used for preparing carbon-coated alpha-Fe for oxidizing various water pollutants by using photo-Fenton2O3The method comprises the following steps:
0.0808g of ferric nitrate is added into a beaker filled with 100mL of distilled water, and stirred in water bath at 80 ℃ for 30 min; then 1.26g of melamine is added into the solution, and the solution is continuously and rapidly stirred for 30 min; adjusting the pH value of the obtained colorless transparent solution to 1 by using concentrated nitric acid or concentrated hydrochloric acid; taking out the beaker, placing the beaker at room temperature, naturally cooling for 60min, and precipitating white floccule with the reduction of temperature to obtain a precursor; transferring the precursor into a refrigerator for freezing at (-25 ℃), taking out the precursor after freezing for 12h, and putting the precursor into a freeze dryer for freeze drying for 24h under the conditions of-50 ℃ and 50MPa to obtain a loose, dry, yellow and white precursor; and finally, putting the precursor into a crucible, transferring the crucible into a muffle furnace for calcination, wherein the calcination condition is that the temperature is raised to 500 ℃ under the air atmosphere, and the temperature is kept for 2 hours.
The carbon-coated α -Fe obtained in this example2O3The graph of the relationship between the residual nitrobenzene quantity of the nano-material photo-Fenton oxidized nitrobenzene and the photo-Fenton reaction time is shown in FIG. 6, from whichTo see carbon coated alpha-Fe2O3The nano composite material (dosage is 0.1g/L) is 5mM H2O294.0% nitrobenzene was completely oxidized in the presence of AM1.5 light for 90min (nitrobenzene solution concentration 100mg/L, pH 3.55).
Example 3:
the template method of the embodiment is used for preparing carbon-coated alpha-Fe for oxidizing various water pollutants by using photo-Fenton2O3The method comprises the following steps:
0.0808g of ferric nitrate is added into a beaker filled with 100mL of distilled water, stirred in a water bath at 80 ℃ for 30min, and then 1.26g of melamine is added into the solution, and the solution is continuously and rapidly stirred for 30 min; adjusting the pH value of the obtained colorless transparent solution to 1 by using concentrated nitric acid or concentrated hydrochloric acid; taking out the beaker, placing the beaker at room temperature, naturally cooling for 60min, and precipitating white floccule with the reduction of temperature to obtain a precursor; transferring the precursor into a refrigerator for freezing at (-25 ℃), taking out the precursor after freezing for 12h, and putting the precursor into a freeze dryer for freeze drying for 24h under the conditions of-50 ℃ and 50MPa to obtain a loose, dry, yellow and white precursor; and finally, putting the precursor into a crucible, transferring the crucible into a muffle furnace for calcination, wherein the calcination condition is that the temperature is raised to 700 ℃ under the air atmosphere, and the temperature is kept for 2 hours.
The carbon-coated α -Fe obtained in this example2O3The graph of the relationship between the residual nitrobenzene quantity of the nano-material photo-Fenton oxidized nitrobenzene and the photo-Fenton reaction time is shown in FIG. 7, and the graph shows that carbon-coated alpha-Fe2O3The nano composite material (dosage is 0.1g/L) is 5mM H2O284.0% nitrobenzene was completely oxidized in the presence of AM1.5 light for 90min (nitrobenzene solution concentration 100mg/L, solution pH 3.55).
Example 4:
the template method of the embodiment is used for preparing carbon-coated alpha-Fe for oxidizing various water pollutants by using photo-Fenton2O3The method comprises the following steps:
0.0808g of ferric nitrate is added into a beaker with 100mL of distilled water, stirred in a water bath at 80 ℃ for 30min, and then 1.26g of melamine is added into the solution, and the solution is continuously and rapidly stirred for 30 min; adjusting the pH value of the obtained colorless transparent solution to 1 by using concentrated nitric acid or concentrated hydrochloric acid; taking out the beaker, placing the beaker at room temperature, naturally cooling for 60min, and precipitating white floccule with the reduction of temperature to obtain a precursor; transferring the precursor into a refrigerator for freezing at (-25 ℃), taking out the precursor after freezing for 12h, and putting the precursor into a freeze dryer for freeze drying for 24h under the conditions of-50 ℃ and 50MPa to obtain a loose, dry, yellow and white precursor; and finally, putting the precursor into a crucible, transferring the crucible into a muffle furnace for calcination, wherein the calcination condition is that the temperature is increased to 800 ℃ under the air atmosphere, and the temperature is kept for 2 hours.
alpha-Fe obtained in this example2O3The graph of the relationship between the residual nitrobenzene quantity of the nano-material photo-Fenton oxidized nitrobenzene and the photo-Fenton reaction time is shown in FIG. 8, and the graph shows that carbon-coated alpha-Fe2O3The nano composite material (dosage is 0.1g/L) is 5mM H2O278.1% nitrobenzene was completely oxidized in the presence of AM1.5 light for 90min (nitrobenzene solution concentration 100mg/L, pH 3.55).
Example 5:
carbon-coated α -Fe prepared in example 12O3The graph of the relationship between the residual nitrobenzene quantity of the nano-material photo-Fenton oxidized nitrobenzene and the photo-Fenton reaction time is shown in FIG. 9, and the graph shows that carbon-coated alpha-Fe2O3The nano composite material (dosage is 0.1g/L) is 5mM H2O296.1% nitrobenzene was completely oxidized in the presence of AM1.5 light for 90min (concentration of nitrobenzene solution 100mg/L, pH 2.55).
Example 6:
carbon-coated α -Fe prepared in example 12O3The graph of the relationship between the residual nitrobenzene quantity of the nano-material photo-Fenton oxidized nitrobenzene and the photo-Fenton reaction time is shown in FIG. 10, and the graph shows that carbon-coated alpha-Fe2O3The nano composite material (dosage is 0.1g/L) is 5mM H2O293.4% nitrobenzene was completely oxidized in the presence of AM1.5 light for 90min (nitrobenzene solution concentration 100mg/L, solution pH 4.55).
Example 7:
carbon-coated α -Fe prepared in example 12O3The graph of the relationship between the residual nitrobenzene quantity of the nano-material photo-Fenton oxidized nitrobenzene and the photo-Fenton reaction time is shown in FIG. 11, and the graph shows that carbon-coated alpha-Fe2O3The nano composite material (dosage is 0.1g/L) is 5mM H2O2After reacting with AM1.5 light for 90min, 91.0% nitrobenzene was completely oxidized (nitrobenzene solution concentration 100mg/L, solution pH 6.55).
Example 8:
carbon-coated α -Fe prepared in example 12O3The nano material is repeatedly recycled, the graph of the relationship between the residual nitrobenzene quantity of the nitrobenzene oxidized by the light Fenton and the reaction time of the light Fenton is shown in figure 12, and the graph shows that the carbon-coated alpha-Fe is coated2O3The nano composite material (dosage is 0.1g/L) is 5mM H2O299.0% nitrobenzene can be completely oxidized in 90min under the illumination of AM1.5 (the concentration of the nitrobenzene solution is 100mg/L, the pH value of the solution is 3.55), and the efficient nitrobenzene oxidation efficiency is still maintained after 5 cycles of repetition, which indicates that the sample structure is stable and can be recycled.
Example 9:
carbon-coated α -Fe prepared in example 12O3The graph of the relationship between the residual total organic carbon amount of the nano-material photo-Fenton oxidized nitrobenzene and the photo-Fenton reaction time is shown in FIG. 13, and the graph shows that the carbon-coated alpha-Fe is coated2O3The nano composite material (dosage is 0.1g/L) is 5mM H2O2After the reaction with AM1.5 light for 90min, 97.0% nitrobenzene was completely mineralized (concentration of nitrobenzene solution is 100mg/L, pH of the solution is 3.55), which indicates that 97.0% nitrobenzene was converted into CO2And H2O。
Example 10:
example 1 carbon coated α -Fe prepared2O3Fe in solution of nano material in process of oxidizing nitrobenzene by light Fenton2+The concentration relationship is shown in FIG. 14, from which it can be seen that carbon-coated α -Fe2O3Nanocomposite (in an amount of 0.1 g-L) at 5mM H2O2When the solution is irradiated by AM1.5 light for 90min, almost no free Fe exists in the solution2+The material is stable and does not cause secondary pollution.
The above description is only a specific embodiment of the present invention, and not all embodiments, and any equivalent modifications of the technical solutions of the present invention, which are made by those skilled in the art through reading the present specification, are covered by the claims of the present invention.
Claims (10)
1. Carbon-coated alpha-Fe2O3The preparation method of the material is characterized by comprising the following steps:
1) adding melamine and ferric nitrate into distilled water, and uniformly mixing;
2) detecting the pH value of the solution obtained in the step 1), and then adding strong acid to adjust the pH value to 1-3;
3) placing the solution after the pH value is adjusted in the step 2) at room temperature until white flocculent precipitate appears;
4) freeze-drying the white flocculent precipitate obtained in the step 3) to obtain a precursor;
5) calcining the precursor obtained in the step 4) in a muffle furnace to obtain carbon-coated alpha-Fe2O3A material.
2. The preparation method according to claim 1, wherein step 1) is specifically: under the condition of stirring at the temperature of 30-80 ℃, adding a certain amount of ferric nitrate into distilled water, stirring for 15-90min, adding a certain amount of melamine, and continuing to stir for 15-90 min.
3. The method according to claim 1, wherein the molar concentration ratio of melamine to ferric nitrate in step 1) is 1: 0.2 to 1.
4. The method according to claim 3, wherein the molar concentration ratio of melamine to ferric nitrate in step 1) is 1: 0.2.
5. the method according to claim 1, wherein the strong acid in step 2) is concentrated nitric acid or concentrated hydrochloric acid.
6. The method according to claim 1, wherein the standing time in the step 3) is 15 to 90 min.
7. The method according to claim 1, wherein the freeze-drying process in step 4) is: placing in a refrigerator, standing at-25 deg.C for 4-24 hr; and placing the mixture in a freeze dryer, wherein the temperature is-50 ℃, the pressure is 35-50 MPa, and the freeze-drying time is 24-48h, so as to obtain the precursor.
8. The preparation method of claim 1, wherein the calcining condition in the step 5) is that the temperature is raised to 500-800 ℃ in an air atmosphere, the temperature is kept for 2-4h, and finally the mixture is naturally cooled to the room temperature.
9. Carbon-coated alpha-Fe2O3Material, characterized in that carbon is coated with α -Fe according to any of claims 1 to 82O3The material is prepared by a preparation method.
10. The carbon-coated α -Fe of claim 92O3The material is applied to the oxidation of various water pollutants by using light Fenton.
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Application publication date: 20210709 |