CN112604703B - A kind of graphitized carbon supported nano zero valent iron material and its preparation method and application - Google Patents
A kind of graphitized carbon supported nano zero valent iron material and its preparation method and application Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
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- 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 description 2
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
-
- 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
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- Life Sciences & Earth Sciences (AREA)
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
本发明属于纳米零价铁碳材料的制备领域，具体涉及一种石墨化碳负载纳米零价铁材料及其制备方法和应用。该石墨化碳负载纳米零价铁材料的制备方法，包括以下步骤：(1)将铁盐和2‑氨基对苯二甲酸置于球磨机反应釜中；(2)向球磨机反应釜中加入研磨介质，研磨得到球磨材料；(3)将球磨材料热解、冷却，即得石墨化碳负载纳米零价铁材料。制成的石墨化碳负载纳米零价铁材料具有更高更持久的催化降解效率，能较好的去除环境水样中的污染物，尤其是有机染料类污染物。
The invention belongs to the field of preparation of nano-zero-valent iron-carbon materials, and particularly relates to a graphitized carbon-supported nano-zero-valent iron material and a preparation method and application thereof. The preparation method of the graphitized carbon-loaded nano-zero-valent iron material comprises the following steps: (1) placing iron salt and 2-aminoterephthalic acid in a ball mill reaction kettle; (2) adding grinding media to the ball mill reaction kettle , grinding to obtain ball-milling material; (3) pyrolyzing and cooling the ball-milling material to obtain graphitized carbon-supported nano-zero valent iron material. The prepared graphitized carbon-supported nano-zero-valent iron material has higher and longer-lasting catalytic degradation efficiency, and can better remove pollutants in environmental water samples, especially organic dye pollutants.
Description
Technical Field
The invention belongs to the field of preparation of nano zero-valent iron-carbon materials, and particularly relates to a graphitized carbon loaded nano zero-valent iron material and a preparation method and application thereof.
Background
Advanced Oxidation Processes (AOPs) are Processes for treating toxic organic pollutants by generating hydroxyl radicals (OH ·) with strong oxidizing properties. The Fenton method is an important component in advanced oxidation technology, and compared with the traditional physical and biological treatment method, the Fenton method using active free radicals as oxidants has the advantages of high reaction speed and high mineralization degree, so that the Fenton method is widely applied to sewage treatment. Iron elements widely exist in nature, and iron-based materials are widely concerned for removing organic matters by a Fenton method. The Fenton reagent is prepared from ferrous ions (Fe)2+) And hydrogen peroxide (H)2O2) Composition of Fe under acidic condition (pH 2-4)2+Decomposition of H2O2Generation of OH and Fe3+OH and H2O2Reaction to generate hydrogen peroxide radical ion O2H, and O2H can also be Fe3+Reduction to Fe2+The organic contaminants are degraded during such cycling. However, in the homogeneous Fenton system, Fe2+Slow regeneration rate, Fe3+The constant accumulation leads to the production of iron sludge. The loss of a large amount of iron causes the reduction of the pollutant treatment efficiencyAnd the catalyst cannot be recycled and reused, so that the preparation of the heterogeneous iron-based material and the research on the performance of the heterogeneous iron-based material become hot spots. The nano zero-valent iron has the characteristics of large specific surface area and extremely strong reactivity, and is loaded on the carbon support material, so that the agglomeration of the nano zero-valent iron is effectively prevented, the stability of the nano zero-valent iron is improved, the loss of iron is reduced, and meanwhile, the specific surface area of the material is increased by the void structure of the carbon support material, and the effective action of pollutants and active ingredients of the nano zero-valent iron is promoted. The nitrogen atoms doped in the carbon material can regulate and control the electronic structure of the material and increase the reactive sites of the material. Therefore, the nitrogen-doped nano zero-valent iron-carbon material which has high catalytic activity, high stability and less iron dissolution and is synthesized by using a simple preparation method has very important practical value.
In the prior art, a common synthetic method of a nitrogen-doped nano zero-valent iron-carbon material is to use different materials as a carbon source, a nitrogen source and an iron source respectively, and synthesize the iron-carbon material with strong catalytic activity by a hydrothermal method-coprecipitation-electroplating combination method or a hydrothermal method-carbothermic reduction method. However, the delicate preparation method is complicated in operation process and synthesis conditions, and is not favorable for large-scale industrial production of materials.
Chinese patent application CN 106044921A provides a preparation method of a carbon sphere loaded nano zero-valent iron composite material, which comprises (1) preparing a carbon sphere containing hydrophilic functional groups (-OH, -COOH) by a hydrothermal method; (2) chelating iron ions with functional groups by soaking; (3) finally, dripping a potassium borohydride or sodium borohydride solution into a carbon sphere mixed solution with iron ions, and forming the carbon sphere loaded nano zero-valent iron composite material through strong reduction; although the preparation method solves the problem of agglomeration of the nano zero-valent iron to a certain extent, the hydrothermal method for preparing the nano carbon spheres has the defects that the particle size control range is limited, the obtained material has uneven particle size distribution, the material performance is influenced, and the wastewater treatment efficiency needs to be further improved.
Therefore, the development of the carbon-loaded nano zero-valent iron material which can better avoid agglomeration and can obtain uniform particle size and controllable size has important significance.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a graphitized carbon loaded nano zero-valent iron material and a preparation method thereof. The preparation process is simple and easy to operate, and the prepared graphitized carbon loaded nano zero-valent iron material has higher and more lasting catalytic degradation efficiency on dyes such as methyl orange and other organic pollutants, and can accelerate the mineralization of the organic pollutants.
In order to achieve the above purpose, the technical scheme provided by the invention is as follows:
a preparation method of a graphitized carbon loaded nano zero-valent iron material comprises the following steps:
(1) putting ferric salt and 2-amino terephthalic acid into a ball mill reaction kettle;
(2) adding a grinding medium into a reaction kettle of the ball mill, and grinding to obtain a ball-milled material;
(3) and pyrolyzing and cooling the ball-milling material to obtain the graphitized carbon loaded nano zero-valent iron material.
Preferably, in the step (1), the iron salt is selected from any one of ferric sulfate, ferric chloride, ferric nitrate or ferrous acetate; ferrous acetate is preferred.
Preferably, in the step (1), the mass ratio of the iron salt to the 2-amino terephthalic acid is 1-4:1, preferably 3: 1.
Preferably, in the step (2), the rotation speed of the ball mill is 290-350rpm, and the grinding time is 4-6 hours.
Preferably, in step (2), the grinding media are selected from any one of zirconia, stainless steel grinding balls, alumina or agate balls.
The grinding media preferably have a diameter of 10mm, 7mm, 5mm or 2 mm;
preferably, in the step (3), the pyrolysis is carried out in a tubular furnace, and the temperature rise rate of the pyrolysis is 5-10 ℃/min; the pyrolysis temperature is 750-1100 ℃;
preferably, the heating rate of the pyrolysis is 6-9 ℃/min; the pyrolysis temperature is 750-900 ℃; preferably 800 ℃;
preferably, in the step (3), the pyrolysis time after reaching the pyrolysis temperature is 2-5 h; preferably 3 hours.
Preferably, in the step (3), the pyrolysis is performed under an inert gas atmosphere, and the inert gas is argon or nitrogen.
Preferably, step (2) further comprises adding a solvent into the reaction kettle of the ball mill;
preferably, the solvent is any one of ethylene glycol, methanol, ultrapure water or dimethylformamide;
preferably, the solvent is added in an amount of 1-3 mL.
Preferably, the solvent is used in an amount of 1 to 3mL/g based on the mass of 2-aminoterephthalic acid (1 to 3mL of solvent is added per 1g of 2-aminoterephthalic acid).
The invention also aims to provide the graphitized carbon loaded nano zero-valent iron material prepared by the preparation method of the graphitized carbon loaded nano zero-valent iron material;
the graphitized carbon loaded nano zero-valent iron material consists of a nitrogen-doped graphitized carbon layer and nano zero-valent iron uniformly distributed in the carbon layer, wherein the graphitized carbon layer has regular and ordered lattice arrangement, is favorable for adsorbing pollutants on the surface of the graphitized carbon layer, protects the zero-valent iron and reduces the corrosion of the zero-valent iron; the grain size of the nanometer zero-valent iron is 4-9 nanometers, and the effective utilization area of the superfine zero-valent iron particles is increased, so that pollutants adsorbed on the surface of the material can be more effectively catalyzed and degraded.
The invention also aims to provide application of the graphitized carbon loaded nano zero-valent iron material in removing organic pollutants in an environmental water sample.
Compared with the prior art, the invention has the technical advantages that:
(1) the invention provides a graphitized carbon loaded nano zero-valent iron material for efficiently removing organic pollutants in an environmental water sample. The material is a nitrogen-doped graphitized carbon supported superfine zero-valent iron material, wherein the zero-valent iron has small particle size and is densely and uniformly distributed, and graphitized carbon is arranged in order, so that the zero-valent iron can be effectively protected, the corrosion of the zero-valent iron is prevented, and the stability and the durability of the material in the using process are improved.
(2) The invention combines mechanical ball milling and carbon thermal reduction, and forms covalent organic polymer by complexing mechanically milled iron salt and aromatic carboxylic acid, wherein the polymer is simultaneously used as iron, carbon and nitrogen sources, and forms the nitrogen-doped nano zero-valent iron-carbon material by high-temperature pyrolysis carbonization. The zero-valent iron particles in the material have small and uniformly distributed particle sizes, and can effectively contact with carbon, accelerate electron transfer and promote the catalytic degradation of organic pollutants. Meanwhile, the graphitized carbon load layer can well protect zero-valent iron, prevent the rapid corrosion of the zero-valent iron, prolong the service life of the material, can be recycled for multiple times, and is a potential heterogeneous Fenton catalyst.
(3) The nitrogen-doped carbon-loaded layer forms a regular graphitized structure, and the structure effectively protects zero-valent iron, reduces the corrosion of the zero-valent iron in the use process, and increases the stability and the reusability of the material. Meanwhile, the graphitized carbon can increase the specific surface area of the material, so that pollutant molecules are more easily adsorbed on the surface of the material. The material still maintained 96% catalytic efficiency after five repeated uses.
(4) The preparation method of the material is simple and easy to operate. Even when no solvent or polyethylene glycol or other dispersing agent is added in the preparation process, the method has a good effect, can reduce the synthesis cost, and meanwhile, iron in the material is not easy to be corroded by dissolved oxygen or aqueous solution, can not be inactivated quickly and generate red mud, so that the subsequent treatment cost is reduced; is suitable for large-scale macro-quantitative industrial production.
(5) The generated zero-valent iron has small particle size and uniform distribution. The zero-valent iron particles reduce the contact area of iron and carbon to a certain extent, promote the transfer of electrons, promote the effective decomposition of materials on hydrogen peroxide, and increase the in-situ generation of hydrogen peroxide, thereby increasing the generation of hydroxyl radical active ingredients and improving the degradation efficiency of pollutants.
(6) The form of a precursor polymer is kept, the graphitized carbon is arranged in order, and the nano zero-valent iron has small particle size and is uniformly and densely dispersed in the carbon layer, so that the active sites of the material are extremely large, hydrogen peroxide can be continuously decomposed to generate OH with strong oxidation activity, and organic pollutants are efficiently removed. Meanwhile, the graphitized carbon layer effectively protects zero-valent iron, prevents the zero-valent iron from being corroded, reduces the loss of iron ions in the using process and prolongs the service life of the material. The zero-valent iron, carbon and nitrogen in the material are cooperated with each other, so that electron transfer is accelerated, and the effect of degrading organic pollutants is remarkably improved, therefore, the nitrogen-doped graphitized carbon loaded nano zero-valent iron material can be applied to removal of various toxic and harmful organic pollutants in polluted water.
(7) The prepared graphitized carbon loaded nano zero-valent iron material has higher and more lasting catalytic degradation efficiency on dyes such as methyl orange and other organic pollutants, and accelerates the mineralization of the organic pollutants.
Drawings
FIG. 1: example 1 TEM photograph of a graphitized carbon-supported nano zero-valent iron material;
FIG. 2: example 1 SEM photograph of graphitized carbon-supported nano zero-valent iron material;
FIG. 3: example 1 XRD spectrum of graphitized carbon-supported nano zero-valent iron material;
FIG. 4: example 1 XPS spectrum of graphitized carbon-supported nano zero-valent iron material;
FIG. 5: example 1 graphitized carbon-supported nano zero-valent iron material N2Adsorption-desorption curve chart;
FIG. 6: example 1 comparison of graphitized carbon loaded nano zero valent iron material before and after treatment of organic pollutant methyl orange.
The invention will now be further illustrated with reference to the accompanying drawings and examples:
Detailed Description
The present invention will be described below with reference to specific examples to make the technical aspects of the present invention easier to understand and grasp, but the present invention is not limited thereto. The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
A preparation method of a graphitized carbon loaded nano zero-valent iron material comprises the following steps:
(1) putting ferrous acetate and 2-amino terephthalic acid into a ball mill reaction kettle according to the mass ratio of 3: 1;
(2) adding a zirconium oxide grinding medium with the diameter of 5mm into a reaction kettle of a ball mill, adjusting the rotating speed of the ball mill to 300rpm, adding 1mL/g of glycol solution, and grinding for 5 hours to obtain a polymer material;
(3) putting a polymer material into a tubular furnace, and heating to 800 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere; and (4) pyrolyzing for 3h, and cooling to obtain the graphitized carbon loaded nano zero-valent iron material.
Example 2
A preparation method of a graphitized carbon loaded nano zero-valent iron material comprises the following steps:
(1) putting ferric sulfate and 2-amino terephthalic acid into a ball mill reaction kettle according to the mass ratio of 2: 1;
(2) adding an alumina grinding medium with the diameter of 5mm into a reaction kettle of a ball mill, adjusting the rotating speed of the ball mill to 350rpm, adding 1mL/g of dimethylformamide solution, and grinding for 4 hours to obtain a polymer material;
(3) putting a polymer material into a tube furnace, and heating to 900 ℃ at a heating rate of 10 ℃/min in an argon atmosphere; and (4) pyrolyzing for 3h, and cooling to obtain the graphitized carbon loaded nano zero-valent iron material.
Example 3
A preparation method of a graphitized carbon loaded nano zero-valent iron material comprises the following steps:
(1) putting ferric chloride and 2-amino terephthalic acid into a ball mill reaction kettle according to the mass ratio of 4: 1;
(2) adding agate ball grinding media with the diameter of 10mm into a reaction kettle of the ball mill, adjusting the rotating speed of the ball mill to 290rpm, adding 1mL/g of glycol solution, and grinding for 5 hours to obtain a polymer material;
(3) putting a polymer material into a tubular furnace, and heating to 750 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere; and (4) pyrolyzing for 3h, and cooling to obtain the graphitized carbon loaded nano zero-valent iron material.
Example 4
A preparation method of a graphitized carbon loaded nano zero-valent iron material comprises the following steps:
(1) putting ferrous acetate and 2-amino terephthalic acid into a ball mill reaction kettle according to the mass ratio of 1: 1;
(2) adding a zirconium oxide grinding medium with the diameter of 5mm into a reaction kettle of a ball mill, adjusting the rotating speed of the ball mill to 290rpm, adding 3mL/g methanol solution, and grinding for 6 hours to obtain a polymer material;
(3) putting a polymer material into a tubular furnace, and heating to 900 ℃ at a heating rate of 6 ℃/min in a nitrogen atmosphere; and (4) pyrolyzing for 3h, and cooling to obtain the graphitized carbon loaded nano zero-valent iron material.
Example 5
The difference compared to example 1 is that no solvent is added during the grinding.
A preparation method of a graphitized carbon loaded nano zero-valent iron material comprises the following steps:
(1) putting ferrous acetate and 2-amino terephthalic acid into a ball mill reaction kettle according to the mass ratio of 3: 1;
(2) adding a zirconium oxide grinding medium with the diameter of 5mm into a reaction kettle of the ball mill, adjusting the rotating speed of the ball mill to 300rpm, and grinding for 5 hours to obtain a polymer material;
(3) putting a polymer material into a tubular furnace, and heating to 800 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere; and (4) pyrolyzing for 3h, and cooling to obtain the graphitized carbon loaded nano zero-valent iron material.
Comparative example 1
(compare with example 1, except that manual grinding is used in the preparation process)
Manually grinding ferrous acetate and 2-amino terephthalic acid according to the mass ratio of 3:1, then placing the ground materials in a tubular furnace, and heating the materials to 800 ℃ at the heating rate of 10 ℃/min in the nitrogen atmosphere; pyrolyzed for 3h and cooled to give comparative material 1.
Comparative example 2
(compared with example 1, difference is in temperature rising rate during preparation)
A preparation method of a graphitized carbon loaded nano zero-valent iron material comprises the following steps:
(1) - (2) Steps (1) - (2) of example 1;
(3) putting a polymer material into a tubular furnace, and heating to 800 ℃ at a heating rate of 20 ℃/min in a nitrogen atmosphere; and (5) pyrolyzing for 3h, and cooling to obtain the comparative material 2.
Comparative example 3
(compared with example 1, difference is in pyrolysis temperature)
A preparation method of a graphitized carbon loaded nano zero-valent iron material comprises the following steps:
(1) - (2) Steps (1) - (2) of example 1;
(3) putting a polymer material into a tubular furnace, and heating to 1500 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere; and (5) pyrolyzing for 3h, and cooling to obtain the comparative material 3.
Comparative example 4
(compared with example 1, difference is in pyrolysis temperature)
A preparation method of a graphitized carbon loaded nano zero-valent iron material comprises the following steps:
(1) - (2) Steps (1) - (2) of example 1;
(3) putting a polymer material into a tubular furnace, and heating to 500 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere; and (5) pyrolyzing for 3h, and cooling to obtain a comparative material 4.
Comparative example 5
(compared with example 1, the difference is the particle size of the ball-milling medium)
A preparation method of a graphitized carbon loaded nano zero-valent iron material comprises the following steps:
(1) putting ferrous acetate and 2-amino terephthalic acid into a ball mill reaction kettle according to the mass ratio of 3: 1;
(2) adding a zirconia grinding medium with the diameter of 15mm into a reaction kettle of a ball mill, adjusting the rotating speed of the ball mill to 300rpm, adding 1mL/g of glycol solution, and grinding for 5 hours to obtain a polymer material;
(3) putting a polymer material into a tubular furnace, and heating to 800 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere; and (5) pyrolyzing for 3h, and cooling to obtain the comparative material 5.
Comparative example 6
(different from example 1 in the ratio of raw materials)
A preparation method of a graphitized carbon loaded nano zero-valent iron material comprises the following steps:
(1) putting ferrous acetate and 2-amino terephthalic acid into a ball mill reaction kettle according to the mass ratio of 1: 3;
(2) adding a zirconium oxide grinding medium with the diameter of 5mm into a reaction kettle of a ball mill, adjusting the rotating speed of the ball mill to 300rpm, adding 1mL/g of glycol solution, and grinding for 5 hours to obtain a polymer material;
(3) putting a polymer material into a tubular furnace, and heating to 800 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere; and (5) pyrolyzing for 3h, and cooling to obtain the contrast material 6.
Comparative example 7
(different from example 1 in the solvent)
A preparation method of a graphitized carbon loaded nano zero-valent iron material comprises the following steps:
(1) putting ferrous acetate and 2-amino terephthalic acid into a ball mill reaction kettle according to the mass ratio of 3: 1;
(2) adding a zirconium oxide grinding medium with the diameter of 5mm into a reaction kettle of a ball mill, adjusting the rotating speed of the ball mill to 300rpm, adding 1mL/g of glycerol, and grinding for 5 hours to obtain a polymer material;
(3) putting a polymer material into a tubular furnace, and heating to 800 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere; and (5) pyrolyzing for 3h, and cooling to obtain a comparative material 7.
Performance characterization
Example 1 structural characterization of the graphitized carbon-supported nano zero-valent iron material specifically includes the following steps:
TEM and SEM images
The particle size and the morphology of the nano zero-valent iron material in example 1 were analyzed by a high-resolution transmission electron microscope. As can be seen from fig. 1, in the resulting material, zero-valent iron having a particle size of about 6nm is closely and uniformly distributed in the carbon framework. Meanwhile, the crystal lattices of the graphitized carbon which are arranged in order can be obviously observed in fig. 1, and the generated graphitized carbon-supported nano zero-valent iron structure is illustrated. FIG. 2 is a scanning electron microscope picture showing that the material has a spherical or polyhedral structure.
XRD spectrum
The X-ray diffraction (XRD) pattern of the material obtained in example 1 was measured on a b/max-RB diffraction meter (Rigaku, Japan) using nickel filtered Cu Ka rays at a scanning speed of 4o/min over a scanning range (2. theta.) from 5 to 90 deg. From FIG. 3, the XRD spectrum of the material is composed of diffraction peaks of zero-valent iron (JCPDS 06-0696) and graphitized carbon (JCPDS No.26-1080), which illustrates the successful synthesis of the graphitized carbon supported nano zero-valent iron material. The particle size of the zero-valent iron nanoparticles calculated by the Scherrer formula was 6nm, consistent with the electron microscope results.
XPS spectra
The material of example 1 was scanned with a full spectrum and a narrow spectrum using an X-ray spectrometer. As shown in fig. 4, the diffraction peaks containing C1s, O1s, N1s and Fe2p on the full spectrum indicate that the graphitized carbon-supported nano zero-valent iron material is composed of C, O, N and Fe elements. The high-resolution XPS spectrum of N1s can fit graphite-N, Fe-N and pyridine-N peaks, and judges that nitrogen mainly exists in the graphitized carbon loaded nano zero-valent iron material by a chemical bond containing iron-nitrogen coordination according to the intensity of the peaks. The high resolution XPS spectrum of Fe2p showed an alpha-Fe peak, which confirmed the formation of zero-valent iron. Meanwhile, the existence of the Fe-N peak indicates that the zero-valent iron nano particles can react with nitrogen in the material at the pyrolysis temperature of 800 ℃, and the existence of the nitrogen increases the content of iron in the material, so that the active sites of the material are increased.
4. Specific surface area, mesoporous diameter and pore volume
The specific surface area, pore volume and pore diameter of the obtained graphitized carbon-supported nano zero-valent iron material were measured by a specific surface area meter (Norcross, usa). The results of the measurements shown in FIG. 5 show that: the specific surface area of the graphitized carbon-supported nano zero-valent iron material is 235.4 (m)2(iv)/g); pore volume 0.35 (cm)3(iv)/g); the pore diameter is 2.2 nm. N thereof2The adsorption-desorption curve is a typical IV-type adsorption isotherm, and a hysteresis loop shows that the material is of a mesoporous structure.
(II) test of catalytic Performance
(1) Methyl orange is selected as a mode pollutant, and the micro-electrolysis performance of the graphitized carbon loaded nano zero-valent iron material in example 1 is tested.
The test procedure was as follows: 50mL of methyl orange dye solution of 50mg/L is prepared and placed in a 100mL beaker. 25mg of the sample of the graphitized carbon-supported nano zero-valent iron material of example 1 was added, the pH of the sample was adjusted to 4, and 25MmH was added2O2. The experiment was performed on a 300rmp shaker. Taking 2ml of the solution every 15min, filtering the solution through a 0.45 mu m filter membrane, and taking the supernatant to be tested. Fig. 6 is a comparison graph of the graphitized carbon supported nano zero-valent iron material of example 1 before and after the treatment of the organic pollutant methyl orange. And washing the reacted material with ultrapure water, and continuously using the washed material in a catalytic degradation experiment after vacuum drying to test the reusability of the material. The absorbance of methyl orange in the supernatant was measured by uv spectrophotometry. The TOC of the supernatant was also measured to indicate the mineralization of the contaminants.
The measurement conditions of the ultraviolet spectrophotometer were as follows: the absorbance of the samples was measured in a quartz cuvette at a wavelength of 460 nm. Firstly, measuring the absorbance of a standard solution, drawing a standard curve, and then obtaining the content of methyl orange in a sample by using the standard curve and the absorbance of methyl orange in the sample.
The TOC measurement conditions were as follows: centrifuging the water sample, taking supernatant, taking deionized water and 0.8% HCl as mobile phases, and detecting by using a TOC/TN analyzer.
The result shows that the methyl orange is completely degraded after 160min fenton reaction of the graphitized carbon loaded nano zero-valent iron material in a pollutant solution with the pH value of 4; the degradation rate of the methyl orange solution and the mineralization degree of the methyl orange after fenton reaction after 5 times of recycling are tested by the same method.
(2) The same method as in step (1) was used to evaluate the catalytic degradation performance of the graphitized carbon-supported nano zero-valent iron materials prepared in examples 2 to 4 and the comparative materials 1 to 7 in comparative examples 1 to 7 after 5 times of recycling.
TABLE 1 catalytic degradation performance of graphitized carbon loaded nano zero-valent iron material
From the test results of examples 1 to 4, it can be known that the graphitized carbon loaded nanoscale zero-valent iron material has a good effect of removing methyl orange organic pollutants in water, has a high degree of mineralization of the pollutants, and has an obvious effect after 5 times of recycling. The graphitized carbon loaded nano zero-valent iron material has important significance for controlling relevant pollution indexes.
As illustrated by comparative example 1, grinding of raw materials using a ball milling method is essential for preparing a highly efficient graphitized carbon-supported nano zero-valent iron material. The ground material is easy to generate superfine zero-valent iron particles in the subsequent carbonization process, and carbon is reduced into graphitized carbon to be coated around the nano zero-valent iron under the high-temperature condition.
Meanwhile, as shown in comparative examples 2 to 7, the heating rate, the pyrolysis temperature, the particle size of the ball-milling medium, the raw material ratio and the selection of the grinding solvent in the preparation process all have great influence on the application effect of the graphitized carbon loaded nano zero-valent iron material.
The above detailed description is specific to one possible embodiment of the present invention, and the embodiment is not intended to limit the scope of the present invention, and all equivalent implementations or modifications without departing from the scope of the present invention should be included in the technical scope of the present invention.
Claims (9)
1. A preparation method of a graphitized carbon loaded nano zero-valent iron material comprises the following steps:
(1) putting ferric salt and 2-amino terephthalic acid into a ball mill reaction kettle;
(2) adding a grinding medium into a reaction kettle of the ball mill, and grinding to obtain a ball-milled material;
(3) pyrolyzing and cooling the ball-milling material to obtain a graphitized carbon loaded nano zero-valent iron material;
the heating rate of the pyrolysis is 10 ℃/min;
the diameter of the grinding medium is 10mm, 7mm, 5mm or 2 mm;
the graphitized carbon loaded nano zero-valent iron material consists of a nitrogen-doped graphitized carbon layer and nano zero-valent iron uniformly distributed in the carbon layer, wherein the particle size of the nano zero-valent iron is 4-9 nanometers;
the ferric salt is ferrous acetate; the mass ratio of the ferric salt to the 2-amino terephthalic acid is 3: 1;
in the step (2), adding a solvent into a reaction kettle of the ball mill; the solvent is any one of ethylene glycol, methanol or ultrapure water;
the amount of the solvent is 1-3mL per 1g of 2-aminoterephthalic acid based on the mass of 2-aminoterephthalic acid.
2. The method for preparing a graphitized carbon-supported nanoscale zero-valent iron material as claimed in claim 1, wherein in the step (2), the rotation speed of the ball mill is 290-350rpm, and the grinding time is 4-6 hours.
3. The method for preparing the graphitized carbon-supported nano zero-valent iron material according to claim 1, wherein in the step (2), the grinding medium is selected from any one of zirconia, stainless steel grinding balls, alumina or agate balls.
4. The method for preparing the graphitized carbon-supported nano zero-valent iron material according to claim 1, wherein in the step (3), the pyrolysis is performed in a tubular furnace, and the pyrolysis temperature is 750-1100 ℃; the pyrolysis time after reaching the pyrolysis temperature is 2-5 h.
5. The method for preparing the graphitized carbon-supported nano zero-valent iron material according to claim 4, wherein in the step (3), the pyrolysis time is 3 hours.
6. The method for preparing the graphitized carbon-supported nano zero-valent iron material of claim 4, wherein the pyrolysis temperature is 750-.
7. The method for preparing the graphitized carbon-supported nano zero-valent iron material of claim 6, wherein the pyrolysis temperature is 800 ℃.
8. A graphitized carbon-supported nano zero-valent iron material prepared by the preparation method of the graphitized carbon-supported nano zero-valent iron material as claimed in any one of claims 1 to 7.
9. The use of the graphitized carbon-supported nano zero-valent iron material of claim 8 in the removal of organic contaminants in an environmental water sample.
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