CN113019420A - Fe derived from MOF0/Fe3C @ C/N magnetic mesoporous composite material and preparation method and application thereof - Google Patents
Fe derived from MOF0/Fe3C @ C/N magnetic mesoporous composite material and preparation method and application thereof Download PDFInfo
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- 229910001567 cementite Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 135
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 57
- 239000000463 material Substances 0.000 claims abstract description 25
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 9
- PIPQOFRJDBZPFR-UHFFFAOYSA-N 1h-benzimidazole-5,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC2=C1NC=N2 PIPQOFRJDBZPFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- FMOYQLHCKHIWFF-UHFFFAOYSA-N carbon monoxide;cyclopenta-1,3-diene;iron(2+);methanone Chemical compound [Fe+2].[Fe+2].O=[CH-].O=[CH-].[O+]#[C-].[O+]#[C-].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 FMOYQLHCKHIWFF-UHFFFAOYSA-N 0.000 claims abstract description 3
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 claims abstract description 3
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- 238000006243 chemical reaction Methods 0.000 claims description 28
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
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- 230000003213 activating effect Effects 0.000 claims description 9
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- 239000012298 atmosphere Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
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- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 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 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
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- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
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- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002114 nanocomposite Substances 0.000 abstract 1
- 239000013110 organic ligand Substances 0.000 abstract 1
- 229960005404 sulfamethoxazole Drugs 0.000 description 33
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 33
- 239000003054 catalyst Substances 0.000 description 14
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- 239000013082 iron-based metal-organic framework Substances 0.000 description 10
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- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 4
- 229910000859 α-Fe Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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Images
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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
-
- B01J35/33—
-
- 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
- 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
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/20—Total organic carbon [TOC]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/44—Time
Abstract
The invention discloses Fe derived from MOF0/Fe3C @ C/N magnetic mesoporous composite material and preparation method and application thereof. Firstly, preparing MOF by using dicarbonyl cyclopentadienyl iron dimer as a metal source and benzimidazole-5, 6-dicarboxylic acid as an organic ligand through a hydrothermal method: fe (hbidc), followed by high temperature calcination to give the carbonized derivative: fe0/Fe3C @ C/N, simple and controllable preparation process and short preparation period. Fe prepared by the method0/Fe3The C @ C/N nitrogen-doped iron-carbon nano composite material has high PS catalytic activity, strong ferromagnetism, easy separation and recovery and recycling, and can be used as a catalytic material in a persulfate environmentThe material has good application prospect.
Description
Technical Field
The invention belongs to the technical field of water pollution control, and particularly relates to a Metal Organic Framework (MOF) derived magnetic mesoporous composite material Fe0/Fe3C @ C/N synthesis and a method for treating organic wastewater by using a persulfate-activated high-grade oxidation system thereof.
Background
Water pollution is a growing global environmental problemThe problem threatens the ecosystem and human survival. How to efficiently remove the organic pollutants which are difficult to degrade in the water and make the sewage become a recyclable water resource is very important. The Advanced Oxidation Technologies (Advanced Oxidation Technologies) based on Persulfate (PS) utilize strong oxidizing free radicals or non-free radical reactive species to degrade pollutants, and have the advantages of high treatment efficiency, rapid reaction, no selectivity, wide pH application range and the like. PS is very stable at normal temperature and pressure and needs to be decomposed by catalytic activation to generate sulfate radical (SO)4 -·) are strongly oxidizing species of the main radical species. SO (SO)4 -Has a high redox potential (E)0The PS system has the advantages of +2.5-3.1V, long half-life period (30-40 mu s), low reaction activity with Natural Organic Matters (NOM) of the water body and the like, so the PS system is widely applied to the elimination of organic pollutants which are difficult to degrade in the water body.
Iron-based metal organic frameworks (Fe-MOFs) have MOF bulk characteristics of flexible synthesis method, adjustable structure and diverse catalytic sites, and simultaneously contain a large amount of accessible Iron active sites to serve as electron donors for activating PS, thus causing great attention of researchers as a novel PS catalytic material. However, Fe-MOFs have the phenomena of coordination dissociation and ligand dissolution in an acidic PS system, and may cause secondary pollution and ecotoxicity effects. In order to avoid the potential environmental risk, the preparation of carbonized derivative products at high temperature of Fe-MOFs to replace MOF bulk activated PS is a key breakthrough for solving the technical problems. The iron-carbon nano mesoporous composite material can be obtained by calcining Fe-MOF at high temperature, and has the following advantages: (1) the highly ordered hierarchical porous structure can provide a large amount of uniformly distributed occupied spaces for Fe active sites, and guest molecules (PS and pollutants) can enter the material through the hierarchical pore passages to fully contact with the Fe sites, so that the high mass transfer efficiency of the reaction is ensured; (2) volatilization of the ligand causes the material to have a defected graphitic carbon structure, and formation of the defects can further improve the catalytic performance of the material. Therefore, it is necessary to develop new Fe-MOFs derivative materials and new technology for treating organic wastewater by activating PS.
In view of the above discussionThe invention discloses a metal organic framework Fe (Hbidc) derivative material Fe0/Fe3C @ C/N, a preparation method thereof and application of activated persulfate to treatment of organic wastewater. By high temperature calcination of the 2D metal organic framework template fe (hbidc), the resulting carbonized product avoids except H in the MOF bulk3In addition to the risk of water environment due to dissolution of bidc ligand, Fe is (1) generated3C and Fe0The composite material shows strong ferromagnetism and remanence capacity due to new magnetic iron phases, and is easy to separate and recover; (2) generating a defective graphite carbon structure doped with nitrogen, and inducing the system to generate singlet oxygen when activating PS: (1O2) Non-radical oxidizing species, with SO4 -The active free radicals are used for oxidizing pollutants in a synergistic manner, so that the treatment effect of the wastewater is enhanced; (3) can circularly activate PS, and can recover catalytic activity through high-temperature calcination after repeated use.
In conclusion, the Fe provided by the invention0/Fe3Compared with the existing Fe-MOFs such as Fe (Hbidc), the C @ C/N activated PS not only solves the technical problems of secondary pollution caused by coordination dissociation and ligand dissolution, but also has unexpected technical effects of being easy to magnetically separate and recycle, being capable of synergistically activating the PS through a non-free radical path to enhance pollutant degradation and the like, and has remarkable progress.
Disclosure of Invention
The invention aims to solve the problems of secondary pollution and ecotoxicity caused by coordination dissociation and ligand dissolution due to insufficient stability of the existing Fe-MOFs in an acidic PS system, and provides Fe-MOF (Fe (Hbidc)) derived Fe for avoiding the potential environmental risk0/Fe3A C @ C/N magnetic mesoporous composite material, a preparation method thereof and a new technology for treating organic wastewater by activating PS. The material is used for degrading pollutants in organic wastewater by catalyzing, activating and oxidizing PS, and has the advantages of strong catalytic activity, recyclability, easy separation and recovery and the like; the wastewater treatment technology has the advantages of high treatment efficiency, rapid reaction, wide pH application range and the like.
The invention is realized by the following technical scheme.
The invention provides Fe derived from MOF0/Fe3The preparation method of the C @ C/N magnetic mesoporous composite material comprises the following steps:
(1) the dicarbonyl cyclopentadienyl iron dimer ([ Fe (Cp)) (CO)2)2]2) And benzimidazole-5, 6-dicarboxylic acid (H)3bidc) is dissolved in a mixed solvent of acetonitrile/water (v/v is 4/3), the mixture is fully stirred for 2 hours at normal temperature to obtain a uniform precursor solution, and the uniform precursor solution is transferred into a hydrothermal reaction kettle with a polytetrafluoroethylene lining;
(2) the reaction kettle carries out hydrothermal reaction at a constant temperature, and then is naturally cooled to room temperature. Washing with methanol and deionized water alternately and repeatedly, and performing suction filtration to obtain a Fe (Hbidc) metal organic framework material;
(3) vacuum drying Fe (Hbidc), and calcining powdered Fe (Hbidc) in inert gas atmosphere at high temperature to obtain carbonized and derived Fe0/Fe3C @ C/N composite material.
Further, said H in step (1)3bidc with [ Fe (Cp)) (CO2)2]2The molar concentration ratio of (A) to (B) is 4: 1.
Further, the acetonitrile and H in the step (1)3The molar ratio of bidc was 154: 1.
Further, the volume ratio of the precursor solution to the hydrothermal reaction kettle in the step (1) is 7/20.
Further, in the step (2), the hydrothermal reaction temperature is 160-220 ℃ and the time is 24 hours.
Further, the inert atmosphere in the step (3) comprises one or more of nitrogen, helium and argon; the heating rate of the calcination is 10 ℃ min-1The calcination temperature is 800 ℃ and the calcination time is 5 h.
The invention also provides Fe0/Fe3Use of C @ C/N as catalyst: the catalyst is used for catalyzing and activating the reaction of persulfate for treating organic wastewater, so that the wastewater is purified.
Further, the persulfate includes sodium persulfate, potassium persulfate, and ammonium persulfate.
Compared with the prior art, the invention has the following advantages:
(1) in conclusion, the Fe provided by the invention0/Fe3C @ C/N activated PS solves the technical problem of secondary pollution caused by coordination dissociation and ligand dissolution compared with the existing Fe-MOFs such as Fe (Hbidc).
(2) The invention provides Fe0/Fe3The C @ C/N material can efficiently catalyze and activate Persulfate (PS), has strong magnetism, and is easy to separate and recover; meanwhile, the catalyst can be recovered through high-temperature calcination, and can be repeatedly regenerated.
(3) The invention provides Fe0/Fe3The method for treating organic wastewater by using C @ C/N activated PS has the advantages of high treatment efficiency, quick reaction and wide application range of initial pH of wastewater, and is suitable for treating various organic wastewater.
Drawings
FIG. 1 shows Fe synthesized by methods 1 and 2 according to the examples of the present invention0/Fe3X-ray diffraction (XRD) pattern of C @ C/N material.
FIG. 2 shows Fe synthesized by methods 1 and 2 according to the examples of the present invention0/Fe3Mossbauer of C @ C/N material
Spectra.
FIG. 3 shows Fe synthesized by methods 1 and 2 according to an embodiment of the present invention0/Fe3Hysteresis curve (B-H curve) of C @ C/N material.
Detailed Description
For a better understanding of the present invention, the present invention is further described below with reference to the following examples and drawings, but the embodiments of the present invention are not limited thereto, and the scope of the present invention as claimed is not limited to the scope shown in the examples.
Sulfonamide antibiotics are a common environmental emerging pollutant, and generally come from human activities such as medical treatment, animal husbandry, aquaculture and the like. Although the discharge concentration is low, the discharge concentration is wide in distribution, difficult to degrade, easy to participate in a water circulation process and enriched and amplified in organisms, so that drug-resistant bacteria and drug-resistant genes are widely spread and spread, and the aquatic ecosystem and human health are threatened. Sulfamethoxazole (SMX) is the most widely used sulfonamide antibiotic and has been classified as the third carcinogen by the world health organization. There is a need to develop an efficient method for treating SMX in wastewater. Therefore, the SMX simulated wastewater is selected as the wastewater to be treated, and the degradation degree of the SMX represents the treatment efficiency of the organic wastewater.
Dicarbonylcyclopentadienyliron dimers ([ Fe (Cp) (CO))2]2) Benzimidazole-5, 6-dicarboxylic acid (H)3bidc), acetonitrile (CH)3CN), sodium Peroxodisulfate (PS), Sulfamethoxazole (SMX), methanol (MeOH) and other chemical reagents were all analytically pure, and the water used was deionized water.
In the present invention, said Fe0/Fe3C @ C/N magnetic mesoporous composite material, as Fe0/Fe3C @ C/N is reused for multiple times, after performance is reduced, the material can recover catalytic activity and be regenerated through the high-temperature calcination in the step (3), namely, the Fe (Hbidc) is subjected to vacuum drying treatment, and then the powdery Fe (Hbidc) is subjected to high-temperature calcination in an inert gas atmosphere, wherein the calcination process parameters are as follows: the heating rate is 10 ℃ min-1The calcination time is 5h after the temperature is raised to 800 ℃.
Example 1
Fe derived from MOF0/Fe3The preparation method 1 of the C @ C/N magnetic mesoporous composite material comprises the following specific operation steps:
(1) 234mg (0.625mmol) of [ Fe (Cp)) (CO2)2]2And 515mg (2.5mmol) of H3bidc is dissolved in 35mL of acetonitrile/water (v/v is 4/3) mixed solvent, the mixture is fully stirred for 2h at normal temperature to obtain uniform precursor solution, and the uniform precursor solution is transferred to a 100mL of polytetrafluoroethylene-lined hydrothermal reaction kettle;
(2) the reaction kettle is subjected to hydrothermal reaction for 24 hours at 160 ℃, and then is naturally cooled to room temperature. Washing with methanol and deionized water alternately and repeatedly, and performing suction filtration to obtain a Fe (Hbidc) metal organic framework material;
(3) the Fe (Hbidc) was dried under vacuum, and then the powdery Fe (Hbidc) was placed in a nitrogen atmosphere at 10 ℃ for min-1At a rate of up to 800 ℃ and calcined at that temperature for 5h to give carbonised derived Fe0/Fe3C @ C/N composite material.
Fe0/Fe3The application of the C @ C/N magnetic mesoporous composite material comprises the following steps: fe prepared as in example 10/Fe3C @ C/N is used as a catalyst, PS is used as an oxidant, and four groups of simulated organic wastewater with the initial SMX concentration of 10mg/L are prepared. Without adjusting the pH of the wastewater, four treatment groups were set, which were: (1) adding only 47.6 mg. L-1PS; (2) adding only 0.4 g.L-1Fe0/Fe3C @ C/N; (3) 0.4 g.L of-1Catalyst Fe0/Fe3C @ C/N and 47.6 mg. L-1An oxidant PS; (4) 0.4 g.L of-1Fe (Hbidc) obtained in step (2) and 47.6 mg. L-1An oxidant PS. The four groups of reaction solutions were added to the wastewater in sequence, stirred at room temperature to effect uniform reaction, samples were taken at regular intervals, and the residual concentration value of SMX in the wastewater was measured by High Performance Liquid Chromatography (HPLC) and converted into the removal rate, and the results are shown in table 1.
TABLE 1
Table 1 results show that Fe alone0/Fe3C @ C/N has a weak adsorption effect on SMX in wastewater (treatment group 2), which is made of Fe0/Fe3The mesoporous structure of the C @ C/N composite material; PS oxidation alone (treatment group 1) did not provide effective removal of SMX from wastewater; when Fe0/Fe3C @ C/N is present with PS (treatment group 3), due to Fe0/Fe3C @ C/N has an effective activation effect on PS, and the PS is decomposed to generate strong oxidizing species, so that the target pollutant SMX is effectively subjected to oxidative degradation. The SMX removal rate reaches 99.5 percent after 180min of reaction, and the wastewater is effectively purified. Compared with Fe (Hbidc) which is not carbonized at high temperature and directly activates PS to degrade SMX, the carbonized Fe0/Fe3The effect of degrading SMX by activating PS by C @ C/N is obviously and greatly improved.
Example 2
Fe derived from MOF0/Fe3The difference between the preparation method 2 of the C @ C/N magnetic mesoporous composite material and the embodiment 1 is that the reaction kettle in the step (1) is placed at 220 ℃ for hydrothermal reaction. The other steps are in accordance with the method of example 1.
Fe0/Fe3The application of the C @ C/N magnetic mesoporous composite material comprises the following steps: preparing simulated organic wastewater with initial SMX concentration of 10mg/L, and adding 0.4 g.L into the wastewater-1Fe prepared in example 20/Fe3C @ C/N and 47.6 mg. L-1Oxidizing agent PS is stirred at room temperature to enable the reaction to be uniform, samples are taken when the reactions are respectively carried out for 5min, 10 min, 20 min, 30 min, 45min, 60min, 90 min, 120 min and 180min, and residual concentration values of SMX in wastewater are measured by HPLC, and the residual concentration values are respectively converted into removal rates: 37.9%, 63.0%, 84.3%, 92.1%, 95.8%, 96.9%, 97.5%, 97.8%, 98.1%. The wastewater treatment efficiency was comparable to that of example 1, and it was found that Fe prepared in example 2 and example 10/Fe3The catalytic activation performance of C @ C/N to PS is consistent.
Example 3
A preparation method of an MOF-derived Fe0/Fe3C @ C/N magnetic mesoporous composite material, in example 3, is different from the method 1 in that a reaction kettle in the step (1) is placed at 200 ℃ for hydrothermal reaction. The other steps are in accordance with preparation method 1.
Fe0The difference between the application of the/Fe 3C @ C/N magnetic mesoporous composite material and the application of the magnetic mesoporous composite material in the example 2 is that the catalyst is Fe prepared in the example 30/Fe3C @ C/N, the other steps are identical to those in example 2. After the wastewater treatment reaction was started, samples were taken at 5, 10, 20, 30, 45, 60, 90, 120, and 180min, respectively, and the remaining concentration values of SMX in the wastewater were measured by HPLC, and the removal rates were calculated as: 40.0%, 58.7%, 79.7%, 89.6%, 95.6%, 97.4%, 98.4%, 98.6%, 98.8%. The wastewater treatment efficiency was comparable to that of examples 1 and 2, and it was found that examples 3 and 1,2 preparation of Fe0/Fe3The catalytic activation performance of C @ C/N to PS is consistent.
Example 4
Fe0/Fe3The difference between the application of the C @ C/N magnetic mesoporous composite material and the application of the C @ C/N magnetic mesoporous composite material in the embodiment 2 is that the catalyst is Fe prepared in the embodiment 10/Fe3C @ C/N, the other steps are identical to those in example 2. After the wastewater treatment reaction starts, samples are taken at intervals, and the residual concentration value of PS and the residual concentration value of TOC in wastewater are respectively measured by a potassium iodide (KI) spectrophotometry and a Total Organic Carbon (TOC) analyzer and are respectively converted into a utilization rate and a removal rate, and the results are shown in Table 2.
TABLE 2
Table 2 shows Fe prepared in example 10/Fe3C @ C/N activates PS to treat an SMC system, and the concentration of residual PS and residual TOC in wastewater changes along with the reaction time. From the results, it was found that when the SMX removal rate was 99.5% after 180min of the reaction (table 1), the PS utilization rate reached 94.7%, and the TOC (total organic matter content in the reaction wastewater) removal rate reached 60.7%; after 360min of reaction, the TOC removal rate is as high as 76.2%. The results show that the oxidation system has high utilization rate of the oxidant PS and strong oxidation removal capacity on total organic matters (including SMX precursors and degradation products) of the wastewater. In the PS system, when the catalyst is unstable and organic components are eluted, TOC of the wastewater rises after a certain reaction time. The effective TOC removal of this example reflects the Fe provided by the present invention0/Fe3C @ C/N activates PS, and the problem of secondary pollution caused by dissolution of organic components of the catalyst does not exist. Thus, Fe0/Fe3C @ C/N has good stability in a PS system.
Example 5
Fe0/Fe3The application of the C @ C/N magnetic mesoporous composite material comprises the following steps: preparing five groups of simulated organic wastewater with initial SMX concentration of 10mg/L, and adding 47.6 mg.L into each group of wastewater-1After the oxidizing agent PS was added, the initial pH of the wastewater was adjusted to 3 (treatment group 1), 5 (treatment group 2), 7 (treatment group 3), 9 (treatment group 4) and 11 (treatment group 5), respectively, and then 0.4 g.L was added to each of the wastewater-1Fe prepared in example 10/Fe3C @ C/N catalyst, stirring at room temperature to make the reaction uniform, sampling at intervals, measuring the residual concentration value of SMX in the wastewater, and converting into the removal rate, and the result is shown in Table 3.
TABLE 3
As can be seen from Table 3, when the initial pH value of the wastewater is gradually increased within the range of 3-11, the treatment time required for the SMX removal efficiency of 5 treatment groups to reach 98% is 45min, 60min and 180min respectively, which indicates that the rate of oxidation of the SMX by the system is not changed greatly when the initial pH value is changed within the range of 3-9; when the oxidation temperature is changed within the range of 9-11, the oxidation rate of SMX is reduced. However, the degradation efficiency of the SMX can reach more than 98 percent after the reaction is carried out for 180 min. The oxidation system provided by the invention has a wide application range to the pH value of the wastewater, and can treat the organic wastewater with the initial pH value of 3-11.
Example 6
Fe0/Fe3The application of the C @ C/N magnetic mesoporous composite material comprises the following steps: preparing SMX simulated wastewater with initial concentration of 10mg/L, and sequentially adding 238 mg/L into the wastewater-1Oxidant PS and catalyst Fe prepared in example 20/Fe3C @ C/N, stirring at room temperature to enable the reaction to be uniform without adjusting the initial pH of the wastewater, and sampling at intervals. After the reaction is finished, separating and recovering the catalyst by using a magnetAdding the same new reaction system (containing 238 mg. L)-1Oxidant PS, SMX simulated wastewater with initial concentration of 10 mg/L) was reused, and this was circulated 5 times. Then the Fe after five times of circulation0/Fe3C @ C/N the high temperature calcination was carried out as described in step (3) of example 1. Calcining the cooled Fe0/Fe3And C @ C/N is added into a new reaction system again. Thus, six treatment groups were set, with treatment groups 1 to 5 being catalyst recycling and treatment group 6 being regenerated catalyst. Samples were taken at the same sampling time points in each reaction cycle, and the residual concentration values of SMX in the wastewater were measured and converted into removal rates, and the results are shown in Table 4.
TABLE 4
As can be seen from Table 4, Fe0/Fe3C @ C/N shows relatively stable repeated recycling characteristics, when PS (polystyrene) is circularly activated in the 5 th period, SMX simulated wastewater is treated by adopting the system, the degradation efficiency of the SMX can reach more than 95% after the SMX reacts for 60min, and the result shows that Fe0/Fe3The recycling property of C @ C/N is better. Fe after 5 times of repeated use0/Fe3C @ C/N is calcined at the high temperature of 800 ℃ and Fe0/Fe3The efficiency of SMX treatment by C @ C/N activated PS is restored to the initial level, which indicates that the Fe after use is treated0/Fe3C @ C/N is subjected to the high-temperature calcination of preparation method step (3) to enable Fe0/Fe3C @ C/N is regenerated.
Fe prepared in examples 1 and 20/Fe3The XRD characterization test is carried out on C @ C/N, and the result is shown in figure 1. It can be seen that Fe prepared in example 10/Fe3The XRD characteristic diffraction peak of the C @ C/N composite material is more complex and mainly comprises alpha-Fe at the positions of 44.6 degrees and 65 degrees of 2 theta, gamma-Fe at the positions of 43.7 degrees and 49.0 degrees of 2 theta, and gamma-Fe at the positions of 2 theta and 2 thetaFe at 37.7 °, 40.6 °, 43.6 °, 45.9 °, 78.4 ° degrees3C and 2 θ equal to amorphous carbon composition at 26.2 °. The relative intensity of the peak attributed to α -Fe at a 2 θ angle of 44.6 ° of the composite material prepared in example 2 was significantly weakened, and it was found that the α -Fe content was reduced when the composite material prepared in example 2 was used.
Using Mossbauer spectra (57 Fe)
) For Fe0/Fe3C @ C/N is characterized, and peak-splitting fitting is carried out on a detection peak on the basis of a Lorentz absorption curve through MossWinn 4.0 software. As shown in fig. 2. According to homoeoheteroenergetic displacement (delta) value and quaternary moment splitting value (delta E)Q) Judging the phase attribution of the composite material iron element, and analyzing the phase ratio according to the relative absorption area of each sub-spectrum. The material prepared in example 1 contained gamma-Fe, alpha-Fe, Fe3C、Fe3C、Fe3+The relative absorption area ratio of the five types of iron with different occupancy is 6: 21: 44: 22: 7, which shows that 27% (mass percent) of the crystalline iron substance phase is zero-valent iron and 66% of the crystalline iron substance phase is iron carbide. Similarly, the material prepared in example 2 contained α -Fe, Fe3C、Fe3C、Fe3+The relative absorption area ratio of the four different occupied irons is 11: 26: 53: 10, which shows that the composite material contains 11% of zero-valent iron and 79% of iron carbide, and the results are consistent with the results of XRD analysis. Thus, Fe0/Fe3C @ C/N contains mainly Fe0And Fe3C two kinds of crystalline iron, the ratio of the two kinds of crystalline iron changes with the change of the hydrothermal reaction temperature of Fe (Hbidc) in the step (2), but Fe3C is always the main crystalline iron phase. After the material prepared in example 2 is recycled for 5 times, the material is subjected to high-temperature heat treatment in the step (3), the spectrogram of the treated material has no obvious difference from the initial spectrogram, and the contents of two kinds of crystalline iron have no obvious change, which shows that Fe0/Fe3C @ C/N is regenerated in the step (3), and the catalytic activity is recovered.
Subjecting the composite to N2Adsorption and desorption test to obtain Fe0/Fe3C @ C/N is a mesoporous material. Examples1 specific surface area (BET), Total pore volume (V) of the composite preparedp) And the diameter of the hole (d)p) Are 189.72m respectively2·g、0.2cm3G and 4.24 nm; composite (BET), Total pore volume (V) prepared in example 2p) And the diameter of the hole (d)p) Are respectively 181.67m2·g、0.24cm3G and 5.2 nm, it can be seen that changes in hydrothermal temperature do not have much effect on the specific surface area and pore structure of the material. By inductively coupled plasma atomic absorption spectroscopy (ICP-OES) and Elemental Analysis (EA), the composite material provided in example 1 was composed of five elements, carbon (C), hydrogen (H), oxygen (O), nitrogen (N), and iron (Fe), with percentage contents of each element being 64.9, 0.4, 3.0, 1.3, and 30.4, respectively; example 2 provides composite C, H, O, N, Fe with element percentages of 70.2, 0.3, 4.0, 0.9, and 24.6, respectively. Therefore, the percentage of each element in the composite material also changes with the change of the hydrothermal reaction temperature of Fe (Hbidc) in the step (2). In addition, the composite material is Fe doped with nitrogen (N)0/Fe3C carbon material, hence the name Fe0/Fe3C@C/N。
Fe at room temperature was measured by Vibrating Sample Magnetometer (VSM)0/Fe3The variation curve (B-H curve) of C @ C/N magnetic induction (B) with magnetic field strength (H) is shown in FIG. 3. Reading the saturation magnetization (M) of the sample according to a hysteresis curveS) Coercive force (H)C) And residual magnetization (M)r) The value is obtained. From the results, it is found that the B-H curve of the material is a typical S-type hysteresis curve. Composite material M prepared in example 1S、MrAnd HCValues of 55.5Am respectively2/Kg、13.0Am2/Kg and 49.6 mT; example 2 composite material Ms、MrAnd HCThe values are respectively 43.0Am2/Kg、 7.0Am2/Kg and 41.8 mT. This confirmed the Fe content of the composite material prepared in example 2 in the Mossbauer spectrum detection results3The C content is higher than in example 1. Due to Fe3The hyperfine magnetic field intensity of C is weaker than that of alpha-Fe, so that the higher the content of the alpha-Fe in the composite material is, the stronger the magnetic induction intensity is. In combination with the above analysis, the present invention provides Fe0/Fe3C @ C/N catalystHas strong ferromagnetism and remanence capacity, and is easy to be magnetically separated and recycled when the PS is activated to treat wastewater.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. Fe0/Fe3The C @ C/N magnetic mesoporous composite material is an N-doped iron-carbon composite and is characterized in that: is composed of C, H, O, N, Fe five elements, and contains Fe3Two crystalline iron phases of C and Fe.
2. Fe of claim 10/Fe3The C @ C/N magnetic mesoporous composite material is characterized in that: containing Fe3The contents of two crystalline iron phases of C and Fe are respectively 66-79% and 11-27%; saturation magnetization (M) of composite materialsS) And residual magnetization (M)r) Are respectively 43 to 55.5Am2(iv)/Kg and 7 to 13Am2/Kg。
3. Fe derived from MOF0/Fe3The preparation method of the C @ C/N magnetic mesoporous composite material is characterized by comprising the following steps of:
step (1) Dicarbonylcyclopentadienyl iron dimer ([ Fe (Cp)) (CO)2)2]2) And benzimidazole-5, 6-dicarboxylic acid (H)3bidc) is dissolved in a mixed solvent of acetonitrile/water (v/v is 4/3), the mixture is fully stirred for 2 hours at normal temperature to obtain a uniform precursor solution, and the uniform precursor solution is transferred into a hydrothermal reaction kettle with a polytetrafluoroethylene lining;
carrying out hydrothermal reaction on the reaction kettle in the step (2) at a constant temperature, naturally cooling to room temperature, alternately and repeatedly washing with methanol and deionized water, and carrying out suction filtration to obtain a Fe (Hbidc) metal organic framework material;
step (3) of vacuum-drying Fe (Hbidc), and then drying the powderPlacing Fe (Hbidc) in an inert gas atmosphere for high-temperature calcination to obtain carbonized and derived Fe0/Fe3C @ C/N composite material.
4. A MOF-derived Fe according to claim 30/Fe3The preparation method of the C @ C/N magnetic mesoporous composite material is characterized by comprising the following steps of (1): said H3bidc with [ Fe (Cp)) (CO2)2]2The molar concentration ratio of (A) to (B) is 4: 1; the acetonitrile and H3The molar concentration ratio of bidc is 154: 1; the volume ratio of the precursor solution to the hydrothermal reaction kettle is 7/20.
5. A MOF-derived Fe according to claim 30/Fe3The preparation method of the C @ C/N magnetic mesoporous composite material is characterized in that the step (2) is as follows: the hydrothermal reaction temperature is 160-220 ℃, and the reaction time is 24 h.
6. A MOF-derived Fe according to claim 30/Fe3The preparation method of the C @ C/N magnetic mesoporous composite material is characterized in that the step (3) is as follows: the inert atmosphere comprises one or more of nitrogen, helium and argon; the calcination process parameters are as follows: the heating rate is 10 ℃ min-1The calcination time is 5 hours after the temperature is raised to 800 ℃, and then the temperature is naturally reduced to the room temperature.
7. Fe as claimed in claim 10/Fe3The application of the C @ C/N magnetic mesoporous composite material is characterized in that the C @ C/N magnetic mesoporous composite material is used for catalytically activating persulfate to oxidize and degrade pollutants in organic wastewater so as to purify the wastewater; the persulfate comprises sodium persulfate, potassium persulfate and ammonium persulfate.
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