CN112844320A - Carbon material-coated spinel iron oxide in-situ growth MOFs adsorption catalysis complex and preparation method and application thereof - Google Patents
Carbon material-coated spinel iron oxide in-situ growth MOFs adsorption catalysis complex and preparation method and application thereof Download PDFInfo
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 115
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 102
- 239000011029 spinel Substances 0.000 title claims abstract description 102
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 63
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 56
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 47
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000010668 complexation reaction Methods 0.000 title description 2
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 42
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 34
- 239000012498 ultrapure water Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000013110 organic ligand Substances 0.000 claims abstract description 24
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 20
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- VEQOALNAAJBPNY-UHFFFAOYSA-N antipyrine Chemical compound CN1C(C)=CC(=O)N1C1=CC=CC=C1 VEQOALNAAJBPNY-UHFFFAOYSA-N 0.000 description 12
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- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
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- 238000000576 coating method Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- DXKGMXNZSJMWAF-UHFFFAOYSA-N copper;oxido(oxo)iron Chemical compound [Cu+2].[O-][Fe]=O.[O-][Fe]=O DXKGMXNZSJMWAF-UHFFFAOYSA-N 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
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- 239000013500 performance material Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
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- 150000003624 transition metals Chemical class 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 239000003403 water pollutant Substances 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Abstract
The invention discloses a carbon material-coated spinel iron oxide in-situ growth MOFs adsorption catalysis complex, a preparation method thereof and application thereof in water treatment catalysis, wherein the preparation method comprises the following steps: 1) preparing magnetic nano material, 2) mixing the nano spinel ferrite obtained in the step 1) with carbon material and ultrapure water to a certain extentProportional preparation of carbon material-coated magnetic spinel iron oxide TFe2O4(ii) a 3) Magnetic TFe wrapping the carbon material obtained in the step 2)2O4Preparing a magnetic carbon material wrapped by the carbon material with an organic ligand and ultrapure water according to a certain proportion to grow the MOFs material in situ, namely preparing the carbon material wrapped spinel iron oxide TFe2O4And growing the MOFs adsorption catalytic complex in situ. The complex preparation process disclosed by the invention is simple to operate, rich in raw material source, low in manufacturing cost, strong in magnetic recovery capacity and excellent in regeneration performance, and can be used for efficiently adsorbing and removing heavy metals and trace organic matters in water.
Description
Technical Field
The invention belongs to the field of water environment combined pollution treatment, and relates to carbon material coated spinel iron oxide (TFe)2O4) An in-situ growth MOFs adsorption catalysis complex, a preparation method thereof and application thereof in water treatment and catalysis.
Background
China is a country with water resource shortage, and the 13 th rank is the arid water shortage in the regions occupying more than 50% of the land area in the world. Due to the pollution of water environment, the limited water resource in China is in short supply. Due to the high-speed development of economy, the national economy has gone through the development process of developed countries for decades in as short as 20 years, but simultaneously China has also generated a special composite pollution problem. The composite pollution of the water environment is characterized in that the water pollution problem of developed countries in different periods is intensively exploded in short term in China, and the release of pollutants in a point source, a surface source, rainfall and bottom mud forms time and space composite for water body pollution: the coexistence of organic matter, nitrogen, phosphorus and other nutrients, refractory organic matter, heavy metal and other toxic matters forms the composite pollution of water environment. Therefore, it is required to develop a new material with high efficiency for removing pollutants to be applied to the field of water pollutant treatment.
Metal-Organic Frameworks (MOFs), which are Organic-inorganic hybrid materials with intramolecular pores formed by self-assembly of Organic ligands and Metal ions or clusters through coordination bonds. MOFs are composed of metal centers and organic ligands that self-assemble through coordination bonds to form an almost infinite crystal network. In addition, MOFs also have ultra-high surface area, thermal and mechanical stability, large pore volume, excellent host-guest chemistry and adaptability functions, which exhibit excellent performance in adsorption, catalysis, gas storage and separation. The practical application of MOFs is limited by the disadvantage that it is difficult to separate it from large amounts of reaction solutions.
TFe2O4Is a magnetic mixed metal oxide (wherein T is a transition metal element) with sulfate radical, H2O2The ferrite material has a large specific surface area and a large number of active sites, so that the ferrite material has strong water purification capacity, and plays an important role in the adsorption and degradation of water treatment. And TFe2O4The metal ions in the catalyst can be used as metal centers of MIL-100(Fe), and the catalyst synthesized by hydrothermal reaction has persulfate catalytic performance and magnetic material without adding extra metal ions as metal centers of MOF materials. However, TFe2O4The high surface area and unique magnetism of the material cause the material to easily aggregate in practical application, and influence the catalytic efficiency. Therefore, some highly conductive carbonaceous materials are used as the TFe2O4The active sites are uniformly distributed on the substrate, and the catalytic performance is improved.
The magnetized MIL-100(Fe) material with a core-shell structure is an attractive functionalized MOFs material, and the MOFs material and the TFe are combined2O4And the carbon material has the advantages of high active site, magnetism and high specific surface area, and can be widely applied to a water pollution treatment system.
Disclosure of Invention
One of the technical problems to be solved by the invention is that MOF materials are difficult to separate in solution in the prior art, and aiming at the technical problem, the invention provides a method which is simple in process operation, rich in raw material source, low in manufacturing cost, strong in magnetic recovery capability, excellent in regeneration performance, and capable of efficiently adsorbing and removing heavy metals and organic matters in water (or capable of efficiently adsorbing and removing heavy metals and organic matters in water)Removing trace organic matters in water) carbon material coated spinel iron oxide TFe2O4In-situ growth MOFs adsorption catalysis complex and a preparation method and application thereof. The complex has the advantages of easy separation and high catalytic activity, and the invention adopts CuFe2O4As the metal active center, the trouble caused by adding foreign metal ions for secondary pollution is correspondingly avoided.
In order to achieve the purpose, the invention adopts the following technical scheme:
carbon material coated spinel iron oxide TFe2O4The preparation method of the in-situ grown MOFs adsorption catalysis complex is characterized by comprising the following steps:
1) preparing a magnetic nano material, wherein the magnetic nano material is nano spinel ferrite synthesized by a synthesis method or purchased;
2) preparing the nano spinel ferrite obtained in the step 1), a carbon material and ultrapure water into magnetic spinel iron oxide TFe wrapped by the carbon material according to a certain proportion2O4；
Wherein T is a transition metal element;
further, the T is one or more of Cu, Co, Mn, Zn and Ni;
furthermore, T is one or more of Cu, Co and Mn;
3) magnetic spinel iron oxide TFe coated by the carbon material obtained in the step 2)2O4Preparing a magnetic carbon material wrapped by the carbon material with an organic ligand and ultrapure water according to a certain proportion to grow the MOFs material in situ, namely preparing the carbon material wrapped spinel iron oxide TFe2O4Growing MOFs adsorption catalysis complex in situ;
further, the magnetic nano material is nano spinel ferrite synthesized by a hydrothermal synthesis method.
Further, as a preferred technical scheme, the preparation method comprises the following steps:
1) preparing nano spinel ferrite: mixing T with a molar ratio of 1:22+/Fe3+(2.5mM-10mM) NH for solution4Adjusting the pH value to be more than 10 by OH, heating and stirring for more than 1h in water bath at 70-100 ℃, keeping the pH value of the solution to be more than 10 in the heating process, collecting magnetic black precipitates by using a magnet after the reaction is finished, respectively washing the precipitates for 3-4 times by using ethanol and ultrapure water, and collecting a product, namely the nano spinel ferrite;
2) mixing the nano spinel ferrite prepared in the step 1) with a carbon material in ultrapure water, and reacting the mixed solution in a constant-temperature magnetic stirrer at room temperature and at the rotating speed of 20-40 rpm for not less than 1h to obtain the carbon material-coated magnetic spinel iron oxide TFe2O4(ii) a Wherein the mass ratio of the nano spinel ferrite to the carbon material is (4-10): (0-1), wherein the mass ratio of the solid (nano spinel ferrite and carbon material) to the ultrapure water is (3-6): 200-300).
3) The carbon material prepared in the step 2) is wrapped by magnetic spinel iron oxide TFe2O4Mixing with organic ligand and ultrapure water, stirring at normal temperature and performing ultrasonic treatment for at least 1h to obtain uniform suspension, transferring the uniform suspension into a polytetrafluoroethylene reaction kettle, reacting at 90-150 ℃ for a period of time, transferring the reacted product into a small beaker, washing with ultrapure water and ethanol respectively, centrifuging, and drying to obtain a product, namely the carbon material-coated spinel iron oxide TFe2O4Growing MOFs adsorption catalysis complex in situ;
wherein the carbon material coated magnetic spinel iron oxide TFe2O4: organic ligand: the mass ratio of the ultrapure water is (2-4): (1-2): (200-);
further, the reaction time of the uniform suspension liquid after being transferred into a polytetrafluoroethylene reaction kettle is more than 10 hours; preferably over 12 h;
further, the drying temperature is above 40 ℃; preferably 55-65 ℃, and further preferably 60 ℃;
further, the drying time is more than 5 hours; preferably more than 8 h; further preferably 8 to 10 hours.
The nano spinel ferrite: the mass ratio of the carbon material is (5-10): 1.
further, the carbon material is a combination of one or more of multi-walled carbon nanotubes, graphene/graphene oxide, biochar.
Preferably, the nano spinel ferrite has a particle size of 20 to 50 nm;
further, the specific surface area of the carbon material is 50 to 300m 2/g;
further, when the carbonized material is a multi-wall carbon nanotube, the specific surface area of the multi-wall carbon nanotube is 80-250m2/g, and the pore volume is 0.4-1.2cm 3/g;
further, the carbon material is graphene oxide.
The organic ligand can be aliphatic carboxylic acid, aromatic carboxylic acid and nitrogen heterocyclic carboxylic acid substances; such as tartaric acid, benzoic acid, trimesic acid, and the like.
Further, the organic ligand is trimesic acid (H)3BTC)；
Further, the carbon material wraps spinel iron oxide TFe2O4In-situ growth MOFs are adsorbed in the catalytic composite body, and the in-situ growth MOFs are grown on ferrite wrapped by carbon materials.
The invention also discloses the carbon material coated spinel iron oxide TFe prepared by the preparation method2O4And growing the MOFs adsorption catalytic complex in situ.
Further, the carbon material wraps spinel iron oxide TFe2O4The size of the in-situ grown MOFs adsorption catalysis complex is 10-100nm, and the saturation magnetization is 15-35 emu/g.
The invention also discloses the carbon material coated spinel iron oxide TFe2O4The application of the in-situ grown MOFs adsorption catalysis complex in preparation of water treatment adsorbents and/or water treatment filter column filling materials.
The invention also discloses the carbon material coated spinel iron oxide TFe2O4In-situ growth of MOFs adsorption catalysis complex in catalysis of PMS, PDS and H2O2、FeO4 2-And FeO4 2-/H2O2Degrading organic substancesAnd (4) application in the aspect of pollutants.
The invention has the advantages that:
1. the invention provides carbon material coated spinel iron oxide TFe2O4A preparation method of an in-situ grown MOFs adsorption-catalysis complex, an adsorption-catalysis complex and application thereof. The magnetic nano material, the carbonized material, the MOFs and the like are selected to prepare the adsorption catalyst which is most suitable for emerging organic pollutants, and the composite pollutant which is harmful greatly, long in environmental persistence and difficult to degrade is particularly suitable for the composite pollutant. The preparation method is simple, the raw material source is rich, the composite adsorption catalysis composite material can be directly generated in situ through hydrothermal synthesis and the like, and the adsorption and catalysis performance is excellent.
2. The carbon material prepared by the invention is used for coating spinel iron oxide (TFe)2O4) In-situ growth MOFs composite material for catalyzing PMS, PDS and H2O2、FeO4 2-And FeO4 2-/H2O2The application of advanced oxidation technology in degrading emerging organic pollutants has high degradation rate, the removal rate can reach 99 percent, the removal rate can reach 99.4 percent within 10min, the removal rate can reach 99.7 percent within 30min, the removal rate of organic trace can reach 99.3 percent, and the effect is still not influenced when heavy metal and organic matters are removed simultaneously.
3. The carbon material provided by the invention wraps spinel iron oxide TFe2O4The preparation method of the in-situ growth MOFs adsorption catalysis complex has the advantages of simple process operation, rich raw material sources and low manufacturing cost; the composite adsorbent has strong magnetic recovery capability and excellent regeneration performance (the composite adsorbent is continuously used for more than 10 times, methanol or water is eluted and recycled again, and the content of the organic pollutants in water can also reach more than 95 percent), and can efficiently catalyze and remove the organic pollutants in water.
4. The carbon material prepared by the invention wraps spinel iron oxide TFe2O4The in-situ grown MOFs adsorption catalysis complex has rich acid-base active sites, and can well catalyze the PMS advanced oxidation technology to generate free radicals to mineralize new organic pollutants in water under a wide pH value.
5. According to the invention, the spinel ferrite nano material synthesized by a hydrothermal method is used for modifying and modifying MIL-100(Fe), so that the magnetic recovery capability of the material is improved, and meanwhile, the dosage of the magnetic nano material can be accurately controlled according to the application environment.
6. The carbon material coated spinel iron oxide TFe prepared by the invention2O4The reusability, stability, magnetic recovery performance and catalytic performance of the in-situ grown MOFs adsorption catalytic complex are obviously improved, the novel pollutants can be efficiently degraded, and the application range is wide.
Drawings
FIG. 1 shows spinel iron oxide (CuFe) coated with carbon material according to the present invention2O4) XRD pattern of the adsorption catalytic complex of MOFs grown in situ.
Detailed Description
The present invention is further illustrated by the following specific examples, it should be noted that, for those skilled in the art, variations and modifications can be made without departing from the principle of the present invention, and these should also be construed as falling within the scope of the present invention.
Carbon material coated spinel iron oxide TFe2O4The preparation method of the in-situ grown MOFs adsorption catalysis complex is characterized by comprising the following steps:
1) preparing a magnetic nano material, wherein the magnetic nano material is nano spinel ferrite synthesized by a synthesis method or purchased;
in some embodiments, as a preferred technical solution, the magnetic nanomaterial is spinel ferrite synthesized by a hydrothermal synthesis method.
2) Preparing the nano spinel ferrite obtained in the step 1), a carbon material and ultrapure water into magnetic spinel iron oxide TFe wrapped by the carbon material according to a certain proportion2O4；
Wherein T is a transition metal element;
in some embodiments, T is one or more of Cu, Co, Mn, Zn, Ni;
as a preferred embodiment, T is one or more of Cu, Co and Mn;
3) magnetic spinel iron oxide TFe coated by the carbon material obtained in the step 2)2O4Preparing a magnetic carbon material wrapped by the carbon material with an organic ligand and ultrapure water according to a certain proportion to grow the MOFs material in situ, namely preparing the carbon material wrapped spinel iron oxide TFe2O4Growing MOFs adsorption catalysis complex in situ;
in some embodiments, the above preparation method comprises the steps of:
1) preparing nano spinel ferrite: mixing T with a molar ratio of 1:22+/Fe3+(2.5mM-10mM) NH for solution4Adjusting the pH value to be more than 10 by OH, heating and stirring for more than 1h in water bath at 70-100 ℃, keeping the pH value of the solution to be more than 10 in the heating process, collecting magnetic black precipitates by using a magnet after the reaction is finished, respectively washing the precipitates for 3-4 times by using ethanol and ultrapure water, and collecting a product, namely the nano spinel ferrite;
2) mixing the nano spinel ferrite prepared in the step 1) with a carbon material in ultrapure water, and reacting the mixed solution in a constant-temperature magnetic stirrer at room temperature and at the rotating speed of 20-40 rpm for not less than 1h to obtain the carbon material-coated magnetic TFe2O4(ii) a Wherein the mass ratio of the nano spinel ferrite to the carbon material is (4-10): (0-1), wherein the mass ratio of the solid (nano spinel ferrite and carbon material) to the ultrapure water is (3-6): 200-300).
In some embodiments, the nano spinel ferrite: the mass ratio of the carbon material is (5-10): 1.
3) the carbon material prepared in the step 2) is wrapped by magnetic spinel iron oxide TFe2O4Mixing with organic ligand and ultrapure water, stirring at normal temperature and performing ultrasonic treatment for at least 1h to obtain uniform suspension, transferring the uniform suspension into a polytetrafluoroethylene reaction kettle, reacting at 90-150 ℃ for a period of time, transferring the reacted product into a small beaker, washing with ultrapure water and ethanol respectively, centrifuging, and drying to obtain a product, namely the carbon material-coated spinel iron oxide TFe2O4Growing MOFs adsorption catalysis complex in situ;
wherein the carbon material is coatedMagnetic spinel iron oxide TFe2O4: organic ligand: the mass ratio of the ultrapure water is (2-4): (1-2): (200-);
as a preferred embodiment, the reaction time of the uniform suspension after being transferred into a polytetrafluoroethylene reaction kettle is more than 10 hours; the reaction time is more than 12 hours for obtaining better effect;
in some embodiments, the drying temperature is above 40 ℃; preferably 55-65 ℃, and further preferably 60 ℃;
in some embodiments, the drying time is 5 hours or more; preferably more than 8 h; further preferably 8 to 10 hours.
As a preferred embodiment, the carbon material of the present invention is a combination of one or more of multi-walled carbon nanotubes, graphene/graphene oxide, and biochar.
In some embodiments, as a preferred technical solution, the particle size of the magnetic nano material is 20-50 nm;
in some embodiments, as a preferred aspect, the carbon material has a specific surface area of 50 to 300m 2/g;
in some embodiments, when the carbonized material is multi-walled carbon nanotubes, the specific surface area of the multi-walled carbon nanotubes is 80-250m2Per g, pore volume of 0.4-1.2cm3/g；
In some embodiments, the carbon material is graphene oxide.
In some embodiments, the organic ligand can be an aliphatic carboxylic acid, an aromatic carboxylic acid, and an azaheterocyclic carboxylic acid; such as aliphatic carboxylic acids, aromatic carboxylic acids, and azaheterocyclic carboxylic acids; such as tartaric acid, benzoic acid, trimesic acid, and the like.
As a preferred embodiment, the organic ligand may be trimesic acid (H)3BTC)；
Further, the carbon material wraps spinel iron oxide TFe2O4In-situ growth MOFs are adsorbed in the catalytic composite body, and the in-situ growth MOFs are grown on ferrite wrapped by carbon materials.
The invention also discloses the carbon material coated spinel iron oxide TFe prepared by the preparation method2O4And growing the MOFs adsorption catalytic complex in situ.
In some embodiments, the resulting carbon material coated spinel iron oxide TFe is prepared2O4The size of the in-situ grown MOFs adsorption catalysis complex is 100-100nm, and the saturation magnetization is 15-35 emu/g.
The invention also discloses the carbon material coated spinel iron oxide TFe2O4The application of the in-situ grown MOFs adsorption catalysis complex in preparation of water treatment adsorbents and/or water treatment filter column filling materials.
The carbon material wraps spinel iron oxide TFe2O4The MOFs adsorption catalysis complex growing in situ can be applied to water treatment adsorbents and filling materials of water treatment filter columns in the prior art, and is not limited here.
For example, in a filter column, there are three ABA layers, a layer of sandstone (e.g., 1cm thick to prevent filler loss) and a layer of B (e.g., 5cm thick) of carbon material-coated spinel iron oxide TFe of the present invention2O4The MOFs adsorption catalysis complex grows in situ, and the sewage to be treated sequentially passes through the ABA layer, so that adsorption filtration can be completed.
The invention also discloses the carbon material coated spinel iron oxide TFe2O4In-situ growth of MOFs adsorption catalysis complex in catalysis of PMS, PDS and H2O2、FeO4 2-And FeO4 2-/H2O2Application in degrading organic pollutant. The following examples are illustrative, but not limiting.
The present invention will be described with reference to specific examples, but the following examples do not limit the scope of the present invention.
Example 1
Carbon material coated spinel iron oxide TFe2O4In-situ growth of MOFs adsorption catalytic complex (CuFe)2O4@ GO @ MIL-100(Fe), the transition metal is copper, the carbon material is graphene oxide, and the organic ligand is trimesic acid):
1) preparing nano spinel ferrite: mixing 3mMCu2+/Fe3+(molar ratio 1:2) NH for solution4Adjusting pH to above 10 with OH, heating in water bath at 90 deg.C for 90min while stirring, maintaining pH of the solution above 10, collecting magnetic black precipitate with magnet after reaction, cleaning with ethanol and ultrapure water for 3-4 times, and collecting the product, i.e. nano spinel ferrite CuFe2O4(ii) a Wherein the iron nitrate (nonahydrate), Cu2+From copper nitrate (trihydrate).
2) Mixing the nano spinel ferrite prepared in the step 1) with a carbon material (GO and graphene oxide are selected in the embodiment) in ultrapure water, and reacting the mixed solution in a constant-temperature magnetic stirrer at room temperature and at the rotating speed of 30rpm for not less than 1.5h to obtain carbon material-coated magnetic spinel iron oxide TFe2O4(suspension); wherein the nano spinel ferrite: the mass ratio of the carbon material is 16: 1; wherein the mass ratio of the solid (nano spinel ferrite and carbon material) to the ultrapure water is 3: 220.
3) The carbon material prepared in the step 2) is wrapped by magnetic spinel iron oxide TFe2O4Mixing with organic ligand and ultrapure water, and stirring at room temperature for at least 1 h; then transferring the product into a polytetrafluoroethylene reaction kettle, reacting for 12h at 120 ℃, transferring the product after reaction into a small beaker, washing and centrifuging respectively by ultrapure water and ethanol (washing the ultrapure water for 3h at 70 ℃, separating the product by using a magnet, then adding 50mL of ethanol, washing the product for 3h at 65 ℃), drying the product overnight at 60 ℃, and obtaining the product, namely the carbon material coated spinel iron oxide CuFe2O4Growing MOFs adsorption catalysis complex in situ;
wherein the content of the first and second substances,
the organic ligand is trimesic acid (H)3BTC)。
The carbon material coated magnetic spinel iron oxide TFe2O4: organic ligand: the mass ratio of the ultrapure water is 3: 1.5: 250.
example 2
Compared with example 1, the only difference lies in the choice of the carbon material, which is selected to be multi-walled carbon nanotubes, which are commercially available, with a specific surface area of 80-250m2Per g, pore volume of 0.4-1.2cm3/g；
Example 3
Compared with example 1, the only difference lies in the selection of the carbon material, which is selected to be graphene, which is commercially available.
Example 4
The only difference compared to example 1 is the choice of carbon material, which is selected to be biochar, which is commercially available.
Example 5
The only difference compared to example 1 is the choice of the organic ligand, which is benzoic acid.
Example 6
Compared with example 1, the difference is only that the carbon material coated magnetic spinel iron oxide TFe2O4: organic ligand: the mass ratio of the ultrapure water is 2: 1: 200.
example 7
Compared with example 1, the only difference is that the ratio of nano spinel ferrite to carbon material is 6: 1.
through detection, the carbon material obtained in the above examples 1 to 7 wraps the spinel iron oxide CuFe2O4The size and saturation magnetization of the in-situ grown MOFs adsorption catalytic complex are shown in the following Table 1:
TABLE 1
| Serial number | Size (nm)10-100 | Saturation magnetization (emu/g) |
| Example 1 | 47 | 19.9 |
| Example 2 | 35 | 17 |
| Example 3 | 40 | 22 |
| Example 4 | 42 | 20.1 |
| Example 5 | 68 | 19 |
| Example 6 | 45 | 29.3 |
| Example 7 | 82 | 20 |
Application example 1
CuFe prepared in examples 1-72O4The application of @ GO @ MIL-100(Fe) in catalyzing PMS to degrade Antipyrine (ANT) is as follows:
under the conditions of 25 ℃ and pH 7, the volume of the solution is 200mL, the concentration of antipyrine is 10mg/L, and a catalyst (carbon material coated tip) is addedSpar iron oxide CuFe2O4In-situ grown MOFs adsorption-catalysis complex) is 50mg, and the target is removed under the action of a constant temperature oscillator. Antipyrine mainly passes through CuFe2O4@ GO @ MIL-100(Fe) catalyzes PMS to generate sulfate radicals, hydroxyl radicals, singlet oxygen and other radicals, and the radicals are removed through oxidation. After a period of time, the catalyst can be recovered through an external magnetic field, and the catalyst is cleaned through methanol or ethanol and recycled again.
Respectively measuring the concentration of Antipyrine (ANT) in the reaction process by using high performance liquid chromatography, wherein the concentration of the initial point is C0Sampling at 0, 1, 2, 3, 4, 5, 10 and 30min time points to obtain the concentration CtThe formula for calculating the removal rate is (C)0-Ce) Co removal rate is shown in Table 2:
TABLE 2
Application example 2
Compared with application example 1, Antipyrine (ANT) is replaced by sulfamethoxazole, and the application example 1 is otherwise the same. The removal rate is shown in table 3:
TABLE 3
| Time (min) | Sulfamethoxazole concentration (mg/L) | Removal Rate (%) |
| 0 | 10.00 | 0 |
| 1 | 1.03 | 89.7 |
| 2 | 0.73 | 92.7 |
| 3 | 0.58 | 94.2 |
| 4 | 0.42 | 95.8 |
| 5 | 0.39 | 96.1 |
| 10 | 0.29 | 97.1 |
| 30 | 0.14 | 98.6 |
Application example 3
Compared with application example 1, Antipyrine (ANT) is replaced by amitriptyline hydrochloride, and the application example 1 is otherwise the same. The removal rate is shown in table 4:
TABLE 4
| Time (min) | Amitriptyline hydrochloride concentration (mg/L) | Removal Rate (%) |
| 0 | 10.00 | 0 |
| 1 | 0.12 | 98.8 |
| 2 | 0.11 | 98.9 |
| 3 | 0.09 | 99.1 |
| 4 | 0.08 | 99.2 |
| 5 | 0.08 | 99.2 |
| 10 | 0.06 | 99.4 |
| 30 | 0.03 | 99.7 |
Application example 4
The difference from application example 3 was only that the concentration of amitriptyline hydrochloride was 30. mu.g/L, and the other application examples were the same as application example 1. The removal rate is shown in table 5:
TABLE 5
Application example 5
Except that Antipyrine (ANT) was replaced with 10mg/L amitriptyline hydrochloride and 10mg/LPb ion mixture, as in application example 1. The removal rate is shown in table 6:
TABLE 6
| Time (min) | Amitriptyline hydrochloride concentration (mg/L) | Removal Rate (%) | Pb concentration (mg/L) | Removal Rate (%) |
| 0 | 10.00 | 0 | 10.00 | 0 |
| 1 | 0.21 | 97.9 | 0.79 | 92.1 |
| 2 | 0.19 | 98.1 | 0.62 | 93.8 |
| 3 | 0.16 | 98.4 | 0.59 | 94.1 |
| 4 | 0.11 | 98.9 | 0.54 | 94.6 |
| 5 | 0.08 | 99.2 | 0.5 | 95 |
| 10 | 0.07 | 99.3 | 0.41 | 95.9 |
| 30 | 0.05 | 99.5 | 0.39 | 96.1 |
It can be seen from the above table that the removal rate can reach 99% within 1min, 99.4% within 10min, and 99.7% within 30min, while the removal rate of the trace organic matter (application example 4) can reach 99.3%, and the effect is still not affected by removing heavy metals and organic matter.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Variations or modifications in other variations may occur to those skilled in the art based upon the foregoing description. Not all embodiments need be illustrated or described herein. And obvious variations or modifications of this embodiment may be made without departing from the spirit or scope of the invention.
Claims (10)
1. A preparation method of a carbon material-coated spinel iron oxide in-situ grown MOFs adsorption catalysis complex is characterized by comprising the following steps:
1) preparing a magnetic nano material, wherein the magnetic nano material is nano spinel ferrite synthesized by a synthesis method or purchased;
2) preparing the nano spinel ferrite obtained in the step 1), a carbon material and ultrapure water into magnetic spinel iron oxide TFe wrapped by the carbon material according to a certain proportion2O4；
Wherein T is a transition metal element;
further, the T is one or more of Cu, Co, Mn, Zn and Ni;
furthermore, T is one or more of Cu, Co and Mn;
3) magnetic spinel iron oxide TFe coated by the carbon material obtained in the step 2)2O4Preparing a carbon material-coated magnetic carbon material in-situ growth MOFs material with an organic ligand and ultrapure water according to a certain proportion, namely preparing a carbon material-coated spinel iron oxide in-situ growth MOFs adsorption catalysis complex;
further, the magnetic nano material is nano spinel ferrite synthesized by a hydrothermal synthesis method.
2. The method for preparing the carbon material coated spinel iron oxide in-situ growth MOFs adsorption catalysis complex according to claim 1, which is characterized by comprising the following steps:
1) preparing nano spinel ferrite: mixing T with a molar ratio of 1:22+/Fe3+(2.5mM-10mM) NH for solution4Adjusting the pH value to be more than 10 by OH, heating and stirring for more than 1h in water bath at 70-100 ℃, keeping the pH value of the solution to be more than 10 in the heating process, collecting magnetic black precipitates by using a magnet after the reaction is finished, respectively washing the precipitates for 3-4 times by using ethanol and ultrapure water, and collecting a product, namely the nano spinel ferrite;
2) mixing the nano spinel ferrite prepared in the step 1) with a carbon material in ultrapure water, and reacting the mixed solution in a constant-temperature magnetic stirrer at room temperature and at the rotating speed of 20-40 rpm for not less than 1h to obtain the carbon material-coated magnetic spinel iron oxide TFe2O4(ii) a Wherein the mass ratio of the nano spinel ferrite to the carbon material is (4-10): (0-1), wherein the mass ratio of the solid (nano spinel ferrite and carbon material) to the ultrapure water is (3-6): 200-300);
3) wrapping the carbon material prepared in the step 2) with magnetic TFe2O4Mixing with organic ligand and ultrapure water, stirring at normal temperature and performing ultrasonic treatment for at least 1h to obtain uniform suspension, transferring the uniform suspension into a polytetrafluoroethylene reaction kettle, reacting at 90-150 ℃ for a period of time, transferring the reacted product into a small beaker, washing with ultrapure water and ethanol respectively, centrifuging, and drying to obtain a product, namely the carbon material-coated spinel iron oxide TFe2O4In-situ growth of MOFsAdsorbing the catalytic complex;
wherein the carbon material coated magnetic spinel iron oxide TFe2O4: organic ligand: the mass ratio of the ultrapure water is (2-4): (1-2): (200-);
further, the reaction time of the uniform suspension liquid after being transferred into a polytetrafluoroethylene reaction kettle is more than 10 hours; preferably over 12 h;
further, the drying temperature is above 40 ℃; preferably 55-65 ℃, and further preferably 60 ℃;
further, the drying time is more than 5 hours; preferably more than 8 h; further preferably 8 to 10 hours.
3. The method for preparing the carbon material coated spinel iron oxide in-situ growth MOFs adsorption catalysis complex according to claim 2, wherein,
the nano spinel ferrite: the mass ratio of the carbon material is (5-10): 1.
4. the method for preparing the carbon material coated spinel iron oxide in-situ growth MOFs adsorption catalysis complex according to claim 2, wherein,
the carbon material is one or more of multi-walled carbon nanotube, graphene/graphene oxide and biochar.
5. The method for preparing the carbon material coated spinel iron oxide in-situ growth MOFs adsorption catalytic composite according to claim 2 or 3,
the particle size of the nano spinel ferrite is 20-50 nm;
further, the specific surface area of the carbon material is 50 to 300m2/g；
Further, when the carbonized material is a multi-walled carbon nanotube, the specific surface area of the multi-walled carbon nanotube is 80 to 250m2Per g, pore volume of 0.4-1.2cm3/g；
Further, the carbon material is graphene oxide.
6. The method for preparing the carbon material coated spinel iron oxide in-situ growth MOFs adsorption catalytic composite according to any one of claims 1 to 5,
the organic ligand can be aliphatic carboxylic acid, aromatic carboxylic acid and nitrogen heterocyclic carboxylic acid substances;
further, the organic ligand is trimesic acid (H)3BTC)；
Further, the carbon material wraps spinel iron oxide TFe2O4In-situ growth MOFs are adsorbed in the catalytic composite body, and the in-situ growth MOFs are grown on ferrite wrapped by carbon materials.
7. The carbon material-coated spinel iron oxide in-situ growth MOFs adsorption catalysis complex prepared by the preparation method according to any one of claims 1 to 6.
8. The carbon material-coated spinel iron oxide in-situ growth MOFs adsorption catalytic composite according to claim 7, wherein said carbon material-coated spinel iron oxide in-situ growth MOFs adsorption catalytic composite has a size of 10-100nm and a saturation magnetization of 15-35 emu/g.
9. The use of the carbon material coated spinel iron oxide in-situ grown MOFs adsorption catalytic composite of claim 7 or 8 in the preparation of water treatment adsorbents and/or water treatment filter column packing materials.
10. The carbon material-coated spinel iron oxide in-situ growth MOFs adsorption catalysis complex of claim 7 or 8 in catalyzing PMS, PDS and H2O2、FeO4 2-And FeO4 2-/H2O2Application in degrading organic pollutant.
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