CN113145062B - Preparation method of magnetic adsorption material based on Prussian blue and hydrotalcite - Google Patents

Preparation method of magnetic adsorption material based on Prussian blue and hydrotalcite Download PDF

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CN113145062B
CN113145062B CN202110466236.4A CN202110466236A CN113145062B CN 113145062 B CN113145062 B CN 113145062B CN 202110466236 A CN202110466236 A CN 202110466236A CN 113145062 B CN113145062 B CN 113145062B
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ldos
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CN113145062A (en
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张瑞康
王灿
高元哲
韩占刚
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Hebei Normal University
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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
    • B01J20/08—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 comprising aluminium oxide or hydroxide; comprising bauxite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing

Abstract

The invention discloses a method for preparing ferroferric oxide (Fe)3O4) A method for preparing a core-shell structure composite material with a magnetic core and a Layered Double metal oxide (LDOs) coated outside the magnetic core. Firstly, forming a coordination nucleation growth site of Layered Double Hydroxides (LDHs) on the surface of Prussian Blue (PB) by regulating and controlling a solvent environment, so that the LDHs are coated and grown on the surface of the PB to form a PB @ LDHs core-shell composite material taking PB as a core and LDHs as a shell, and further converting PB into Fe by high-temperature treatment3O4LDHs are transformed into LDOs by dehydration to obtain Fe3O4Fe with magnetic core and LDOs as shell3O4@ LDOs magnetic adsorbent material. LDOs of the shell layer has good adsorption property, and Fe of the nuclear layer3O4Has excellent magnetic property. Under the action of a magnetic field, Fe3O4The @ LDOs composite material is capable of being rapidly separated from water. Fe obtained3O4The @ LDOs composite material has a core-shell structure, and can be widely applied to the fields of pollutant adsorption, degradation, photocatalysis and the like.

Description

Preparation method of magnetic adsorption material based on Prussian blue and hydrotalcite
Technical Field
The invention belongs to the field of inorganic nano material synthesis, and particularly relates to Fe obtained by using hydrotalcite coated Prussian blue as a precursor through roasting treatment3O4A preparation method of a magnetic adsorption material with magnetic cores and LDOs as shell layers.
Background
The industrial wastewater often contains high-concentration organic pollutants such as dyes, tetracycline, floating oils, phenolic compounds and the like) or inorganic pollutants such as heavy metals, fluorides and the like, and is difficult to treat by a common biological method so as to reach the emission standard. The commonly used treatment methods are chemical, ion exchange and physical adsorption. Among them, the chemical precipitation or oxidation process can only treat some waste water with simple components. The cost of the membrane material in the ion exchange method is high, the service life is short, and the equipment investment and the energy consumption are large. Compared with chemical method and ion exchange method, the physical adsorption method has the advantages of large adsorption capacity, high adsorption speed, simple equipment and the like, thereby being widely applied. However, the cost of the adsorbent in the adsorption method, the secondary treatment problem of the adsorbent after adsorbing the pollutants and the like limit the application of the method to a certain extent. For this reason, the development of low-cost, high-capacity and easily recyclable adsorbents is the current trend of preparing adsorbent materials.
Previous researches show that Layered Double Hydroxides (LDHs) are commonly called hydrotalcite, and have the advantages of stable physical and chemical properties, no toxicity or harm to the environment and low price. The LDHs material has a sandwich structure, an interlayer anion guest is combined with an upper main body laminate and a lower main body laminate through weak interaction such as coulomb force, hydrogen bonds and the like, and the components, the proportion and the like of the main body laminate and the interlayer anion have great modification. After the medium-temperature calcination, the hydroxyl groups on the metal layer plate are dehydrated and decomposed, and interlayer anions are separated out to form Layered Double metal Oxides (LDOs). The LDOs material obtained by moderate temperature calcination has a memory effect, namely, the LDHs material is recombined with water and dehydrated anions in aqueous solution and is restored to the original LDHs structure, thereby showing excellent selective adsorption performance to specific ions. LDHs recovered through the memory effect can be dehydrated again and interlayer ions are changed into LDOs through medium-temperature roasting, and the LDOs material can be recycled for multiple times, so that the LDOs material is a promising adsorption material. In order to realize the rapid recovery of the adsorbent material from the water body, the adsorbent material can be combined with a magnetic substance, and the recovery of the adsorbent material from the treated water body can be realized under the action of an external magnetic field. Prussian Blue (PB) is low in cost, easy to synthesize and stable in property, and can be converted into magnetic ferroferric oxide (Fe) by taking Prussian Blue as a precursor and roasting the Prussian Blue3O4)，Fe3O4Can be easily separated from the treated water under the action of an external magnetic field. Based on the characteristics, the magnetic LDOs composite material prepared by using the PB and the LDHs has the advantages of selective adsorption of specific pollutants in water, repeated utilization for many times, rapid recovery under the action of a magnetic field and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a magnetic adsorption material based on Prussian blue and hydrotalcite
The method is carried out. Fe obtained3O4The @ LDOs composite magnetic adsorption material has a core-shell structure, has excellent anion adsorption performance, can be recycled for many times, can be quickly separated from a water body under the action of a magnetic field, and solves the problems of adsorption material recovery and secondary treatment.
The invention has the conception that aiming at the defects of difficult recovery and poor recycling effect of the traditional adsorbing material, the LDHs material with the memory effect is selected and grows on the magnetic nano-core in situ, thereby achieving the purpose of preparing the adsorbing material which can be rapidly recovered and recycled under the action of a magnetic field. LDHs material grows in situ on PB by regulating and controlling solvent environment, and PB is converted into Fe after roasting treatment3O4LDHs are transformed into LDOs by dehydration to obtain Fe3O4Is magnetic core, LDOs is shell Fe3O4@ LDOs magnetic adsorbent material. Wherein, magnetic core Fe3O4Provides magnetic force for separating from water under magnetic field, and the shell LDOs provides adsorption sites for adsorbing pollutants such as anionic dye.
Specifically, the invention provides a preparation method of a magnetic adsorption material based on Prussian blue and hydrotalcite
The method comprises the following steps:
(1) weighing a certain mass of Prussian blue precursor, and dispersing the Prussian blue precursor in an aqueous solution dissolved with metal salt, urea and citric acid, wherein the concentration of the urea is 0.1-1 mol.L–1The concentration of citric acid is 0.01-0.5 mol.L–1The total concentration of metal ions is 0.03-0.1 mol.L–1；
(2) Putting the solution prepared in the step (1) into a reaction kettle, reacting for 2-24 h at 50-200 ℃, and washing and drying the obtained solid product to obtain a PB @ LDHs material;
(3) roasting the PB @ LDHs material prepared in the step (2) for 2-10 h at 200-600 ℃ in a high-temperature furnace in an inert gas atmosphere to obtain Fe3O4@ LDOs magnetic composite material. The Fe3O4@ LDOs magnetic composite materialNamely, the magnetic adsorbent of the present invention.
In the present invention, the metal salt used in step (1) may be any combination of two or more of zinc, cobalt, magnesium, aluminum, and nickel salts.
The invention has the following beneficial effects: the invention realizes the Fe which is easy to rapidly recover and can be recycled for multiple times3O4And (3) preparing the @ LDOs magnetic composite material. The raw materials are cheap and easy to obtain, and the preparation method is simple and can be applied to large-scale batch production. The invention provides Fe3O4The synthesis method of the magnetic adsorption material with magnetic cores and LDOs as shells solves the problem of secondary treatment of water body caused by difficult recovery of the adsorption material, and meanwhile, the adsorption material can be recycled for many times, thus reducing cost. The prepared metal oxide coated ferroferric oxide magnetic nano composite material can be widely applied to the water treatment fields of pollutant adsorption, degradation and the like.
Drawings
FIG. 1 is a scheme for preparing Fe by using PB as a template in example 13O4A flow schematic diagram of the @ ZnAl-LDO core-shell material.
FIG. 2 is a scanning electron micrograph of PB used in example 1.
FIG. 3 is a scanning electron micrograph of ZnAl-LDH grown on the surface of PB in example 1.
FIG. 4 shows Fe obtained by calcination treatment in example 13O4Scanning electron microscope picture of @ ZnAl-LDO.
FIG. 5 is the PB, PB @ ZnAl-LDH and Fe in example 13O4XRD pattern of @ ZnAl-LDO.
FIG. 6 is Fe in example 13O4A graph of the rate of adsorption of the @ ZnAl-LDO dye and a graph of a real object rapidly separated under the action of a magnetic field.
As can be seen from FIG. 1, Fe was produced3O4The @ ZnAl-LDO core-shell material needs two steps from PB.
As can be seen from FIG. 2, the particle size of PB nano-cubic was 2 to 5 μm.
As can be seen from FIG. 3, the particle size of the PB @ ZnAl-LDH nano cubic block is 3-6 μm.
As can be seen from FIG. 4, Fe3O4The particle size of the @ ZnAl-LDO nano cubic block is 3-6 mu m.
As can be seen from FIG. 5, PB @ ZnAl-LDH and Fe were successfully prepared3O4The sample of @ ZnAl-LDO.
As can be seen from FIG. 6, Fe3O4The dye adsorption rate of the @ ZnAl-LDO is 99% after 15 minutes, and the dye can be quickly separated from a water body through a magnetic field.
Detailed Description
The following examples serve to illustrate the invention.
EXAMPLE 1 Synthesis of ZnAl-LDH on the surface of PB, formation of Fe after calcination3O4The preparation process of the @ ZnAl-LDO magnetic composite material comprises the following steps:
a, 0.3 g PB is dispersed in 70 mL of aqueous solution dissolved with zinc chloride, aluminum nitrate, urea and citric acid, wherein the concentration of the urea is 0.1 mol.L–1The concentration of citric acid is 0.02 mol.L–1The concentration of zinc ions is 0.03 mol.L–1The concentration of aluminum ions was 0.01 mol. L–1；
b, putting the mixture into a 100 mL reaction kettle, reacting for 24 hours at 100 ℃, and washing and drying the obtained solid product;
c, putting the product obtained in the step b into a tubular furnace, wherein the heating rate is 5 ℃ per minute–1Roasting at 400 ℃ for 5 h in nitrogen atmosphere to obtain Fe3O4@ ZnAl-LDO magnetic composite material.
Example 2 CoAl-LDH Synthesis on PB surface and formation of Fe after calcination3O4The preparation process of the @ CoAl-LDO magnetic composite material comprises the following steps:
a, 0.4 g PB is dispersed in 100 mL of aqueous solution dissolved with cobalt chloride, aluminum nitrate, urea and citric acid, wherein the concentration of the urea is 0.4 mol.L–1The concentration of citric acid is 0.08 mo.L–1The concentration of cobalt ion was 0.02 mo.L–1The concentration of aluminum ions is 0.08 mol.L–1；
b, putting the mixture into a 200 mL reaction kettle, reacting for 20 hours at 110 ℃, and washing and drying the obtained solid product;
c, putting the product obtained in the step b into a tubular furnace, wherein the heating rate is 2 ℃ per minute–1Roasting at 500 ℃ for 5 h in helium atmosphere to obtain Fe3O4@ CoAl-LDO magnetic composite material.
EXAMPLE 3 MgAl-LDH Synthesis on PB surface and Fe formation after calcination3O4The preparation process of the @ MgAl-LDO magnetic composite material comprises the following steps:
a, 1.0 g of PB is dispersed in 300 mL of aqueous solution dissolved with magnesium chloride, aluminum nitrate, urea and citric acid, wherein the concentration of the urea is 0.8 mol.L–1The concentration of citric acid is 0.1 mol.L–1The concentration of magnesium ions was 0.05 mol. L–1The concentration of aluminum ions is 0.03 mol.L–1；
b, putting the mixture into a 500 mL reaction kettle, reacting for 20 hours at 110 ℃, and washing and drying the obtained solid product;
c, putting the product obtained in the step b into a tubular furnace, wherein the heating rate is 2 ℃ per minute–1Roasting at 600 ℃ for 4 h in nitrogen atmosphere to obtain Fe3O4@ MgAl-LDO magnetic composite material.
Example 4 CoNi-LDH Synthesis on PB surface, formation of Fe after calcination3O4The preparation process of the @ CoNi-LDO magnetic composite material comprises the following steps:
a, dispersing 2.0 g of PB in 700 mL of aqueous solution dissolved with cobalt chloride, nickel nitrate, urea and citric acid. Wherein the concentration of urea is 0.5 mol.L–1The concentration of citric acid is 0.2 mol.L–1The concentration of cobalt ion is 0.02 mol.L–1The concentration of nickel ions is 0.08 mol.L–1；
b, putting the mixture into a 1000 mL reaction kettle, reacting for 16 h at 90 ℃, and washing and drying the obtained solid product;
c, putting the product obtained in the step b into a tubular furnace, wherein the heating rate is 2 ℃ per minute–1Roasting at 600 ℃ for 4 h in nitrogen atmosphere to obtain Fe3O4@ CoNi-LDO magnetic composite material.

Claims (2)

1. A preparation method of a magnetic adsorption material based on Prussian blue and hydrotalcite is characterized by comprising the following steps:
(1) weighing a certain mass of Prussian blue precursor, and dispersing the Prussian blue precursor in an aqueous solution dissolved with metal salt, urea and citric acid, wherein the concentration of the urea is 0.1-1 mol.L–1The concentration of citric acid is 0.01-0.5 mol.L–1The total concentration of metal ions is 0.03-0.1 mol.L–1；
(2) Putting the solution prepared in the step (1) into a reaction kettle, reacting for 2-24 h at 50-200 ℃, and washing and drying the obtained solid product to obtain a PB @ LDHs material;
(3) roasting the PB @ LDHs material prepared in the step (2) for 2-10 h at 200-600 ℃ in a high-temperature furnace in an inert gas atmosphere to obtain Fe3O4@ LDOs magnetic composite material.
2. The method according to claim 1, wherein the metal salt used in step (1) is any combination of two or more of zinc, cobalt, magnesium, aluminum, and nickel salts.
CN202110466236.4A 2021-04-28 2021-04-28 Preparation method of magnetic adsorption material based on Prussian blue and hydrotalcite Active CN113145062B (en)

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CN114849675A (en) * 2022-05-18 2022-08-05 哈尔滨工业大学 Preparation method of magnetic NiFe-LDH composite material for adsorbing uranium
CN115025749A (en) * 2022-06-07 2022-09-09 江苏大学 Preparation method and application of modified hydrotalcite-like adsorbent material
CN115477329B (en) * 2022-09-14 2023-06-20 北京信息科技大学 Preparation method of carbon-based core-shell structure pine cone-shaped nanoflower magnetic composite material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017046252A1 (en) * 2015-09-18 2017-03-23 Consejo Superior De Investigaciones Científicas (Csic) A core-shell composition for purifying contaminated water and/or biological-medical systems such as tissues, cells or blood
CN108927169A (en) * 2018-08-17 2018-12-04 太原理工大学 A kind of preparation method and application of hydrotalcite CoMnFe metal composite oxide denitrating catalyst
CN109174105A (en) * 2018-10-11 2019-01-11 天津工业大学 A kind of preparation method of magnetic catalyst derived from double MOFs
CN109847786A (en) * 2019-03-06 2019-06-07 常州大学 A kind of preparation method and application of Z-type photochemical catalyst MgAlLDH/CN-H

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017046252A1 (en) * 2015-09-18 2017-03-23 Consejo Superior De Investigaciones Científicas (Csic) A core-shell composition for purifying contaminated water and/or biological-medical systems such as tissues, cells or blood
CN108927169A (en) * 2018-08-17 2018-12-04 太原理工大学 A kind of preparation method and application of hydrotalcite CoMnFe metal composite oxide denitrating catalyst
CN109174105A (en) * 2018-10-11 2019-01-11 天津工业大学 A kind of preparation method of magnetic catalyst derived from double MOFs
CN109847786A (en) * 2019-03-06 2019-06-07 常州大学 A kind of preparation method and application of Z-type photochemical catalyst MgAlLDH/CN-H

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