CN116726882A - Multi-size octahedral MIL-88B (Fe) -derived Fe 3 O 4 Preparation method of @ C composite material - Google Patents
Multi-size octahedral MIL-88B (Fe) -derived Fe 3 O 4 Preparation method of @ C composite material Download PDFInfo
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- 239000013215 MIL-88B Substances 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 15
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 13
- 239000003463 adsorbent Substances 0.000 claims description 11
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- 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]
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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
- 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
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
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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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- B01J20/28009—Magnetic properties
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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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- B01J20/28014—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 form
- B01J20/28042—Shaped bodies; Monolithic structures
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- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
- B01J20/3057—Use of a templating or imprinting material ; filling pores of a substrate or matrix followed by the removal of the substrate or matrix
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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Abstract
The invention discloses a multi-sized octahedral MIL-88B (Fe) -derived Fe 3 O 4 Firstly, obtaining multi-size octahedral MIL-88B (Fe) by changing the concentration of metal salt and organic ligand and the filling degree of solution; then take it as a precursor, at N 2 Next calcining to obtain the mesoporous carbon coated magnetic Fe 3 O 4 A composite material. The composite material keeps the morphology of the precursor, and the preparation method is simple, green and environment-friendly and has low cost. The invention discloses a method for preparingPrepared Fe 3 O 4 The @ C composite material has good stability, mesoporous structure, large specific surface and paramagnetism. Can be used as an adsorption material in the field of heavy metal ion removal, has high removal efficiency and low energy consumption, and has certain practical application potential.
Description
Technical Field
The invention belongs to the field of MOF materials of metal-organic framework compounds, in particular to Fe derived from multi-size octahedral MIL-88B (Fe) 3 O 4 A preparation method of the @ C composite material.
Background
Along with the rapid development of the industry in China, the heavy metal wastewater generated in the industrial production processes of mining and metallurgy, mechanical manufacturing, chemical industry and the like is one of the industrial wastewater with the most serious water pollution and the greatest ecological hazard. Heavy metal ions in the wastewater cannot be decomposed and destroyed by a common water treatment method, cannot be biodegraded after entering the environment, and can only participate in food chain circulation and be enriched in organisms by changing the physical and chemical states or being transferred and diluted, so that the normal physiological and metabolic activities of the organisms are finally destroyed and the health of human bodies is endangered.
The methods commonly used for treating heavy metal wastewater mainly comprise a chemical method, an ion exchange method, an electrolytic method, an adsorption method and the like. The adsorption method has the advantages of easy operation, high efficiency and the like, but has the bottleneck problems of high treatment cost, difficult separation of adsorption materials and the like. Therefore, a new adsorption material which is simple to synthesize, green, efficient and easy to separate and is used for adsorbing Pb in wastewater is needed to be searched 2+ And (3) an isoparaffinic metal ion.
The MIL-88B (Fe) synthesis method reported at present comprises hydrothermal, solvothermal, oil bath and the like, the obtained morphology is in a regular octahedron or spindle shape, the size is single, multi-scale particles cannot be simultaneously provided, the nano-scale size of about 100nm is lacked, the specific surface area is small, and the preparation process is complex.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a multi-size octahedral MIL-88B (Fe) -derived Fe 3 O 4 A preparation method of the @ C composite material. The material retains the basic morphology of original MIL-88B (Fe) material, has good stability, mesoporous structure, large specific surface area, and paramagnetism, and can be used asIs an adsorption material used in the field of heavy metal ion removal.
The technical scheme adopted for solving the technical problems is as follows:
a first aspect of the invention provides a multi-sized octahedral MIL-88B (Fe) -derived Fe 3 O 4 The preparation method of the @ C composite material comprises the following steps:
(1) Dissolving ferric trichloride hexahydrate into an N, N-dimethylformamide solvent, and magnetically stirring until the solution is uniform and transparent to obtain a solution A, wherein the concentration of the ferric trichloride hexahydrate in the solution A is 0.092-0.138 mol/L; dissolving terephthalic acid into an N, N-dimethylformamide solvent, and magnetically stirring until the solution is uniform and transparent to prepare a solution B;
(2) Dropwise adding the solution A into the solution B in the process of continuous magnetic stirring, wherein the mole ratio of ferric trichloride hexahydrate to terephthalic acid is 1-2: 1-2, continuing magnetic stirring until uniformity after complete addition, and preparing a solution C;
(3) Carrying out solvothermal reaction on the solution C, centrifuging to separate out solid after the reaction is finished, washing and drying to obtain pink powder, namely MIL-88B (Fe);
(4) Taking MIL-88B (Fe) prepared in the step (3) as a precursor, and adding the precursor into N 2 Carbonization and graphitization are carried out by lower calcination, and finally the Fe derived from multi-size octahedral MIL-88B (Fe) can be obtained 3 O 4 @ C composite.
Carbonization of terephthalic acid serving as a carbon source serving as an organic ligand to form amorphous carbon, fe 3+ Is reduced and combined with O element in the organic ligand to generate Fe 3 O 4 Then at Fe 3 O 4 Is graphitized by the catalytic action of the catalyst.
Further, the concentration of the ferric trichloride hexahydrate in the step (1) is 0.092-0.11 mol/L
Further, the mole ratio of the ferric trichloride hexahydrate to the terephthalic acid in the step (2) is 1-1.5: 1 to 1.5.
Further, after the solution A in the step (2) is added into the solution B dropwise, the magnetic stirring is continued for 30-40 minutes.
Further, the solvothermal reaction temperature in the step (3) is 100-120 ℃ and the reaction time is 20-30 h. Further preferably the reaction temperature is 105 to 115℃and the reaction time is 23 to 25 hours.
Further, after the solvothermal reaction in the step (3), the centrifugal revolution is 2000-5000 r/min, and the solvent is washed with DMF and absolute ethyl alcohol for 2-3 times respectively.
Further, the step (3) is vacuum drying, the drying temperature is 50-70 ℃, and the drying time is 12-24 hours. Further preferably the drying temperature is 55 to 65℃and the drying time is 16 to 20 hours.
Further, the calcination in the step (4) is performed in a quartz tube furnace, the temperature rising rate during the calcination is 2-10 ℃/min, the calcination temperature is 700-900 ℃ and the time is 0.5-2 h. Further preferably, the temperature rising rate is 4-8 ℃/min, the calcining temperature is 700-800 ℃ and the calcining time is 0.5-1 h.
In a second aspect, the invention provides multi-sized octahedral MIL-88B (Fe) -derived Fe prepared by the method 3 O 4 The dimension of the @ C composite material is contracted compared with that of a precursor MIL-88B (Fe), the overall material is still in an octahedron shape, the side length is in the range of 40-900 nm, and the main dimension is concentrated in the range of 400-700 nm.
The third aspect of the invention provides the composite material for adsorbing heavy metal ions Pb in the comprehensive wastewater of the garbage power plant 2+ The application of the catalyst as an adsorbent.
The invention prepares multi-size octahedron MIL-88B (Fe) in N by solvothermal method 2 MIL-88B (Fe) -derived Fe prepared by next calcination (carbonization, graphitization) 3 O 4 @ C composite. It is mainly Fe 3 O 4 The surface is coated with a layer of porous carbon mixed by amorphous carbon and graphite carbon. The cladding structure maintains the basic morphology of the original MIL-88B (Fe) material, and has the characteristics of mesoporous structure and large specific surface area; the super-paramagnetic ion-free high-efficiency separation of the adsorption material can be realized under the action of an external magnetic field, the separation energy consumption is greatly reduced, and the super-paramagnetic ion-free high-efficiency separation of the adsorption material can be used as the adsorption material to realize heavy metal ions Pb in comprehensive wastewater of a garbage power plant 2+ Has the fast removing functionHas great application potential.
The invention has the advantages and positive effects that:
the invention obtains multi-size octahedral MIL-88B (Fe) by setting the concentration of metal salt and organic ligand and the filling degree of solution; then take it as a precursor, at N 2 Next calcining to obtain the mesoporous carbon coated magnetic Fe 3 O 4 A composite material. The small-size effect of the nanoscale material is beneficial to increasing the specific surface area of the material, promoting the material to be fully contacted with the comprehensive wastewater of the garbage power plant, and the large-size octahedron with the microscale can provide more pores for adsorbing heavy metal ions. In conclusion, the mutual cooperation of the particles with multiple sizes can greatly promote the adsorption of the material on heavy metal ions in the comprehensive wastewater of the garbage power plant. The composite material keeps the morphology of the precursor, and the preparation method is simple, green and environment-friendly and has low cost. Fe prepared by the method 3 O 4 The @ C composite material has good stability, mesoporous structure, large specific surface and paramagnetism. Can be used as an adsorption material in the field of heavy metal ion removal, has high removal efficiency and low energy consumption, and has certain practical application potential.
Drawings
FIG. 1 is a low resolution SEM image of MIL-88B (Fe) prepared according to example 1 of the present invention;
FIG. 2 is a high resolution SEM image of MIL-88B (Fe) prepared according to example 1 of the present invention;
FIG. 3 is an SEM image of MIL-88B (Fe) prepared in comparative example 1 according to the present invention;
FIG. 4 shows Fe prepared in example 1 of the present invention 3 O 4 XRD pattern of @ C;
FIG. 5 shows Fe prepared in example 1 of the present invention 3 O 4 N of @ C 2 Adsorption-desorption isotherm curves;
FIG. 6 shows Fe prepared in example 1 of the present invention 3 O 4 Pore size distribution plot @ C;
FIG. 7 shows Fe prepared in example 1 of the present invention 3 O 4 Adsorption capacity plot at different pH;
FIG. 8 shows Fe prepared in example 1 of the present invention 3 O 4 A graph of removal for five cycles of @ C at ph=5;
FIG. 9 shows Fe prepared in example 2 of the present invention 3 O 4 Adsorption capacity plot at different pH;
FIG. 10 shows Fe prepared in example 2 of the present invention 3 O 4 A graph of removal for five cycles of @ C at ph=6;
FIG. 11 shows Fe prepared in example 3 of the present invention 3 O 4 Adsorption capacity plot at different pH;
FIG. 12 shows Fe prepared in example 3 of the present invention 3 O 4 A graph of removal for five cycles of @ C at ph=5;
FIG. 13 shows Fe prepared in comparative example 1 of the present invention 3 O 4 Adsorption capacity plot at different pH;
FIG. 14 shows Fe prepared in comparative example 2 of the present invention 3 O 4 Adsorption capacity plot at different pH;
FIG. 15 shows Fe prepared in comparative example 2 of the present invention 3 O 4 A graph of removal for five cycles of @ C at ph=5;
FIG. 16 shows Fe prepared in comparative example 3 of the present invention 3 O 4 Adsorption capacity plot at different pH;
FIG. 17 shows Fe prepared in comparative example 3 of the present invention 3 O 4 A graph of removal for five cycles of @ C at ph=5;
Detailed Description
The invention is further illustrated by the following examples, which are intended to be illustrative only and not limiting in any way.
In the examples below, the reagents used, unless specifically indicated, were all commercially available chemical reagents analytically pure.
The filling degree refers to the percentage of the total volume of the solvent to the total volume of the solvothermal reactor.
Example 1
Multi-size octahedral MIL-88B (Fe) -derived Fe 3 O 4 The preparation method of the @ C composite material comprises the following steps:
1) 622mg (2.3 mmol) of ferric trichloride hexahydrate is weighed and dissolved in 25 mM LDMF solvent, and the solution A is prepared by magnetic stirring uniformly; 382mg (2.3 mmol) of terephthalic acid is weighed and dissolved in 25 mM (L-DMF) solvent, and the solution B is prepared by magnetic stirring uniformly, wherein the filling degree is 50%;
2) Dropwise adding the solution A into the solution B in the continuous ultrasonic process, and continuing magnetic stirring for 30min until uniformity after the solution A is completely added to obtain a solution C;
3) Transferring the mixed solution C into a stainless steel reaction kettle with a polytetrafluoroethylene lining of 100mL, sealing, carrying out solvothermal reaction for 24 hours at the temperature of 110 ℃ in a blast drying box, naturally cooling to room temperature after the reaction is finished, respectively centrifugally washing 3 times with DMF and absolute ethyl alcohol, and finally drying for 10 hours at the temperature of 60 ℃ in a vacuum drying box to obtain a final product MIL-88B (Fe);
4) Spreading 200mg of MIL-88B (Fe) pink powder in a porcelain boat, placing in a tube furnace, and adding into N 2 Heating from room temperature to 700 ℃ in the atmosphere, keeping the temperature at the heating rate of 5 ℃/min and the temperature of 700 ℃ for 0.5h, and naturally cooling to room temperature to obtain black powder which is Fe derived from MIL-88B (Fe) 3 O 4 @ C composite.
The low resolution SEM result of the precursor MIL-88B (Fe) prepared in step 3) of this example is shown in FIG. 1, the morphology is regular, all are regular octahedrons, the side length is in the range of 50-1500 nm, and the main dimension is concentrated at 700-1300 nm.
The high resolution SEM results of the precursor MIL-88B (Fe) prepared in step 3) of this example are shown in FIG. 2, and octahedral particles within 100nm are clearly seen.
Step 4) of the present example Fe obtained 3 O 4 XRD results for the @ C composite are shown in FIG. 4. Diffraction peaks in the figure can be respectively attributed to Fe 3 O 4 (JCPDS#88-0315) and graphitic carbon (JCPDS#34-0567), indicating that the MIL-88B (Fe) derivative prepared is Fe 3 O 4 @ C composite.
Step 4) of the present example Fe obtained 3 O 4 N of the @ C composite 2 The adsorption-desorption isothermal curve is shown in FIG. 5, which is a characteristic of typical type IV mesoporous materialsCharacterization curve, BET specific surface area calculated as 295m 2 /g。
Step 4) of the present example Fe obtained 3 O 4 The pore size distribution results of the @ C composite are shown in FIG. 6, where the very high peak at 3.8nm is a false peak caused by the hysteresis loop of the desorption curve. The true pore diameter of the material is mostly concentrated at 6.9nm, which proves that Fe 3 O 4 The @ C composite is a typical mesoporous material.
Fe 3 O 4 the@C composite material is used for adsorbing heavy metal ions Pb 2+ The application in the field specifically comprises the following steps:
10mL of waste plant integrated wastewater (COD) was added to a 100mL Erlenmeyer flask Cr Less than or equal to 170mg/L; SS is less than or equal to 480mg/L; the pH is 6.5-8.5; cl - The concentration is less than or equal to 330mg/L; pb 2+ Concentration less than or equal to 110 mg/L) and regulating Pb by using 0.1M NaOH or HCl solution 2+ The initial pH of the solution was 1,3,5,7,9, 11 and 13, respectively, and 1g/L Fe was added 3 O 4 And @ C is an adsorbent, and after being mechanically stirred for 30min and centrifuged for 10min at room temperature (or under the action of an external magnetic field), supernatant is taken and properly diluted, and the concentration of residual heavy metal ions in the solution is measured by an atomic absorption spectrophotometer. The results are shown in FIG. 7, and the Fe produced 3 O 4 The @ C is effective for adsorption over a wide pH range.
After the adsorption test was completed, the solid adsorbent was separated, desorbed with 0.1mol/L HCl solution for 2 hours, washed with ultrapure water 3 times, and dried sufficiently. The adsorbent was subjected to recycling test at ph=5 according to the above-described experimental method, and the result is shown in fig. 8. Heavy metal ion Pb after 5 times of circulation of adsorbent 2+ The removal rate is still maintained to be more than 99 percent.
Example 2
The preparation method is the same as in example 1, except that the concentration of ferric trichloride hexahydrate is 0.11mol/L, and the calcination (carbonization and graphitization) temperature is 900 ℃. The prepared Fe is subjected to the adsorption experimental method 3 O 4 @C vs Pb 2+ The pollutant adsorption is effective in a wide pH range (as shown in figure 9), the adsorbent can be recycled for multiple times, and the adsorbent after 5 times of recycling has a pH value of =Heavy metal ion Pb under 6 conditions 2+ The removal rate was still higher than 90% (see fig. 10).
Example 3
The preparation method is the same as in example 1, except that the calcination (carbonization, graphitization) time is 1h. The prepared Fe is subjected to the adsorption experimental method 3 O 4 @C vs Pb 2+ The pollutant adsorption is effective in a wide pH range (as shown in fig. 11), and the adsorbent is subjected to 5 cycles of heavy metal ion Pb at ph=5 2+ The removal rate was still higher than 89% (see fig. 12).
Comparative example 1
The preparation method is the same as in example 1, except that the concentration of ferric trichloride hexahydrate is 0.023mol/L and the filling degree is 20%. The precursor MIL-88B (Fe) prepared in the comparative example is octahedral in morphology and has the size of about 1200nm (shown in figure 3). The prepared Fe is subjected to the adsorption experimental method 3 O 4 At a broad pH range, p Pb 2+ The adsorption efficiency of the contaminants was less than 60% (see fig. 13).
Comparative example 2
The preparation process was identical to example 1, except that the calcination temperature was 600 ℃. The prepared Fe is subjected to the adsorption experimental method 3 O 4 At a broad pH range, p Pb 2+ The adsorption efficiency of the pollutant is low (as shown in fig. 14) and the heavy metal ion Pb of the adsorbent after 5 cycles at ph=7 2+ Poor removal and recovery performance (see fig. 15).
Comparative example 3
The preparation process was identical to example 1, except that the calcination time was 3h. The prepared Fe is subjected to the adsorption experimental method 3 O 4 At a broad pH range, p Pb 2+ The adsorption efficiency of the pollutant is low (as shown in fig. 16) and the heavy metal ion Pb of the adsorbent after 5 cycles at ph=7 2+ Poor removal and recovery performance (see fig. 17).
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that it will be apparent to those skilled in the art that variations and modifications can be made without departing from the scope of the invention.
Claims (8)
1. Multi-size octahedral MIL-88B (Fe) -derived Fe 3 O 4 The preparation method of the @ C composite material is characterized by comprising the following steps of:
(1) Dissolving ferric trichloride hexahydrate into an N, N-dimethylformamide solvent, magnetically stirring until the solution is uniform and transparent to obtain a solution A, wherein the concentration of the ferric trichloride hexahydrate is 0.092-0.138 mol/L; dissolving terephthalic acid into an N, N-dimethylformamide solvent, and magnetically stirring until the solution is uniform and transparent to prepare a solution B;
(2) Dropwise adding the solution A into the solution B in the process of continuous magnetic stirring, wherein the mole ratio of ferric trichloride hexahydrate to terephthalic acid is 1-2: 1-2, continuing magnetic stirring until uniformity after complete addition, and preparing a solution C;
(3) Carrying out solvothermal reaction on the solution C, centrifuging to separate out solid after the reaction is finished, washing and drying to obtain pink powder, namely MIL-88B (Fe);
(4) Taking MIL-88B (Fe) prepared in the step (3) as a precursor, and adding the precursor into N 2 Carbonization and graphitization are carried out by lower calcination, and finally the Fe derived from multi-size octahedral MIL-88B (Fe) can be obtained 3 O 4 @ C composite.
2. The method according to claim 1, wherein the concentration of ferric trichloride hexahydrate is 0.092 to 0.11mol/L.
3. The process according to claim 1, wherein the molar ratio of ferric trichloride hexahydrate to terephthalic acid is from 1 to 1.5:1 to 1.5.
4. The method according to claim 1, wherein the solvothermal reaction temperature in step (3) is 100-120 ℃ and the reaction time is 20-30 h.
5. The preparation method according to claim 1, wherein the drying in the step (3) is vacuum drying at a drying temperature of 50-70 ℃ for 12-24 hours.
6. The method according to claim 1, wherein the calcination in step (4) is performed in a quartz tube furnace at a temperature rising rate of 2 to 10 ℃/min, at a calcination temperature of 700 to 900 ℃ for 0.5 to 2 hours.
7. A multi-sized octahedral MIL-88B (Fe) -derived Fe prepared according to the method of any one of claims 1-6 3 O 4 The @ C composite material is in an octahedron shape, has a side length of 40-900 nm and has a size concentrated at 400-700 nm.
8. A method for adsorbing heavy metal ions Pb in comprehensive wastewater of garbage power plant by using composite material as claimed in claim 7 2+ The application of the catalyst as an adsorbent.
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