CN114289019B - Magnetic iron-carbon composite material and preparation and application methods thereof - Google Patents
Magnetic iron-carbon composite material and preparation and application methods thereof Download PDFInfo
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Abstract
The invention discloses a magnetic iron-carbon composite material and a preparation and application method thereof. The preparation method comprises the following steps: carrying out hydrothermal reaction on a mixed aqueous solution of ferric salt and fumaric acid at 60-90 ℃ to obtain an iron-based precursor; calcining the iron-based precursor at 350-750 ℃ in an inert atmosphere to obtain the magnetic iron-carbon composite material. The magnetic iron-carbon composite material can be synthesized by a two-step method at low cost, has ultrahigh specific surface area and porosity, has a large number of active sites, is easy to capture and degrade the aggregated organic pollutants in a short time, has good magnetic separation efficiency, can be recycled, is environment-friendly, and does not produce secondary environmental pollution.
Description
Technical Field
The invention relates to the technical field of magnetic iron-carbon composite materials.
Background
In recent years, endocrine disruptors (Endocrine disruptors, EDS) have been continuously detected in water environments, sediments, and drinking water. EDS can interfere with the synthesis of natural hormones in organisms, creating a hazard to the reproductive system and immune system. Bisphenol a (BPA) is a typical estrogenic substance in the environment, and is widely used in the production of plasticizers, polycarbonate plastics and other chemicals, and is detected in various water bodies, soils and living goods. Bisphenol A in the environment is mainly derived from two ways, one is leaching of various consumer products containing bisphenol A, and the other is discharge of wastewater in the production process of the products. Bisphenol A has carcinogenic, teratogenic, mutagenic "tri-effect" and is hydrophobic, low in volatility and difficult to degrade. Therefore, there is an urgent need to find an efficient and environmentally friendly method to achieve bisphenol a repair.
Advanced oxidation technology is considered to be one of the practical, rapid, economical and efficient remediation methods for removing organic contaminants from water and soil. Among them, advanced oxidation techniques based on activated Persulfates (PS) have been used for the degradation of various pollutants, in which application sulfate radicals (SO 4 ·- ) Mainly by metal ions, nanomaterials, photo-or thermally activated persulfates. Among these, nanomaterials are distinguished in the technology of activating persulfates by higher specific surface area and reactivity.
However, the traditional nano activated material has the defects of high preparation cost, strict pH range requirement, sludge generation in use, secondary pollution and the like, and is difficult to widely apply in actual production and life.
Such as Kong et al (Kong L, fang G, chen Y, et al efficiency activation of persulfate decomposition by Cu) 2 FeSnS 4 nanomaterial for bisphenol A degradation:Kinetics,performance and mechanism studies[J]Applied Catalysis B: environmental,2019, 253:278-285.) to prepare CTFS (Cu) 2 FeSnS 4 ) Nanomaterial to activate persulfate to degrade bisphenol A, its preparation process includes the use of CuCl 2 ·2H 2 O、FeCl 3 ·6H 2 O、SnCl 4 ·5H 2 O、NH 2 CSNH 2 Carrying out long-time hydrothermal reaction in a high-pressure reaction kettle with a polytetrafluoroethylene lining at a specific ratio to obtain the CTFS material, wherein the CFTS has activated persulfate and generates sulfate radical (SO) 4 ·- ) The method has the advantages of degrading pollutant, having complex and expensive components in the preparation process, having poor recycling property of metal and being difficult to achieve the expected effect.
Or as Lu et al (Gan L, wang L, xu L, et al Fe 3 C-porous carbon derived from Fe 2 O 3 loaded MOF-74(Zn)for the removal of high concentration BPA:The integrations of adsorptive/catalytic synergies and radical/non-radical mechanisms[J]Journal of Hazardous Materials,2021, 413:125305.) proposes loading Fe by pyrolysis 2 O 3 Preparation of novel Fe by MOF-74 (Zn) 3 C-porous carbon composite (Fe) 3 C-C), the Fe 3 The C-C material can activate Peroxymonosulfate (PMS) to degrade bisphenol A with high concentration, the preparation process is also complex, the preparation cost is high, the calcination temperature required in the preparation is high, the energy consumption is high, and the material is difficult to be widely applied in actual production and life.
Or as disclosed in Chinese patent document CN109482233A, a ferrous metal-organic framework material, a normal pressure synthesis method thereof and a method for treating organic pollutants by catalytically activating persulfate, which comprises the steps of mixing terephthalic acid and FeCl under normal pressure 2 ·4H 2 O is dissolved in N, N-dimethylformamide, then methanol is added, hydrofluoric acid is added dropwise to make the solution light green, and then the solution is heated to 100-140 ℃ under nitrogen atmosphere and stirred for reaction. After cooling, the reacted mixture was centrifuged, washed and dried to obtain pale green Fe (II) -MOFs material powder. The Fe (II) -MOFs material has higher ferrous content, has rich unsaturated metal active centers, enhances the effect of persulfate on generating sulfate radical, does not need to consume extra energy, comprises ultrasound, light and electricity, and reduces the cost. However, in the preparation method, solvents of N, N-dimethylformamide and hydrofluoric acid are needed, so that the cost is high, secondary pollution is easy to generate, and the obtained MOFs material has no magnetism, so that the recycling difficulty is increased.
Disclosure of Invention
Aiming at the problems of high cost, poor recycling effect, secondary pollution and the like of the existing activating agent for activating persulfate, the invention aims to provide a novel persulfate activating agent material which can be synthesized by a two-step method at low cost, and a preparation method and an application method thereof.
The invention firstly provides the following technical scheme:
a method for preparing a magnetic iron-carbon composite material, comprising:
carrying out hydrothermal reaction on a mixed aqueous solution of ferric salt and fumaric acid at 60-90 ℃ to obtain an iron-based precursor;
calcining the iron-based precursor at 350-750 ℃ in an inert atmosphere to obtain the magnetic iron-carbon composite material.
According to some preferred embodiments of the invention, the calcination is carried out at a rate of temperature rise of 1.5 to 2.5 ℃/min.
According to some preferred embodiments of the invention, the calcination time is 2 to 4 hours.
According to some preferred embodiments of the invention, the calcination temperature is 350-750 ℃.
According to some preferred embodiments of the invention, the hydrothermal reaction time is 8 to 14 hours.
According to some preferred embodiments of the invention, the ferric salt is selected from one or more of ferric chloride, ferric sulfate, ferric nitrate.
According to some preferred embodiments of the invention, the molar ratio of the trivalent iron salt to the fumaric acid is 1:1.
according to some preferred embodiments of the invention, the solid-to-liquid ratio of the trivalent iron salt to the solvent water in the mixed aqueous solution is 0.02-0.04g/mL.
The invention further provides the magnetic iron-carbon composite material prepared by the preparation method.
The magnetic iron-carbon composite material is Fe 3 C/nano Fe 3 O 4 -graphene nanoplatelets or nano Fe 0 -graphene nanoplatelet composite material in hexagonal rod-like structure.
The invention further provides application of the magnetic iron-carbon composite material prepared by the preparation method to activation of persulfate and degradation of organic pollutants.
According to some preferred embodiments of the invention, the organic contaminant is selected from endocrine disruptors, further, the organic contaminant is selected from estrogens such as bisphenol a.
According to some preferred embodiments of the invention, the application comprises: adding the magnetic iron-carbon composite material and persulfate into the polluted water body containing the organic pollutants, and carrying out degradation reaction at normal temperature and normal pressure.
According to some preferred embodiments of the invention, the persulfate is selected from one or more of sodium persulfate, potassium persulfate, ammonium persulfate.
According to some preferred embodiments of the invention, the molar ratio of the persulfate to the organic contaminant is 1:1 to 50:1, further preferably, is 50:1.
according to some preferred embodiments of the present invention, the amount of the magnetic iron-carbon composite material added to the polluted water body is 0.1-0.5g/L, and more preferably 0.5g/L.
According to some preferred embodiments of the invention, the degradation reaction is carried out at a pH of 3 to 9.
The invention discloses a method for preparing magnetic iron-carbon composite catalyst activated persulfate by a two-step method. The method takes ferric salt as a central metal ion, fumaric acid as an organic ligand and water as a solvent, and prepares the magnetic iron-carbon composite material through a low-temperature hydrothermal-calcining two-step method, and the preparation process is simple and the reaction condition is mild. In addition, in the preparation process, the cost of the raw materials of the MOFs is low, the iron-based materials are widely distributed worldwide, the reserves are rich, and the preparation cost is obviously reduced.
The preparation method of the invention has simple operation and strong repeated operability, can regulate and control the forms of iron and carbon in the catalyst, and prepares Fe 3 C/nano Fe 3 O 4 -graphene nanoplatelets or nano Fe 0 The graphene nano-sheet composite material can activate persulfate at normal temperature to generate sulfate radical, hydroxyl radical or singlet oxygen to efficiently degrade endocrine disruptors.
The preparation method of the invention carries out calcination on the basis of obtaining the iron-based MOFs precursor, increases the specific surface area and the porosity of the material, and can generate Fe 3 C/nano Fe 3 O 4 -graphene nanoplatelets or nano Fe 0 The catalyst taking the graphene nano-sheet composite material as the main active substance, namely the MOFs-derived magnetic iron-carbon composite catalyst, has the specific surface area of the calcined composite material of 8m 3 Increase/g to 117m 3 And/g, a large number of active sites are exposed, the accumulated organic pollutants are easy to capture, and the degradation of the organic pollutants is realized in a shorter time.
The magnetic iron-carbon composite material has magnetism, can be magnetically separated and recycled conveniently, can show a good catalytic effect in a wider pH range, has strong environment interference resistance and has wide application prospect in the aspect of degrading endocrine disruptors
In the magnetic iron-carbon composite material, persulfate can be activated to degrade organic pollutants at normal temperature, the reaction process time is short, and the degradation efficiency is high; meanwhile, the magnetic separation device has good magnetic separation efficiency, reusability, environmental friendliness and no secondary environmental pollution, and has wider application prospect.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) of the MOFs-derived magnetic iron-carbon composite catalyst of example 1.
Fig. 2 is an X-ray crystal diffraction pattern (XRD) of the MOFs-derived magnetic iron-carbon composite catalyst calcined at different temperatures in example 2.
Detailed Description
The present invention will be described in detail with reference to the following examples and drawings, but it should be understood that the examples and drawings are only for illustrative purposes and are not intended to limit the scope of the present invention in any way. All reasonable variations and combinations that are included within the scope of the inventive concept fall within the scope of the present invention.
According to the technical scheme of the invention, the preparation method of the magnetic iron-carbon composite material comprises the following steps:
(1) Ferric salt and fumaric acid are dissolved in deionized water, then transferred to a hydrothermal reaction kettle, placed in a baking oven at 60-90 ℃ for reaction for 8-14 h, naturally cooled to room temperature, and finally an orange solid powder iron-based MOFs precursor is obtained;
(2) And (3) placing the obtained iron-based MOFs precursor into a porcelain boat, placing the porcelain boat into the middle part of a quartz tube of a tube furnace, heating to 350-750 ℃ at a heating rate of 2 ℃/min under the protection of nitrogen, and naturally cooling the porcelain boat after heat preservation for 2-4 hours to obtain the MOFs-derived magnetic iron-carbon composite catalyst, namely the magnetic iron-carbon composite material.
Wherein, the iron-based MOFs precursor obtained in the step (1) is hexagonal rod-shaped crystal, the diameter of which is 450-550nm and the length of which is 4-6 mu m.
The magnetic iron-carbon composite material obtained in the step (2) is Fe 3 C/nano Fe 3 O 4 -graphene nanoplatelets or nano Fe O -graphene nanoplatelet composite material preserving the hexagonal rod-like crystal structure of the precursor.
Among them, it is preferable that,
the ferric salt in the step (1) is selected from ferric chloride (FeCl) 3 ) Ferric sulfate (Fe) 2 (SO 4 ) 3 ) Ferric nitrate (Fe (NO) 3 ) 3 ) One or more of (a) and (b).
The molar ratio of the ferric salt to the fumaric acid in the step (1) is 1:1.
the solid-to-liquid ratio of the ferric salt to the deionized water in the step (1) is 0.02-0.04g/mL.
Further, some specific methods for degrading organic pollutants by the magnetic iron-carbon composite material comprise:
and adding the magnetic iron-carbon composite material to catalyze persulfate to generate sulfate radical, hydroxyl radical or singlet oxygen at normal temperature, and degrading environmental endocrine disruptors in the water body.
Still further, it may include:
adding the magnetic iron-carbon composite material and persulfate into a polluted water body containing estrogen pollutants such as bisphenol A, and carrying out degradation reaction at normal temperature and normal pressure.
Preferably, the method comprises the steps of,
the persulfate is selected from one or more of sodium persulfate, potassium persulfate and ammonium persulfate.
The molar ratio of the persulfate to the pollutant is 1:1-50:1.
the addition amount of the magnetic iron-carbon composite material is 0.1-0.5g/L.
Example 1
Preparing conditions by taking 12h/80 ℃ as an iron-based MOFs precursor, calcining the MOFs-derived magnetic iron-carbon composite catalyst at 550 ℃, and testing the removal effect of the activated persulfate on bisphenol A through the change of the bisphenol A peak area in liquid chromatography. The method specifically comprises the following steps:
(1) Preparation of MOFs derived magnetic iron-carbon composite catalyst: the molar ratio was set to 1:1 FeCl 3 ﹒6H 2 Dissolving O and fumaric acid in ionized water, stirring for half an hour, transferring the solution into a hydrothermal reaction kettle, keeping the temperature at 80 ℃ for 12 hours, cooling the reaction kettle, centrifuging for 8 minutes at 8000rpm, washing with deionized water, and drying in an oven at 80 ℃ to obtain an orange solid powder iron-based MOFs precursor; placing the powder into a porcelain boat, placing the porcelain boat into the middle part of a quartz tube of a tube furnace, heating to 550 ℃ at a heating rate of 2 ℃/min under the protection of nitrogen, and naturally cooling the porcelain boat after heat preservation for 2 hours to obtain the MOFs-derived magnetic iron-carbon composite catalyst which is mainly nano Fe 3 O 4 -graphene nanoplatelet composite.
(2) 40mg/L bisphenol A solution and 50mmol/L persulfate solution were prepared for use.
(3) A conical flask is used as a reactor, 10mL of 40mg/L bisphenol A solution, 0.2mL of 50mmol/L persulfate solution and deionized water are added into the reactor, the volume of the solution in the reactor is kept to be 20mL, meanwhile, 2mg of magnetic iron-carbon composite catalyst is added into the reactor, as a comparison, the magnetic iron-carbon composite catalyst is not added into the reactor, or the persulfate solution is not added into the reactor, and each conical flask is placed in a shaking table of 200rpm for reaction at normal temperature to perform fixed-point sampling analysis.
The removal rates of bisphenol A in the three different reaction systems are shown in the following table:
table 1: bisphenol A removal rate in different reaction systems in example 1
As can be seen from table 1: when MOFs derived magnetic iron-carbon composite catalyst or persulfate is independently added, the removal effect on bisphenol A is very weak; when MOFs derived magnetic iron-carbon composite catalyst and persulfate are added simultaneously, the removal effect of bisphenol A is obviously enhanced, and the catalyst has good activation effect on the persulfate.
And (3) carrying out Scanning Electron Microscope (SEM) characterization on the obtained MOFs-derived magnetic iron-carbon composite catalyst, and as shown in the attached figure 1, the catalyst basically keeps the regular hexagonal rod shape presented by the precursor and has more pore structures on the surface.
Example 2
The iron-based MOFs precursor obtained in the example 1 is calcined at different temperatures (350 ℃,550 ℃ and 750 ℃) to obtain the magnetic iron-carbon composite catalyst with different iron-carbon structures, and the influence of different calcining temperatures on the catalytic activation reaction is tested. The method specifically comprises the following steps:
(1) Preparation of the catalyst at different calcination temperatures: placing the iron-based MOFs precursor into a porcelain boat, placing the porcelain boat into the middle of a quartz tube of a tube furnace, respectively heating to 350 ℃,550 ℃ and 750 ℃ at a heating rate of 2 ℃/min under the protection of nitrogen, and naturally cooling the porcelain boat after heat preservation for 2 hours, wherein magnetic Fe is mainly obtained by calcination at 350 DEG C 3 C material (MOFs-350), and calcining at 550 ℃ mainly to obtain magnetic nano Fe 3 O 4 Graphene nanoplatelet composite (MOFs-550) calcined at 750 ℃ to obtain mainly magnetic nano Fe 0 -graphene nanoplatelet composites (MOFs-750).
(2) 40mg/L bisphenol A solution and 50mmol/L persulfate solution were prepared for use.
(3) A conical flask is used as a reactor, 10mL of 40mg/L bisphenol A solution, 0.2mL of 50mmol/L persulfate solution and deionized water are added into the reactor, the volume of the solution in the reactor is kept to be 20mL, 2mg of MOFs-350 catalyst, MOFs-550 catalyst or MOFs-750 catalyst is added into the reactor, and each conical flask is placed in a shaking table of 200rpm for reaction at normal temperature, so that fixed-point sampling analysis is performed.
The bisphenol A removal rates under the three different catalyst conditions are shown in the following table:
table 2: bisphenol A removal rate at different catalysts
As can be seen from table 2: when the calcination temperature is increased from 350 ℃ to 550 ℃, the removal rate of bisphenol A is in an increasing trend; when the calcination temperature is increased from 550 ℃ to 750 ℃, the removal rate of bisphenol A tends to decrease; the bisphenol A removal effect is best at 550℃as the optimum calcination temperature.
X-ray diffraction (XRD) characterization is carried out on the MOFs-derived magnetic iron-carbon composite catalyst calcined at different temperatures, and as shown in figure 2, the position of the peak of the catalyst is compared with that of the existing Fe 0 And Fe (Fe) 3 O 4 The peak positions in the PDF card are well matched.
Example 3
The MOFs derived magnetic iron-carbon composite catalyst obtained in example 1 was used to test the degradation effect of different catalyst addition amounts (0.2 mg, 1mg, 2mg, 10 mg) on bisphenol A. The method specifically comprises the following steps:
(1) 40mg/L bisphenol A solution and 50mmol/L persulfate solution were prepared for use.
(2) Using conical flasks as reactors, adding 10mL of bisphenol A solution and 0.2mL of persulfate solution with the concentration of 50mmol/L and deionized water with the concentration of the persulfate solution with the concentration of 20mL in the reactors, simultaneously adding 0.2mg of catalyst or 1mg of catalyst or 2mg of catalyst or 10mg of catalyst into the reactors, placing the conical flasks in a shaking table with the concentration of 200rpm, reacting at normal temperature, and then performing fixed-point sampling analysis.
The bisphenol A removal rates at the four different catalyst addition amounts are shown in the following table:
table 3: bisphenol A removal rate under different catalyst addition amounts
As can be seen from table 3: with the increase of the adding amount of the MOFs-derived magnetic iron-carbon composite catalyst, the bisphenol A removal rate is in an ascending trend, and when the adding amount is increased to 10mg, the bisphenol A removal rate reaches equilibrium in a short time. Considering the removal effect and the removal cost comprehensively, 2mg is the optimal addition amount of the catalyst.
Example 4
The MOFs derived magnetic iron-carbon composite catalyst obtained in example 1 was used to test the degradation effect of different persulfate addition amounts (0.04 mL, 0.2mL, 0.4mL, 0.8mL, 2 mL) on bisphenol A. The method specifically comprises the following steps:
(1) Preparing 40mg/L bisphenol A solution and 50mmol/L persulfate solution for later use;
(2) Using a conical flask as a reactor, 10mL of 40mg/L bisphenol a solution and 0.04mL, or 0.2mL, or 0.4mL, or 0.8mL, or 2mL of 50mmol/L persulfate solution, and deionized water were added to the multiple reactors, keeping the volume of the solution in the reactor at 20mL, while 0.2mg of catalyst was added to the reactor. The flask was placed in a 200rpm shaker, the reaction was performed at normal temperature, and then fixed-point sampling analysis was performed.
The removal rate of bisphenol A under the above five different persulfate addition amounts is shown in the following table:
table 4: bisphenol A removal rate at different Persulfate (PS) addition levels
As can be seen from table 4: with the increase of the addition amount of the persulfate solution, the removal rate of bisphenol A is in an ascending trend, and when the addition amount is increased to 2mL, the removal rate of bisphenol A reaches equilibrium in a shorter time. Considering the removal effect and the removal cost comprehensively, 0.2mL is the optimal addition amount of the persulfate solution.
Example 5
The MOFs-derived magnetic iron-carbon composite catalyst obtained in example 1 was used to investigate the degradation effect of different reaction solutions pH (ph=3, ph=5, ph=7, ph=9) on bisphenol a. The method specifically comprises the following steps:
(1) 40mg/L bisphenol A solution and 50mmol/L persulfate solution were prepared for use.
(2) Using a conical flask as a reactor, adding 10mL of bisphenol a solution and 0.2mL of persulfate solution at 50mmol/L and deionized water to a plurality of reactors, keeping the volume of the solution in the reactors at 20mL, adding 0.2mg of catalyst to the reactors, and adjusting the pH of the solution in each reactor to be ph=3, ph=5, ph=7, or ph=9, respectively. Each conical flask was placed in a 200rpm shaker, and the reaction was performed at room temperature, after which point sampling analysis was performed.
The bisphenol a removal rates at the above four different solution pH are shown in the following table:
table 5: bisphenol A removal rate under different solution pH conditions
As can be seen from table 5: bisphenol A exhibits good degradation effect when the pH of the reaction solution is 3-9, but the bisphenol A removal efficiency is stronger when the reaction condition of the solution is acidic.
Example 6
Using the MOFs-derived magnetic iron-carbon composite catalyst obtained in example 1, the coexistence of anions (Cl) in the reaction solution was investigated - ) The degradation effect of the concentration (5 mmol/L, 50mmol/L, 100 mmol/L) on bisphenol A. The method specifically comprises the following steps:
(1) 40mg/L bisphenol A solution, 50mmol/L persulfate solution, and 1mol/LNaCl solution were prepared for use.
(2) A conical flask was used as a reactor, 10mL of 40mg/L bisphenol A solution, 0.2mL of 50mmol/L persulfate solution, and 0.1mL, 1mL, or 2mL of 1mol/L NaCl, and deionized water were added to each of the reactors, keeping the volume of the solution in the reactor at 20mL, and simultaneously adding 0.2mg of catalyst to the reactor. Each flask was placed in a 200rpm shaker, and the reaction was performed at room temperature, followed by fixed-point sampling analysis.
In the above three different Cl - Bisphenol A removal rates at the concentrations shown in the following table:
table 6: different Cl - Bisphenol A removal at concentration
As can be seen from table 6: along with Cl - The removal rate of bisphenol A decreases with increasing concentration. Cl in solution - Has stronger inhibition effect on the degradation of bisphenol A.
Example 7
Using the MOFs-derived magnetic iron-carbon composite catalyst obtained in example 1, the coexistence of anions (NO 3 - ) The degradation effect of the concentration (5 mmol/L, 50mmol/L, 100 mmol/L) on bisphenol A. The method specifically comprises the following steps:
(1) Preparing 40mg/L bisphenol A solution, 50mmol/L persulfate solution and 1mol/LNaNO 3 The solution was ready for use.
(2) Using a conical flask as a reactor, adding 10mL of 40mg/L bisphenol A solution and 0.2mL of 50mmol/L persulfate solution to the multiple reactors, and adding 1mol/LNaNO to each reactor 3 0.1mL, 1mL or 2mL, and deionized water,the volume of solution in the reactor was maintained at 20mL while 0.2mg of catalyst was added to the reactor. The conical flask was placed in a 200rpm shaker and reacted at room temperature, and the samples were taken and analyzed at fixed points.
At the above three different NO 3 - Bisphenol A removal rates at the concentrations shown in the following table:
table 7: different NO 3 - Bisphenol A removal at concentration
As can be seen from table 7: with NO 3 - The removal rate of bisphenol A was not significantly changed by the increase of the concentration. NO in solution 3 - Has no significant effect on the degradation of bisphenol A.
Example 8
Using the MOFs-derived magnetic iron-carbon composite catalyst obtained in example 1, the coexistence of anions (HCO) in the reaction solution was investigated 3 - ) The degradation effect of the concentration (5 mmol/L, 50mmol/L, 100 mmol/L) on bisphenol A. The method specifically comprises the following steps:
(1) Preparation of 40mg/L bisphenol A solution, 50mmol/L persulfate solution, 1mol/LNaHCO 3 The solution was ready for use.
(2) A conical flask was used as a reactor, 10mL of 40mg/L bisphenol A solution, 0.2mL of 50mmol/L persulfate solution were added to the multiple reactors, and 1mol/LNaHCO was added, respectively 3 0.1mL, 1mL, or 2mL, and deionized water, the volume of solution in the reactor was maintained at 20mL while 0.2mg of catalyst was added to the reactor. Each conical flask was placed in a 200rpm shaker and reacted at room temperature, and was sampled and analyzed at fixed points.
In the above three different HCO 3 - Bisphenol A removal rates at the concentrations shown in the following table:
table 8: different HCO 3 - Bisphenol A removal at concentration
As can be seen from table 8: HCO in solution 3 - The degradation of bisphenol A is obviously inhibited by the addition of the components. But with HCO 3 - The concentration is increased, and the inhibition effect is weakened. HCO at low concentration 3 - The degradation effect of bisphenol A is more obvious.
Example 9
Using the MOFs-derived magnetic iron-carbon composite catalyst obtained in example 1, the coexistence of anions (H) 2 PO 4 - ) The degradation effect of the concentration (5 mmol/L, 50mmol/L, 100 mmol/L) on bisphenol A. The method specifically comprises the following steps:
(1) Preparation of 40mg/L bisphenol A solution, 50mmol/L persulfate solution, 1mol/LNaH 2 PO 4 The solution is ready for use;
(2) Using conical flask as reactor, adding 40mg/L bisphenol A solution 10mL, 50mmol/L persulfate solution 0.2mL, and adding 1mol/L NaH respectively 2 PO 4 0.1mL, 1mL, or 2mL, and deionized water, the volume of solution in the reactor was maintained at 20mL while 0.2mg of catalyst was added to the reactor. Each conical flask was placed in a 200rpm shaker, reacted at normal temperature, and sampled and analyzed at fixed points.
In the three different H 2 PO 4 - Bisphenol A removal rates at the concentrations shown in the following table:
table 9: different H 2 PO 4 - Bisphenol A removal at concentration
As can be seen from table 9: h in solution 2 PO 4 - The degradation of bisphenol A is obviously inhibited by the addition of the components. But with H 2 PO 4 - The concentration is increased, and the inhibition effect tends to be enhanced. High concentration of H 2 PO 4 - The degradation effect of bisphenol A is more obvious.
The above examples are only preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the concept of the invention belong to the protection scope of the invention. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be within the scope of the present invention.
Claims (7)
1. The application of the magnetic iron-carbon composite material in activating persulfate and degrading organic pollutants is characterized in that the magnetic iron-carbon composite material is prepared by the following steps:
(1) Dissolving ferric salt and fumaric acid in deionized water, transferring to a hydrothermal reaction kettle, placing into a 60-90 ℃ oven for reaction for 8-14 h, and naturally cooling to room temperature to obtain an orange solid powder iron-based MOFs precursor;
(2) Placing the obtained iron-based MOFs precursor into a porcelain boat, placing the porcelain boat into the middle part of a quartz tube of a tube furnace, heating to 350-750 ℃ at a heating rate of 2 ℃/min under the protection of nitrogen, and naturally cooling the porcelain boat after heat preservation for 2-4 hours to obtain the MOFs-derived magnetic iron-carbon composite catalyst, namely the magnetic iron-carbon composite material;
wherein, the iron-based MOFs precursor obtained in the step (1) is hexagonal rod-shaped crystal, the diameter of which is 450-550nm and the length of which is 4-6 mu m;
the magnetic iron-carbon composite material obtained in the step (2) is Fe 3 C/nano Fe 3 O 4 -graphene nanoplatelets or nano Fe O -graphene nanoplatelet composite material preserving the hexagonal rod-like crystal structure of the precursor.
2. The use according to claim 1, characterized in that the ferric salt is selected from one or more of ferric chloride, ferric sulphate, ferric nitrate.
3. The use according to claim 1, characterized in that the molar ratio of the ferric salt to the fumaric acid is 1:1, a step of; and/or, the solid-to-liquid ratio of the ferric salt to the water is 0.02-0.04g/mL.
4. The use according to claim 1, wherein the organic contaminant is selected from estrogenic endocrine disruptors.
5. The application according to claim 1, characterized in that it comprises: adding the magnetic iron-carbon composite material and persulfate into a polluted water body containing organic pollutants, and carrying out degradation reaction at normal temperature and normal pressure.
6. The use according to claim 5, wherein the persulfates are selected from one or more of sodium persulfate, potassium persulfate, ammonium persulfate.
7. The use according to claim 5, characterized in that the molar ratio of persulfate to organic contaminant is 1:1-50:1, a step of; the adding amount of the magnetic iron-carbon composite material in the polluted water body is 0.1-0.5 g/L; the degradation reaction is carried out under the condition that the pH value is 3-9.
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