CN110841714A - Iron-cobalt bimetal-organic framework material based on 2, 5-dihydroxy terephthalic acid ligand and preparation method and application thereof - Google Patents
Iron-cobalt bimetal-organic framework material based on 2, 5-dihydroxy terephthalic acid ligand and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an iron-cobalt bimetallic-organic framework material based on a 2, 5-dihydroxy terephthalic acid ligand, a preparation method and application thereof, wherein cobalt nitrate hexahydrate, ferrous chloride tetrahydrate and 2, 5-dihydroxy terephthalic acid are dissolved in an organic solvent to obtain a precursor solution; carrying out solvothermal reaction on the precursor solution at the temperature of 110-170 ℃; and after the reaction is finished, carrying out post-treatment to obtain the Fe-Co bimetallic-organic framework material. The highly dispersed active center ions of cobalt and iron in the iron-cobalt bimetallic-organic framework material can enhance the effective contact of the cobalt ions and iron with peroxymonosulfate to generate sulfate radicals with strong oxidizing property, thereby removing the refractory organic pollutants in the wastewater. The iron-cobalt bimetal-organic framework material based on the 2, 5-dihydroxy terephthalic acid ligand is suitable for treating various organic wastewater, has high efficiency, good durability, convenient operation and environmental protection, and provides wide prospect for treating toxic, harmful and nonbiodegradable organic wastewater.
Description
Technical Field
The invention belongs to the technical field of water pollution control, and particularly relates to an iron-cobalt bimetallic-organic framework material based on a 2, 5-dihydroxy terephthalic acid ligand, and a preparation method and application thereof.
Background
With the rapid development of industry, the treatment of water pollution environment becomes a worldwide problem, and the wide existence of refractory organic pollutants makes the water treatment more and more concerned by people. The persistent organic pollutants are difficult to remove by traditional biological, physical and chemical methods due to complex components, stable structure and long half-life. And most of the organic pollutants which are difficult to degrade have certain toxicity and are easy to be retained in organisms, so that people and animals are cancerated, distorted, feminized and the like. The advanced oxidation technology has the characteristics of rapidness, no selectivity, thorough oxidation and the like, has better treatment effect on trace refractory organic pollutants, high-concentration organic wastewater and the like in the environment, and improves an effective solution for solving the environmental problem. Therefore, advanced oxidation technology is becoming the first choice for treating refractory organic pollutants.
In recent years based on SO4 －·The advanced oxidation technology has attracted more and more researchers' attention and research due to the advantages of strong oxidation capability, wide applicable pH range, simple operation and the like. Activation of PS with transition metals to generate free radicals SO4 －·Is the most efficient way. The decomposition of Persulfate (PS) to produce SO with strong oxidizing power4 －·. SO vs. hydroxyl radical (. OH), SO4 －·Having a structure of (. OH, E) with02.6vs. nhe) comparable redox potential, E02.5 to 3.1vs. NHE, and SO4 －·Has better treatment effect on organic wastewater under neutral condition, which makes the organic wastewater based on SO4 －·The advanced oxidation technology of (2) is more prominent in the aspect of water treatment. SO (SO)4 -·Can be produced by decomposition of Peroxodisulfate (PDS) and Peroxomonosulfate (PMS). The radiation, ultraviolet light and high temperature can catalyze PMS to generate SO4 -·However, the transition metal catalytic method does not require an external heat source or light source, and the reaction system is simple, so that the transition metal catalytic method is widely concerned. Metal-Organic Framework Materials (MOFs) are composed ofThe novel material with a periodic structure is obtained by coordination self-assembly of inorganic metal nodes and organic bridging ligands. Recent research shows that MOFs as a heterogeneous catalyst shows outstanding performance in the aspect of pollution environment treatment, and particularly shows great application prospect in the aspect of removing water pollutants.
Disclosure of Invention
The invention provides a Fe-Co bimetallic-organic framework material, a preparation method thereof and application thereof in the field of wastewater treatment, and aims to overcome the problems and disadvantages that treatment processes such as ion exchange, adsorption, precipitation separation and the like are required to be further added to increase the treatment cost and the like because cobalt ions in a cobalt ion activated hydrogen peroxymonosulfate reaction system cannot be recycled and cause secondary pollution to the environment in the prior art.
An iron-cobalt bimetallic-organic framework material (FeCo-DHTA) based on a 2, 5-dihydroxy terephthalic acid ligand is prepared from the following raw material components: cobalt nitrate hexahydrate, ferrous chloride tetrahydrate and 2, 5-dihydroxyterephthalic acid, wherein the molar ratio of the cobalt nitrate hexahydrate, the ferrous chloride tetrahydrate and the 2, 5-dihydroxyterephthalic acid is 4: 1: 2.5-1: 4: 2.5.
preferably, the form of the iron-cobalt bimetallic-organic framework material based on the 2, 5-dihydroxyterephthalic acid ligand is a regular hollow polyhedron or rod-like structure.
The invention also provides a preparation method of the iron-cobalt bimetallic-organic framework material based on the 2, 5-dihydroxy terephthalic acid ligand, which comprises the following steps:
(1) preparing a precursor solution: dissolving cobalt nitrate hexahydrate, ferrous chloride tetrahydrate and 2, 5-dihydroxy terephthalic acid in an organic solvent, and then uniformly mixing to obtain a precursor solution;
(2) preparation of a 2, 5-dihydroxyterephthalic acid ligand-based iron-cobalt bimetallic-organic framework material: carrying out solvothermal reaction on the precursor solution prepared in the step (1) at the temperature of 110-170 ℃; and cooling, washing and drying to obtain the iron-cobalt bimetallic-organic framework material based on the 2, 5-dihydroxy terephthalic acid ligand.
Preferably, the organic solvent is N, N-dimethylformamide and absolute ethyl alcohol, and the volume ratio of the N, N-dimethylformamide to the absolute ethyl alcohol is 1: 1 or 1: 0. the method can effectively reduce the consumption of N, N-dimethylformamide, improve the environmental friendliness, and in addition, avoid using toxic and harmful solvents such as hydrofluoric acid and the like, and has the advantages of simpler and more convenient operation and more environmental friendliness.
Preferably, the solvothermal reaction is carried out in a polytetrafluoroethylene-lined high-pressure reaction kettle, and the solvothermal reaction time is 24-48 h; the washing conditions are as follows: washing the precipitate alternately and repeatedly by adopting absolute ethyl alcohol, N-dimethylformamide and deionized water; the drying conditions are as follows: drying for 12-24 h at 60-100 ℃.
In addition, the invention also provides application of the iron-cobalt bimetallic-organic framework material based on the 2, 5-dihydroxy terephthalic acid ligand in the field of wastewater treatment.
Preferably, the application of the iron-cobalt bimetallic-organic framework material based on 2, 5-dihydroxyterephthalic acid ligand comprises the following steps: adding peroxymonosulfate as oxidant and Fe-Co bimetallic-organic skeleton material based on 2, 5-dihydroxy terephthalic acid ligand as catalyst into waste water to perform waste water treating reaction. The iron-cobalt bimetallic-organic framework material based on the 2, 5-dihydroxy terephthalic acid ligand can efficiently catalyze and activate peroxymonosulfate to quickly and effectively remove toxic, harmful and non-biodegradable organic matters in wastewater.
Preferably, the hydrogen peroxymonosulfate is sodium peroxymonosulfate or potassium peroxymonosulfate.
Preferably, the molar ratio of the peroxymonosulfate to the organic pollutants in the wastewater is 6-300: 1, the adding amount of the iron-cobalt bimetal-organic framework material based on the 2, 5-dihydroxy terephthalic acid ligand is 20-200 mg/L. The adding amount of the peroxymonosulfate is determined according to the concentration of the organic pollutants in the wastewater, and the larger the concentration of the organic pollutants is, the more the adding amount of the peroxymonosulfate is.
Preferably, the temperature of the wastewater treatment reaction is 20-60 ℃, and the time is 2-30 min; the wastewater treatment reaction is carried out under the condition of stirring or oscillation, and the rotating speed of the stirring or oscillation is 50-200 rpm; the wastewater is organic wastewater, and the pH value of the organic wastewater is 3.0-11.0.
The principle of the invention is as follows: the invention provides a water treatment technology for efficiently activating peroxymonosulfate by using an iron-cobalt bimetal-organic framework material based on a 2, 5-dihydroxy terephthalic acid ligand, which is characterized in that the iron-cobalt bimetal-organic framework material based on the 2, 5-dihydroxy terephthalic acid ligand is used as a heterogeneous catalyst of the peroxymonosulfate, the heterogeneous catalyst reacts with organic wastewater to be treated in the presence of the iron-cobalt bimetal-organic framework material based on the 2, 5-dihydroxy terephthalic acid ligand and the peroxymonosulfate, the iron-cobalt bimetal-organic framework material based on the 2, 5-dihydroxy terephthalic acid ligand is uniformly dispersed, and iron ions and cobalt metal ions can efficiently activate the peroxymonosulfate to generate SO with strong oxidizing property4 -·Further, the purpose of efficiently removing the organic pollutants difficult to degrade can be achieved. The reaction can be carried out within a wider pH value range, the using amount of the catalyst is small, the reaction time is short, and meanwhile, the method has the advantages of high catalytic oxidation rate, simple equipment, convenience in operation, environmental friendliness, easiness in recycling of the catalyst and the like, and has great application potential in the field of advanced treatment of wastewater.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation method of the iron-cobalt bimetallic-organic framework material provided by the invention is simple, the reaction condition is mild, no special requirement is required on the external environment condition, the operation is simple, the repeatability is strong, and the implementation is easy;
(2) the iron-cobalt bimetallic-organic framework material based on the 2, 5-dihydroxyterephthalic acid ligand, which is provided by the invention and used as a heterogeneous catalyst for activating peroxymonosulfate, can be applied to wastewater treatment, and the iron-cobalt bimetallic-organic framework material based on the 2, 5-dihydroxyterephthalic acid ligand is applied to the reaction for treating organic pollutants by an advanced oxidation method based on sulfate radicals for the first time; iron ions and cobalt ions in the iron-cobalt bimetal-organic framework material based on the 2, 5-dihydroxy terephthalic acid ligand are uniformly dispersed in the framework material, so that the catalytic activity can be obviously improved, the invention fully utilizes highly dispersed cobalt and iron active central ions in the iron-cobalt bimetal-organic framework material based on the 2, 5-dihydroxy terephthalic acid ligand, and enhances the effective contact of transition metal ions and peroxymonosulfate to enhance the generation of sulfate radicals with strong oxidizing property, thereby accelerating the oxidative degradation of refractory organic pollutants in wastewater; the iron-cobalt bimetallic-organic framework material of the 2, 5-dihydroxy terephthalic acid ligand with high catalytic activity enables the peroxymonosulfate to be effectively decomposed to generate sulfate radicals, the utilization rate of the radicals is high, the reaction time is short, and the removal effect on pollutants is good;
(3) the method adopts the Fe-Co bimetallic-organic framework material as the heterogeneous phase catalyst to catalyze the peroxymonosulfate, and has high catalytic activity within the pH range of 3.0-11.0, so that the pH value of the wastewater suitable for treatment is greatly widened, and the acid-base adjusting cost is effectively reduced;
(4) the invention adopts the iron-cobalt bimetallic-organic framework material based on the 2, 5-dihydroxy terephthalic acid ligand as the heterogeneous catalyst, has high activity and less dosage, can efficiently catalyze the peroxymonosulfate at normal temperature without illumination and other conditions, reduces the cost of sewage treatment, and ensures that the catalyst is easier to recycle from the solution after reaction and has no secondary pollution;
(5) the method has the advantages of simple operation, easily controlled conditions, high catalytic efficiency, economy and feasibility, and is suitable for the advanced treatment of various organic wastewater;
(6) the method still keeps higher pollutant removal rate under the condition of higher pH, is suitable for treating various organic wastewater, has high efficiency, good durability, convenient operation and environmental protection, can efficiently remove toxic and harmful pollutants in the wastewater within a wider pH range, and provides wide prospects for treating the toxic, harmful and nonbiodegradable organic wastewater.
Drawings
FIG. 1 is a scanning electron microscope image of a 2, 5-dihydroxyterephthalic acid ligand-based Fe-Co bimetallic-organic framework material prepared under 150 ℃ conditions according to the present invention at a magnification of 1000 ten thousand times;
FIG. 2 is a scanning electron microscope image of a 2, 5-dihydroxyterephthalic acid ligand-based Fe-Co bimetallic-organic framework material prepared under 110 ℃ conditions according to the present invention at a magnification of 500 ten thousand times;
FIG. 3 is a scanning electron microscope image of a 2, 5-dihydroxyterephthalic acid ligand-based Fe-Co bimetallic-organic framework material prepared under 170 ℃ conditions according to the present invention at a magnification of 1000 ten thousand times;
FIG. 4 is an X-ray crystal diffraction pattern of a 2, 5-dihydroxyterephthalic acid ligand-based Fe-Co bimetallic-organic framework material prepared under 150 ℃ conditions in accordance with the present invention;
fig. 5 is an infrared spectrum of a 2, 5-dihydroxyterephthalic acid ligand-based iron-cobalt bimetallic-organic framework material prepared under 150 ° conditions according to the present invention.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited thereto.
Cobalt nitrate hexahydrate (Co (NO) used in examples of the present invention3)2·6H2O), ferrous chloride tetrahydrate (Cu (NO)3)2)2, 5-dihydroxyterephthalic acid (C)8H6O6) N, N-dimethylformamide (DMF, C)3H7NO), absolute ethanol (C)2H6O), potassium hydrogen peroxymonosulfate and the like are analytically pure, methylene blue is chromatographically pure, and the used water is deionized water.
According to statistics, the variety of the dyes for commercial use exceeds 100000, the annual output of the dyes in the world is about 80 ten thousand to 90 ten thousand tons, while the annual output of the dyes in China is about 15 ten thousand tons, and the dye output in the world is in the forefront. Wherein 10% to 15% of the dye is released into the environment during production and use. Most dyes are extremely stable and are difficult to naturally degrade after entering a water body, so that the chromaticity of a polluted water area is increased, the quantity of incident light is influenced, the normal life activities of aquatic animals and plants in the water body are further influenced, and the ecological balance of the water environment is damaged. More seriously, most dyes have carcinogenic and teratogenic effects and are discharged into aqueous environments to pose significant harm to humans and other organisms. The invention considers that the dye is widely applied to industries such as medicine, food, printing and dyeing, cosmetic manufacturing and the like. Therefore, the invention selects and uses wider Methylene Blue (MB) as a representative of pollutants, and researches on decolorization and degradation of the MB can represent degradation of the organic wastewater difficult to biochemically degrade to a certain extent. Therefore, the MB solution is used as the organic wastewater in the following examples.
The method is adopted to treat the organic wastewater containing Methylene Blue (MB).
Example 1
Preparation of Fe-Co bimetallic-organic framework material
(1) Preparing a precursor solution: 0.873g (3mM) of Co (NO)3)2·6H2O、0.596g(3mM)FeCl2·4H2Dissolving O and 0.498g (3mM) of 2, 5-dihydroxyterephthalic acid (DTPA) in 60mL of a mixture of N, N-Dimethylformamide (DMF) and ethanol (DMF: ethanol ═ 1: 1), and stirring the mixture until the mixture is completely dissolved to obtain a precursor solution;
(2) iron-cobalt bimetallic-organic framework materials based on 2, 5-dihydroxyterephthalic acid ligands: transferring the precursor solution prepared in the step (1) into a 100mL high-pressure reaction kettle with a polytetrafluoroethylene lining, putting the reaction kettle into a program-controlled oven, and carrying out solvothermal reaction for 24h at 150 ℃; cooling, naturally cooling to room temperature, filtering by a vacuum pump, and repeatedly washing with absolute ethyl alcohol, N-Dimethylformamide (DMF) and deionized water to obtain a coffee precipitate; and (3) drying the precipitate in a vacuum drying oven at 100 ℃ for 12h to obtain black solid powder, namely the Fe-Co bimetallic-organic framework material based on the 2, 5-dihydroxy terephthalic acid ligand.
Scanning electron microscope, X-ray crystal diffraction and infrared are adopted to characterize the iron-cobalt bimetal-organic framework material, wherein fig. 1 is a scanning electron microscope image with the magnification of 1000 ten thousand times of the iron-cobalt bimetal-organic framework material in the embodiment, fig. 4 is an X-ray crystal diffraction pattern of the iron-cobalt bimetal-organic framework material in the embodiment, and fig. 5 is an infrared spectrogram of the iron-cobalt bimetal-organic framework material in the embodiment. From the above illustration, the invention really prepares the Fe-Co bimetallic-organic framework material, the shape of which is regular polyhedral crystal, and ICP-MS detection results show that the molar ratio of the Co element to the Fe element in the material prepared by the preparation method is close to 1: 1, indicating that the Fe-Co bimetallic-organic framework material is successfully prepared.
Example 2
(1) Preparing a precursor solution: 0.873g (3mM) of Co (NO)3)2·6H2O、0.596g(3mM)FeCl2·4H2Dissolving O and 0.498g (3mM) of 2, 5-dihydroxyterephthalic acid (DTPA) in 60mL of a mixture of N, N-Dimethylformamide (DMF) and ethanol (DMF: ethanol ═ 1: 1), and stirring the mixture until the mixture is completely dissolved to obtain a precursor solution;
(2) iron-cobalt bimetallic-organic framework materials based on 2, 5-dihydroxyterephthalic acid ligands: transferring the precursor solution prepared in the step (1) into a 100mL high-pressure reaction kettle with a polytetrafluoroethylene lining, putting the reaction kettle into a program-controlled oven, and carrying out solvothermal reaction for 24h at 110 ℃; cooling, naturally cooling to room temperature, filtering by a vacuum pump, and repeatedly washing with absolute ethyl alcohol, N-Dimethylformamide (DMF) and deionized water to obtain a coffee precipitate; and (3) drying the precipitate in a vacuum drying oven at 100 ℃ for 12h to obtain black solid powder, namely the Fe-Co bimetallic-organic framework material based on the 2, 5-dihydroxy terephthalic acid ligand.
Scanning electron microscopy is adopted to characterize the iron-cobalt bimetal-organic framework material, wherein fig. 2 is a scanning electron microscopy image with the magnification of 500 ten thousand times of the iron-cobalt bimetal-organic framework material in the embodiment.
Example 3
(1) Preparing a precursor solution: 0.873g (3mM) of Co (NO)3)2·6H2O、0.596g(3mM)FeCl2·4H2Dissolving O and 0.498g (3mM) of 2, 5-dihydroxyterephthalic acid (DTPA) in 60mL of a mixture of N, N-Dimethylformamide (DMF) and ethanol (DMF: ethanol ═ 1: 1), and stirring the mixture until the mixture is completely dissolved to obtain a precursor solution;
(2) iron-cobalt bimetallic-organic framework materials based on 2, 5-dihydroxyterephthalic acid ligands: transferring the precursor solution prepared in the step (1) into a 100mL high-pressure reaction kettle with a polytetrafluoroethylene lining, putting the reaction kettle into a program-controlled oven, and carrying out solvothermal reaction for 24h at 170 ℃; cooling, naturally cooling to room temperature, filtering by a vacuum pump, and repeatedly washing with absolute ethyl alcohol, N-Dimethylformamide (DMF) and deionized water to obtain a coffee precipitate; and (3) drying the precipitate in a vacuum drying oven at 100 ℃ for 12h to obtain black solid powder, namely the Fe-Co bimetallic-organic framework material based on the 2, 5-dihydroxy terephthalic acid ligand.
Scanning electron microscopy is adopted to characterize the iron-cobalt bimetal-organic framework material, wherein fig. 3 is a scanning electron microscopy image of the iron-cobalt bimetal-organic framework material with the magnification of 1000 ten thousand times in the embodiment.
Example 4
The removal rate of MB under the condition of adding the Fe-Co bimetal-organic framework material based on the 2, 5-dihydroxyterephthalic acid ligand and potassium peroxymonosulfate, or the Fe-Co bimetal-organic framework material based on the 2, 5-dihydroxyterephthalic acid ligand or potassium peroxymonosulfate
A conical flask is adopted as a reactor, the reaction volume of the wastewater is 100mL, the initial concentration of the wastewater containing methylene blue is 0.2mM, and the pH value is 6.1; three processing groups were set: wherein, the processing group 1 simultaneously adds the iron-cobalt bimetallic-organic framework material (prepared by the method of example 1) based on the 2, 5-dihydroxyterephthalic acid ligand and the potassium peroxymonosulfate (the final concentrations are respectively 0.05g/L and 2mM) into a reaction bottle, and the processing group 2 separately adds the iron-cobalt bimetallic-organic framework material (the final concentration is 0.1g/L) based on the 2, 5-dihydroxyterephthalic acid ligand without adding the potassium peroxymonosulfate; treatment group 3 added potassium hydrogen peroxymonosulfate alone (final concentration of 2mM) without the addition of an iron cobalt bimetallic-organic framework material based on 2, 5-dihydroxyterephthalic acid ligand; placing the three reaction bottles in a shaking bed, reacting at the rotation speed of 100rpm and the temperature of 25 ℃, detecting the MB content in the reaction system at regular time, and calculating the MB removal rate; the results of comparing the MB removal rates for the different treatment groups are shown in table 1.
TABLE 1
The results in table 1 show that both the iron-cobalt bimetallic-organic framework material based on the 2, 5-dihydroxyterephthalic acid ligand alone and the potassium peroxymonosulfate system alone can not effectively degrade and remove the MB, while the iron-cobalt bimetallic-organic framework material based on the 2, 5-dihydroxyterephthalic acid ligand activates the potassium peroxymonosulfate system to have a very significant treatment effect on the MB, and after the reaction is carried out for 30min, the removal rate of the MB reaches 98.2%, which indicates that the method can quickly and effectively treat the wastewater difficult to be biochemically treated.
Example 5
Removal rate of MB (methyl methacrylate) under acidic, neutral and alkaline conditions by activating potassium peroxymonosulfate through iron-cobalt bimetal-organic framework material based on 2, 5-dihydroxy terephthalic acid ligand
A conical flask is adopted as a reactor, the reaction volume of the wastewater is 100mL, and the initial concentration of MB contained in the wastewater is 0.2 mM; four processing groups are set: adding potassium hydrogen peroxymonosulfate into a reaction bottle before the reaction starts to enable the concentration of the potassium hydrogen peroxymonosulfate to be 2mM, respectively adjusting the pH value of wastewater to be 3.0 (treatment group 1), 5.0 (treatment group 2), 7.0 (treatment group 3), 9.0 (treatment group 4) and 11.0 (treatment group 5), then adding an iron-cobalt bimetal-organic framework material based on a 2, 5-dihydroxy terephthalic acid ligand (prepared by the method of example 1) into the reaction bottle to enable the reaction concentration to be 0.05g/L, placing the reaction bottle into a shaking bed, carrying out reaction under the conditions that the rotating speed is 100rpm and the temperature is 25 ℃, regularly detecting the MB content in the reaction system, and calculating the MB removal rate; the results of the effect of pH on the degradation of MB by activating potassium peroxymonosulfate of an iron-cobalt bimetallic-organic framework material based on 2, 5-dihydroxyterephthalic acid ligands are shown in table 2.
TABLE 2
The results in table 2 show that the oxidation method of activating potassium peroxymonosulfate by the iron-cobalt bimetallic-organic framework material has a very good degradation effect on MB under acidic and near-neutral conditions, saves the acid feeding cost, and ensures the high efficiency of the advanced oxidation technology. The treatment effect is best under the condition that the pH value is 5.0, the dosage of the iron-cobalt bimetallic-organic framework material based on the 2, 5-dihydroxyterephthalic acid ligand is small, and the activation efficiency is high.
Example 6
Influence of different adding amounts of iron-cobalt bimetal-organic framework materials on MB removal rate based on 2, 5-dihydroxy terephthalic acid ligand
Using a conical flask as a reactor, the reaction volume of wastewater was 100mL, the initial concentration of MB in the wastewater was 0.2mM, pH was 6.1, potassium monopersulfate was added to the reaction flask to a concentration of 2mM before the start of the reaction, and four treatment groups were set: wherein, adding a Fe-Co bimetallic-organic framework material (prepared by the method of example 3) based on a 2, 5-dihydroxyterephthalic acid ligand into a reaction bottle to ensure that the reaction concentration is 0.05g/L (treatment group 1), 0.1g/L (treatment group 2), 0.2g/L (treatment group 3) and 0.3g/L (treatment group 4), finally placing the reaction bottle into a shaking bed, carrying out reaction under the conditions of the rotating speed of 100rpm and the temperature of 25 ℃, regularly detecting the MB content in the reaction system, and calculating the MB removal rate; the effect of the concentration of the iron-cobalt bimetallic-organic framework material based on 2, 5-dihydroxyterephthalic acid ligand on the degradation of MB by activated potassium hydrogen peroxymonosulfate results are shown in table 3.
TABLE 3
The results in Table 3 show that the concentration of the Fe-Co bimetallic-organic framework material based on the 2, 5-dihydroxyterephthalic acid ligand has certain influence on the degradation of MB by activated potassium peroxymonosulfate, the degradation rate of MB is increased along with the increase of the concentration of the Fe-Co bimetallic-organic framework material, the degradation rate of MB is highest when the concentration of the Fe-Co bimetallic-organic framework material based on the 2, 5-dihydroxyterephthalic acid ligand is 0.1g/L, and MB is degraded within 10min by 100%. The iron-cobalt bimetallic-organic framework material based on the 2, 5-dihydroxy terephthalic acid ligand has high activity and small dosage. Therefore, the method has wide application prospect in organic wastewater difficult to biochemically treat.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. An iron-cobalt bimetallic-organic framework material based on a 2, 5-dihydroxy terephthalic acid ligand is characterized by being prepared from the following raw material components: cobalt nitrate hexahydrate, ferrous chloride tetrahydrate and 2, 5-dihydroxyterephthalic acid, wherein the molar ratio of the cobalt nitrate hexahydrate, the ferrous chloride tetrahydrate and the 2, 5-dihydroxyterephthalic acid is 4: 1: 2.5-1: 4: 2.5.
2. the iron-cobalt bimetallic-organic framework material based on 2, 5-dihydroxyterephthalic acid ligands according to claim 1, characterized in that: the shape of the iron-cobalt bimetal-organic framework material is a regular hollow polyhedron or rod-shaped structure.
3. A method for preparing a 2, 5-dihydroxyterephthalic acid ligand-based iron-cobalt bimetallic-organic framework material according to claim 1, characterized by comprising the following steps:
(1) preparing a precursor solution: dissolving cobalt nitrate hexahydrate, ferrous chloride tetrahydrate and 2, 5-dihydroxy terephthalic acid in an organic solvent, and then uniformly mixing to obtain a precursor solution;
(2) preparation of a 2, 5-dihydroxyterephthalic acid ligand-based iron-cobalt bimetallic-organic framework material: carrying out solvothermal reaction on the precursor solution prepared in the step (1) at the temperature of 110-170 ℃; and cooling, washing and drying to obtain the iron-cobalt bimetallic-organic framework material based on the 2, 5-dihydroxy terephthalic acid ligand.
4. The method of preparing a 2, 5-dihydroxyterephthalic acid ligand-based Fe-Co bimetallic-organic framework material according to claim 3, characterized in that: the organic solvent is N, N-dimethylformamide and absolute ethyl alcohol, and the volume ratio of the N, N-dimethylformamide to the absolute ethyl alcohol is 1: 1 or 1: 0.
5. the method of preparing a 2, 5-dihydroxyterephthalic acid ligand-based Fe-Co bimetallic-organic framework material according to claim 3, characterized in that: the solvothermal reaction is carried out in a high-pressure reaction kettle with a polytetrafluoroethylene lining, and the solvothermal reaction time is 24-48 hours; the washing conditions are as follows: washing the precipitate alternately and repeatedly by adopting absolute ethyl alcohol, N-dimethylformamide and deionized water; the drying conditions are as follows: drying for 12-24 h at 60-100 ℃.
6. Use of a Fe-Co bimetallic-organic framework material based on 2, 5-dihydroxyterephthalic acid ligands according to claim 1 in the field of wastewater treatment.
7. Use of a 2, 5-dihydroxyterephthalic acid ligand-based Fe-Co bimetallic-organic framework material according to claim 6, characterized in that it comprises the following steps: adding peroxymonosulfate as oxidant and Fe-Co bimetallic-organic skeleton material based on 2, 5-dihydroxy terephthalic acid ligand as catalyst into waste water to perform waste water treating reaction.
8. Use of an iron-cobalt bimetallic-organic framework material based on 2, 5-dihydroxyterephthalic acid ligands according to claim 7, characterized in that: the hydrogen peroxymonosulfate is sodium peroxymonosulfate or potassium peroxymonosulfate.
9. Use of an iron-cobalt bimetallic-organic framework material based on 2, 5-dihydroxyterephthalic acid ligands according to claim 8, characterized in that: the molar ratio of the peroxymonosulfate to the organic pollutants in the wastewater is 6-300: 1, the adding amount of the iron-cobalt bimetal-organic framework material based on the 2, 5-dihydroxy terephthalic acid ligand is 20-200 mg/L.
10. Use of an iron-cobalt bimetallic-organic framework material based on 2, 5-dihydroxyterephthalic acid ligands according to claim 7, characterized in that: the temperature of the wastewater treatment reaction is 20-60 ℃, and the time is 2-30 min; the wastewater treatment reaction is carried out under the condition of stirring or oscillation, and the rotating speed of the stirring or oscillation is 50-200 rpm; the wastewater is organic wastewater, and the pH value of the organic wastewater is 3.0-11.0.
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