CN112206828A - Preparation method, product and application of ferrous-doped Fe-MOFs Fenton catalyst - Google Patents
Preparation method, product and application of ferrous-doped Fe-MOFs Fenton catalyst Download PDFInfo
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Abstract
The invention provides a preparation method, a product and an application of a ferrous iron-doped Fe-MOFs Fenton catalyst, wherein the preparation method comprises the following steps: dissolving an organic ligand in a solvent to obtain an organic ligand solution; adding mixed metal salt of ferric salt and ferrous salt into the organic ligand solution, and uniformly stirring to obtain a ferrous-doped Fe-MOFs Fenton catalyst precursor mixed solution; and carrying out solvothermal reaction on the mixed solution, then carrying out solid-liquid separation, and drying a solid phase to obtain the ferrous-doped Fe-MOFs Fenton catalyst. The ferrous iron-doped Fe-MOFs Fenton catalyst can improve the adsorption and catalytic decomposition rate of Fenton-like mass transfer, and the efficiency of catalyzing Fenton-like oxidative degradation and mineralization of organic pollutants in water. The method is applied to the field of organic wastewater pollution treatment, can improve the catalytic Fenton-like activity of Fe-MOFs, promotes the decomposition rate of Fenton-like reaction, and enhances the removal of organic pollutants in water.
Description
Technical Field
The invention belongs to the technical field of organic wastewater pollution enhancement treatment, and particularly relates to a preparation method, a product and application of a ferrous iron-doped Fe-MOFs Fenton catalyst.
Background
In recent years, people have more and more high call for green chemistry and green life, and the problem of industrial water pollution becomes more and more acute. The industrial wastewater is different from the conventional domestic wastewater, mainly contains a large amount of organic additives, intermediates and partial organic micromolecular compounds, and has the outstanding characteristics of complex components, good chemical stability, difficult biodegradation and the like. The advanced treatment technology represented by an advanced oxidation method can form OH species with higher oxidation activity in a system, greatly improves the reaction capacity and the rate of degrading organic matters compared with the traditional direct oxidation, and can achieve the aim of thoroughly oxidizing macromolecular organic matters. Therefore, the advanced oxidation method is one of effective approaches for advanced treatment of printing and dyeing wastewater.
Fenton technology, which is one of the advanced oxidation methods, can exert an excellent oxidation effect on many kinds of organic substances by the combination of hydrogen peroxide and ferrous ions. The fenton technology was rapidly developed in the 70's of the 20 th century and was initially studied for application in the field of industrial wastewater treatment. Nowadays, the research on advanced oxidation methods based on hydrogen peroxide is abundant, and the improvement and innovation of the traditional fenton reagent and the traditional fenton reaction method are the hot spots of the current research.
However, in the field of water pollution control, the conventional fenton reaction has problems that the pH working range is limited to a strong acid environment, and the reaction is accompanied by generation of a large amount of iron sludge. Therefore, in order to overcome the disadvantages of the conventional fenton reactions and improve the economic benefit of the advanced oxidation method of the fenton reaction, a better strategy of the heterogeneous fenton-like reaction is developed, namely, different from the conventional (homogeneous) fenton catalyst of metal salt, transition metal oxide which is insoluble in a reaction system, an iron-based metal organic framework material and some non-metallic carbon materials are adopted as catalysts. The Fenton-like advanced oxidation technology has a wider pH working range, so that the utilization rate of hydrogen peroxide, the oxidation efficiency and the economic benefit are better improved, and the Fenton-like advanced oxidation technology is favored by people.
For the Fenton-like advanced oxidation process, the most important is the catalyst. Transition metal (hydr) oxides, e.g. Fe2O3、Fe3O4、FeOOH、Al2O3、MnO2And Fe (II) O2And the like are commonly used as catalysts for fenton-like reactions. The catalysts have the problems of metal ion precipitation, low specific surface area, weak mass transfer capacity and the like, so that the catalytic efficiency is difficult to effectively improve.
Iron-based metal organic frameworks (Fe-MOFs) materials such as MIL-53(Fe), MIL-88A (Fe), MIL-88B (Fe), MIL-100(Fe) and MIL-101(Fe) are novel Fenton-like catalysts, and the iron-based metal organic frameworks (Fe-MOFs) are good in stability, low in metal ion precipitation rate, uniform and rich in active site distribution, excellent in mass transfer capacity and capable of serving as novel Fenton-like catalysts with good application prospects. However, due to the inherent structure of ferrite nodes, the heterogeneous Fenton performance of the catalyst is limited by the relatively low redox cycle rate of Fe (III)/Fe (II) and the density of coordinated unsaturated metal centers, and the problems of less ideal removal efficiency and mineralization capability of organic pollutants still exist.
Disclosure of Invention
Aiming at the problems that the novel Fe-MOFs have relatively low redox cycle rate and low coordinated unsaturated metal center density due to the inherent structure of ferrite nodes, and the removal and mineralization efficiency of organic pollutants in industrial wastewater is low, the invention aims to provide a preparation method of Fe (II) -doped Fe-MOFs Fenton catalyst.
The invention aims to: providing a Fe (II) doped Fe-MOFs Fenton catalyst product prepared by the method; provides an application of the product.
The purpose of the invention is realized by the following scheme:
a preparation method of a ferrous iron-doped Fe-MOFs Fenton catalyst comprises the step of forming a porous Fe (II) doped Fe-MOFs Fenton catalyst through solvothermal (including hydrothermal or other organic solvothermal) self-assembly of ferrous iron ions doped Fe-MOFs, wherein the Fe-MOFs is an iron-based metal organic framework material. A preparation method of a ferrous iron-doped Fe-MOFs Fenton catalyst comprises the following steps:
(1) dissolving an organic ligand in a solvent to obtain an organic ligand solution;
(2) adding mixed metal salt of ferric salt and ferrous salt into the organic ligand solution, and uniformly stirring to obtain a ferrous-doped Fe-MOFs Fenton catalyst precursor mixed solution;
(3) and carrying out solvothermal reaction on the mixed solution, then carrying out solid-liquid separation, and drying a solid phase to obtain the ferrous-doped Fe-MOFs Fenton catalyst.
In the above preparation method, in step (1):
preferably, the organic ligand is one or more of terephthalic acid and 2-methylimidazole, and is further preferably terephthalic acid. The solvent is preferably water or N, N-Dimethylformamide (DMF), and more preferably N, N-Dimethylformamide (DMF). In the organic ligand solution, the molar ratio of the organic ligand to the solvent is 1: (100-800); more preferably 1: (300-600), more preferably 1: 500.
the step (1) can be carried out under stirring, and mechanical stirring or magnetic stirring and the like can be adopted; certain heat treatments may also be employed to promote rapid dissolution of the organic ligand. And dissolving the organic ligand to obtain the organic ligand solution for later use.
In the above preparation method, in the step (2):
in the mixed solution, the percentage of Fe (ii) to the total mole content of Fe, calculated as the total amount (Fe) of ferrous iron (Fe (ii)) and ferric iron (Fe (iii)), is preferably 5 to 50%, more preferably 10 to 40%, and even more preferably 20 to 30%.
Preferably, the molar ratio of the total amount of Fe (II) and Fe (III) in the mixed solution to the organic ligand is 1: (0.5 to 1), and more preferably 1: 1.
preferably, the mixed metal salt is a mixture of a ferric salt and a ferrous salt, the ferric salt is one or more of ferric chloride, ferric sulfate and ferric nitrate, and the ferrous salt is one or more of ferrous chloride, ferrous sulfate and ferrous nitrate. The ferric chloride can be ferric chloride hexahydrate; the ferrous chloride can be ferrous chloride tetrahydrate.
In the above preparation method, in the step (3):
the reaction temperature of the solvothermal reaction is preferably 60-150 ℃, more preferably 100-150 ℃, and still more preferably 150 ℃. The reaction time of the thermal reaction is preferably 3 to 24 hours, more preferably 3 to 12 hours, and even more preferably 3 hours.
The drying temperature is preferably 60 to 100 ℃, more preferably 80 to 100 ℃, and still more preferably 100 ℃. The drying time is preferably 10 to 30 hours, more preferably 15 to 25 hours, and still more preferably 24 hours.
And (3) performing solvothermal reaction, centrifugal separation, precipitation washing and drying in a stainless steel reaction kettle with a polytetrafluoroethylene lining to obtain the porous ferrous iron-doped Fe-MOFs Fenton catalyst.
The invention also provides a ferrous iron-doped Fe-MOFs Fenton catalyst prepared by the preparation method in any one of the technical schemes.
The invention also provides an application of the ferrous iron-doped Fe-MOFs Fenton catalyst in degrading pollutants in organic wastewater.
Preferably, the contaminant is salicylic acid, p-nitrophenol, rhodamine B, carbamazepine or an analog of the above compounds or a combination of two or more of the above.
In practical application, the Fe (II) -doped Fe-MOFs Fenton catalyst can be added into organic wastewater pollutants, and hydrogen peroxide is added to perform Fenton-like reaction.
In the Fenton-like reaction, the hydrogen peroxide concentration is preferably 5 to 20mM, more preferably 5 to 10mM, and still more preferably 10 mM. The pH is preferably 3 to 6, more preferably 4 to 6, and still more preferably 4. The concentration of the contaminant is preferably 20 to 200ppm, more preferably 100 to 200ppm, and further preferably 200 ppm. The weight ratio of the pollutants to the ferrous iron-doped Fe-MOFs Fenton catalyst is preferably 1: (1-10).
Specifically, the test of the catalytic activity of the ferrous iron-doped Fe-MOFs Fenton catalyst can be carried out in an intermittent Fenton-like catalytic reactor, the porous ferrous iron-doped Fe-MOFs Fenton catalyst is added into organic wastewater with the pollutant concentration of 20-200 ppm, the pH is adjusted to 3-6, and hydrogen peroxide with the concentration of 5-20 mM is added to enable the porous ferrous iron-doped Fe-MOFs Fenton catalyst to generate the Fenton-like reaction. And (3) measuring the concentration of p-nitrophenol and the total organic carbon content (TOC) value in the treated solution, and calculating the degradation rate constant and the mineralization rate of the p-nitrophenol solution subjected to catalytic Fenton-like oxidative degradation treatment.
The invention utilizes the ferrous ion doped Fe-MOFs solvent to carry out thermal self-assembly to form the porous Fe (II) doped Fe-MOFs Fenton catalyst, and regulates and controls the structure of an iron-oxygen cluster in the Fenton catalyst by a Fe (II) substitution method, so that the Fe-MOFs material with mixed valence (Fe (II)/Fe (III)) is obtained, and the material has extremely high heterogeneous Fenton performance. The substituted Fe (II) center can be used as a stronger active center, and Fe (II) → Fe (III) half-reaction occurs on the original Fe (III) center, so that hydrogen peroxide is quickly activated, and organic pollutants are effectively decomposed.
The preparation method adopts a simple solvent thermal synthesis method to prepare the porous Fe (II) -doped Fe-MOFs Fenton catalyst, the catalyst has rich pore structure, larger specific surface area and more corrected oxidation-reduction potential, can efficiently adsorb and accelerate Fe (II)/Fe (III) circulation to promote powerful activation of hydrogen peroxide decomposition to generate more active oxygen species, and greatly improves the degradation rate and mineralization rate of organic pollutants in water.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention relates to a preparation method of Fe (II) -doped Fe-MOFs Fenton catalyst, which comprises the steps of forming a porous Fe (II) -doped Fe-MOFs Fenton catalyst by means of ferrous ion-doped Fe-MOFs solvent thermal self-assembly, adjusting an iron-oxygen cluster structure in Fe-MOFs by means of Fe (II), so that the circulation rate of Fe (III)/Fe (II) pairs of Fe-MOFs catalytic materials in a Fenton-like reaction is improved, unsaturated metal sites of the materials are enriched, and the Lewis acidity is improved, so that the Fenton-like catalytic performance of Fe-MOFs is improved, the adsorption and catalytic decomposition of Fe-MOFs on hydrogen peroxide are promoted, more active oxygen species such as hydroxyl radicals are further generated, the oxidative degradation of organic pollutants in water is enhanced, and the mineralization degree of the organic pollutants is remarkably improved.
(2) According to the preparation method of the Fe (II) -doped Fe-MOFs Fenton catalyst, the doping proportion of the impurity metal Fe (II) is changed, the substitution of Fe (II) can induce the formation of a large amount of Fe (III) coordination unsaturated sites in the material, and the Lewis acidity of the material is enriched, so that the Fe (II) -doped Fe-MOFs Fenton catalyst exposes more catalytic Fenton active sites, the catalytic Fenton capacity of the Fe (II) -doped Fe-MOFs Fenton catalyst is improved, and the removal efficiency of p-nitrophenol is enhanced.
(3) The Fe (II) doped Fe-MOFs Fenton catalyst can improve the adsorption and catalytic decomposition rate of Fenton-like mass transfer and the efficiency of catalyzing Fenton-like oxidative degradation and mineralization of organic pollutants in water.
(4) The Fe (II) -doped Fe-MOFs Fenton catalyst disclosed by the invention is applied to the field of organic wastewater pollution enhancement treatment, can effectively improve the catalytic Fenton activity of Fe-MOFs, promotes the decomposition rate of Fe (II) -doped Fe-MOFs to Fenton-like reaction, and enhances the deep removal of organic pollutants in water.
Drawings
FIG. 1 shows 30% Fe obtained in example 1IISEM topography for MIL-53(Fe) catalyst;
FIG. 2 is 30% FeII-in situ pyridine adsorption ir spectrum of MIL-53(Fe) catalyst;
FIG. 3 is a pseudo first order kinetic fit of the effect of degradation time on p-nitrophenol concentration change (a) and the p-nitrophenol oxidative degradation process (b);
FIG. 4 is 30% FeIIComparative monitoring of MIL-53(Fe) versus the original MIL-53(Fe) catalyst/Fenton-like system active oxygen species EPR.
Detailed Description
The invention will now be further illustrated by the following examples.
Example 1
A preparation method of Fe (II) doped Fe-MOFs Fenton catalyst comprises the following steps of forming porous Fe (II) doped Fe-MOFs Fenton catalyst by means of ferrous ion doped Fe-MOFs solvent thermal self-assembly:
(1) under magnetic stirring, adding an organic ligand into an N, N-dimethylformamide solution according to the molar ratio of the N, N-dimethylformamide to the organic ligand terephthalic acid of 500:1, and completely dissolving to obtain an organic ligand terephthalic acid solution;
(2) adding mixed metal salts (ferrous chloride tetrahydrate and ferric chloride hexahydrate) with the molar ratio of n (Fe (II): n (Fe)) being 0.30:0.70 into an organic ligand terephthalic acid solution (wherein the molar ratio of the total molar amount of n (Fe) (II): n (Fe) to terephthalic acid is 1:1), and uniformly stirring to obtain a Fe (II) -doped Fe-MOFs Fenton catalyst precursor mixed solution;
(3) transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, carrying out solvothermal reaction for 3h at 150 ℃, carrying out centrifugal separation, precipitating and washing, drying for 24h at 100 ℃ to obtain a porous Fe (II) doped Fe-MOFs Fenton catalyst which is marked as 30% FeII-MIL-53(Fe)。
The Fe (II) doped Fe-MOFs Fenton catalyst prepared by the method is in a regular needle-like shape with the length of about 2 μm and the width of about 0.5 μm (shown in figure 1). The in-situ pyridine adsorption infrared spectroscopy is adopted to detect the surface acid sites of the Fe (II) doped Fe-MOFs Fenton catalyst prepared by the method, and the result is shown in figure 2.
According to the formula for calculating the Lewis acid site density:
wherein LA is the Lewis acid site density on the surface of Fe (II) -doped Fe-MOFs Fenton catalyst, MacIs molar absorptivity (M)ac＝0.6)，SpWave number of 1069.7cm-1Calculating the surface of Fe (II) doped Fe-MOFs Fenton catalystThe acid site density was found to be 3.49mmol g-1。
And (3) detecting the degradation performance:
with 30% Fe in FIG. 3II-MIL-53(Fe)+H2O2The group shown is an example, hydrogen peroxide with a specification of analytical purity of 30% is selected. 500mL of 20mg L was prepared-1Adjusting the pH value of the p-nitrophenol mother liquor (water is used as a solvent) to be 4, and adding the p-nitrophenol mother liquor into a reaction container. 200mg of the Fe (II) -doped Fe-MOFs Fenton catalyst is accurately weighed and added into p-nitrophenol mother liquor, the mixture is subjected to ultrasonic treatment for 60s to be uniformly dispersed, then a liquid transfer gun is used for transferring a quantitative hydrogen peroxide solution into the p-nitrophenol mother liquor (the concentration of hydrogen peroxide in the p-nitrophenol mother liquor is 10mM), and Fenton-like degradation reaction is triggered. Sampling 5mL (0min, 10min, 20min, 30min, 40min, 50min, 60 min) at intervals of 10min, then sampling 5mL (90min, 120min) at intervals of 30min along with the reaction, filtering with a 0.22 μm needle filter head, and adding 0.1mL of tert-butyl alcohol into the residual active oxygen species in the filtrate for quenching. The total treatment time was 120 min. Each set of experiments was repeated three times.
The method adopts an Agilent 1260 type high performance liquid chromatograph to measure the concentration of the p-nitrophenol, and the analysis conditions are as follows: an Agilent ZORBAX Eclipse XDB-C18 chromatographic column (3.5 μm,4.6x 150mm) is used as a stationary phase, the column temperature is 30 ℃, the mobile phase is a mixed solution of ultrapure water and methanol (30/70), and the flow rate and the sample injection amount are respectively 0.8mL min-1And 20. mu.L. The retention time of p-nitrophenol was 2.37 min.
The p-nitrophenol concentrations and corresponding time points of the samples sampled at 0min, 10min, 20min, 30min, 40min, 50min, 60min, 90min and 120min are calculated according to a pseudo first-order kinetic formula
Wherein k is a degradation rate constant in min-1，CtAt different time p-nitrophenol concentrations, C0The concentration of p-nitrophenol at the initial time, and t is the corresponding processing time in min; performing kinetic fitting on the degradation process by using the detection data and formula (see FIG. 3), wherein the obtained slope k value is the degradation rate constant of p-nitrophenol, and the result is 0.022min-1。
In FIG. 3, reference is made to the above degradation Performance test, H2O2alone represents: only introducing hydrogen peroxide; 30% FeII-MIL-53(Fe) represents: only 30% Fe prepared by the above preparation method was addedII-MIL-53(Fe), without hydrogen peroxide; 30% FeII-MIL-53(Fe)+H2O2Represents: adding 30% Fe prepared by the above preparation methodIIMIL-53(Fe), with introduction of H2O2As indicated above; MIL-53(Fe) + H2O2Represents: adding undoped Fe-MOFs Fenton catalyst and introducing H2O2. As can be seen from FIG. 3, the Fe-MOFs-doped Fenton-type catalyst (30% Fe) prepared by the preparation method in example 1IIMIL-53(Fe)) has obviously improved catalytic Fenton-like oxidative degradation efficiency.
Measuring the total organic carbon content before and after (treating for 30min) water sample treatment by using Liquid TOC analyzer of Elementar according to a formula
Wherein R isTOCFor mineralization rate, TOCtThe TOC value and the TOC of the water sample after 30min of treatment0The mineralization rate of p-nitrophenol was calculated as the TOC value of the initial sample and found to be 48.1%. The degradation rate constant and the mineralization rate are respectively about 3 times of those of the undoped Fe-MOFs Fenton catalyst (the degradation rate of the undoped Fe-MOFs Fenton catalyst is usually 0.0073min-1) And 1.39 times (mineralization rate of 34.3% for undoped Fe-MOFs fenton-type catalysts). The undoped Fe-MOFs Fenton catalyst is prepared by only taking ferric iron as a raw material under the same condition, and the involved degradation experimental process is consistent with that of Fe (II) doped Fe-MOFs.
Reactive oxygen species EPR detection
For 30% Fe prepared in the above preparation method, respectivelyIIActive oxygen species EPR test is carried out on MIL-53(Fe) and the original MIL-53(Fe) catalyst/Fenton-like system, the test result is shown in figure 4, and compared with the undoped Fe-MOFs Fenton-like catalyst (MIL-53(Fe)), the 30% Fe prepared by the method isIIMIL-53(Fe) has more reactive oxygen species.
According to the invention, ferrous ion doped Fe-MOFs solvent is adopted for thermal self-assembly to form the porous Fe (II) doped Fe-MOFs Fenton catalyst, and nitrogen adsorption and desorption experiments show that the Fenton catalyst is rich in pore structure (the pore diameter is distributed at 2-60 nm) and large in specific surface area (187.14 m)2The concentration/g) and the surface Lewis acid site density are high, the catalytic Fenton activity of the Fe-MOFs can be obviously improved, the Fe-MOFs catalytic material is promoted to generate more active oxygen species for Fenton adsorption and catalytic decomposition, and the removal efficiency of organic pollutants in water is enhanced. The process is simple and convenient to operate, the prepared Fe (II) -doped Fe-MOFs Fenton catalyst has remarkable Fenton oxidation degradation efficiency, and the provided preparation method of Fe (II) -doped Fe-MOFs provides a practical scheme for strengthening treatment of organic pollutants in industrial wastewater.
Example 2
A preparation method of Fe (II) doped Fe-MOFs Fenton catalyst comprises the following steps:
(1) under magnetic stirring, adding an organic ligand into a DMF solution according to the molar ratio of N, N-Dimethylformamide (DMF) to the organic ligand terephthalic acid of 500:1, and obtaining the organic ligand terephthalic acid solution after complete dissolution;
(2) adding mixed metal salts (ferrous chloride tetrahydrate and ferric chloride hexahydrate) with the molar ratio of n (Fe (II): n (Fe)) being 0.20:0.80 into an organic ligand terephthalic acid solution (wherein the molar ratio of the total molar amount of n (Fe) (II): n (Fe) to terephthalic acid is 1:1), and uniformly stirring to obtain a Fe (II) -doped Fe-MOFs Fenton catalyst precursor mixed solution;
(3) transferring the mixed solution into a stainless steel reaction kettle containing a polytetrafluoroethylene lining, carrying out solvothermal reaction for 3h at 150 ℃, carrying out centrifugal separation, precipitating and washing, and drying for 24h at 100 ℃ to obtain a porous Fe (II) -doped Fe-MOFs Fenton catalyst product.
The testing and calculating method in example 1 is adopted to obtain the Lewis acid site density of the Fe (II) doped Fe-MOFs Fenton catalyst prepared in the embodiment to be 3.22mmol g-1The degradation rate constant of the p-nitrophenol solution is 0.020min-1The mineralization rate was 45.2%.
Example 3
A preparation method of Fe (II) doped Fe-MOFs Fenton catalyst comprises the following steps:
(1) under magnetic stirring, adding an organic ligand into a DMF solution according to the molar ratio of N, N-Dimethylformamide (DMF) to the organic ligand terephthalic acid of 500:1, and obtaining the organic ligand terephthalic acid solution after complete dissolution;
(2) adding mixed metal salts (ferrous chloride tetrahydrate and ferric chloride hexahydrate) with the molar ratio of n (Fe (II): n (Fe)) being 0.10:0.90 into an organic ligand terephthalic acid solution (wherein the molar ratio of the total molar amount of n (Fe) (II): n (Fe)) to terephthalic acid is 1:1), and uniformly stirring to obtain a Fe (II) -doped Fe-MOFs Fenton catalyst precursor mixed solution;
(3) transferring the mixed solution into a stainless steel reaction kettle containing a polytetrafluoroethylene lining, carrying out solvothermal reaction for 3h at 150 ℃, carrying out centrifugal separation, precipitating and washing, and drying for 24h at 100 ℃ to obtain a porous Fe (II) -doped Fe-MOFs Fenton catalyst product.
The testing and calculating method in example 1 is adopted to obtain the Lewis acid site density of the Fe (II) -doped Fe-MOFs Fenton catalyst prepared in the embodiment to be 2.60mmol g-1The degradation rate constant of p-nitrophenol solution is 0.012min-1The mineralization rate was 40.8%.
Example 4
A preparation method of Fe (II) doped Fe-MOFs Fenton catalyst comprises the following steps:
(1) under magnetic stirring, adding an organic ligand into a DMF solution according to the molar ratio of N, N-Dimethylformamide (DMF) to the organic ligand terephthalic acid of 500:1, and obtaining the organic ligand terephthalic acid solution after complete dissolution;
(2) adding mixed metal salts (ferrous chloride tetrahydrate and ferric chloride hexahydrate) with the molar ratio of n (Fe (II): n (Fe)) being 0.05:0.95 into an organic ligand terephthalic acid solution (wherein the molar ratio of the total molar amount of n (Fe) (II): n (Fe) to terephthalic acid is 1:1), and uniformly stirring to obtain a Fe (II) -doped Fe-MOFs Fenton catalyst precursor mixed solution;
(3) transferring the mixed solution into a stainless steel reaction kettle containing a polytetrafluoroethylene lining, carrying out solvothermal reaction for 3h at 150 ℃, carrying out centrifugal separation, precipitating and washing, and drying for 24h at 100 ℃ to obtain a porous Fe (II) -doped Fe-MOFs Fenton catalyst product.
The testing and calculating method in example 1 is adopted to obtain the Lewis acid site density of the Fe (II) doped Fe-MOFs Fenton catalyst prepared in the embodiment to be 2.55mmol g-1The degradation rate constant of the p-nitrophenol solution is 0.0086min-1The mineralization rate was 38.1%.
Example 5
The application of Fe (II) doped Fe-MOFs Fenton catalyst comprises the following steps:
(1) respectively preparing 1L of organic pollutant solution of p-nitrophenol, rhodamine B and carbamazepine with the concentration of 200mg/L, and adjusting the pH value to be 4 for later use;
(2) 0.4g of the catalyst prepared in example 1, 30% Fe respectively, was stirred under magnetic forceIIAdding MIL-53(Fe) into the three organic pollutant solutions prepared in the step (1), and performing ultrasonic treatment for 1min to uniformly disperse the three organic pollutant solutions to form a suspension;
(3) selecting 30% hydrogen peroxide with analytical purity, then transferring a certain amount of hydrogen peroxide solution into an organic pollutant solution (the concentration of the hydrogen peroxide in the organic pollutant solution is 10mM) by using a liquid transfer gun, and triggering a Fenton-like degradation reaction;
(4) determining the total organic carbon content value of the water sample before and after treatment by using a total organic carbon analyzer, and calculating 30% FeII-mineralization rate of different kinds of organic pollutants by Fenton-like oxidation system of MIL-53(Fe) and hydrogen peroxide.
The results showed 30% FeIIThe mineralization rates of p-nitrophenol, rhodamine B and carbamazepine in a Fenton-like oxidation system of MIL-53(Fe) and hydrogen peroxide are respectively 48.5%, 53.2% and 55.1%.
Claims (10)
1. A preparation method of a ferrous iron-doped Fe-MOFs Fenton catalyst is characterized in that a porous ferrous iron-doped Fe-MOFs Fenton catalyst is formed by the thermal self-assembly of a ferrous iron ion-doped Fe-MOFs solvent; wherein the Fe-MOFs is an iron-based metal organic framework material.
2. The method for preparing the ferrous iron-doped Fe-MOFs Fenton catalyst according to claim 1, comprising the following steps:
(1) dissolving an organic ligand in a solvent to obtain an organic ligand solution;
(2) adding mixed metal salt of ferric salt and ferrous salt into the organic ligand solution, and uniformly stirring to obtain a ferrous-doped Fe-MOFs Fenton catalyst precursor mixed solution;
(3) and carrying out solvothermal reaction on the mixed solution, then carrying out solid-liquid separation, and drying a solid phase to obtain the ferrous-doped Fe-MOFs Fenton catalyst.
3. The method for preparing the ferrous iron-doped Fe-MOFs Fenton catalyst according to claim 2, wherein said organic ligand is one or more of terephthalic acid and 2-methylimidazole; the solvent is water or N, N-dimethylformamide or a mixed solvent of the water and the N, N-dimethylformamide; in the organic ligand solution, the molar ratio of the organic ligand to the solvent is 1: (100-800).
4. The method for preparing the ferrous iron-doped Fe-MOFs Fenton catalyst according to claim 2, wherein the percentage of ferrous iron in the mixed solution in the total molar content of Fe is 5-50%.
5. The method for preparing a ferrous iron-doped Fe-MOFs Fenton catalyst according to claim 2, wherein the molar ratio of the total amount of ferrous iron and ferric iron in said mixed solution to the organic ligand is 1: (0.5 to 1).
6. The method for preparing a ferrous iron-doped Fe-MOFs Fenton catalyst according to claim 2, wherein said mixed metal salt is a mixture of a ferric salt and a ferrous salt, the ferric salt is one or more of ferric chloride, ferric sulfate and ferric nitrate, and the ferrous salt is one or more of ferrous chloride, ferrous sulfate and ferrous nitrate.
7. The preparation method of the ferrous iron-doped Fe-MOFs Fenton catalyst according to claim 2, wherein in the step (3), the reaction temperature of the solvothermal reaction is 60-150 ℃, and the reaction time is 3-24 h; the drying temperature is 60-100 ℃, and the drying time is 10-30 h.
8. A ferrous iron-doped Fe-MOFs Fenton catalyst, which is characterized by being prepared by the preparation method of any one of claims 1 to 7.
9. Use of the ferrous iron-doped Fe-MOFs fenton-like catalyst according to claim 8 for degrading pollutants in organic wastewater.
10. The application of claim 9, wherein the ferrous iron-doped Fe-MOFs Fenton catalyst is added into the organic wastewater, hydrogen peroxide is introduced, wherein the concentration of the hydrogen peroxide is 5-20 mM, the pH is 3-6, the concentration of pollutants is 20-200 ppm, and the weight ratio of the pollutants to the ferrous iron-doped Fe-MOFs Fenton catalyst is 1: (1-10).
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