CN113351254A - Copper-manganese doped iron metal organic framework material, preparation method thereof and method for treating organic wastewater by catalytically activating persulfate - Google Patents
Copper-manganese doped iron metal organic framework material, preparation method thereof and method for treating organic wastewater by catalytically activating persulfate Download PDFInfo
- Publication number
- CN113351254A CN113351254A CN202110651265.8A CN202110651265A CN113351254A CN 113351254 A CN113351254 A CN 113351254A CN 202110651265 A CN202110651265 A CN 202110651265A CN 113351254 A CN113351254 A CN 113351254A
- Authority
- CN
- China
- Prior art keywords
- copper
- salt
- manganese
- organic framework
- metal organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
Abstract
The invention discloses a copper-manganese doped iron metal organic framework material, a preparation method thereof and a method for treating organic wastewater by catalytically activating persulfate, and belongs to the technical field of water pollution control. Adding diaminoterephthalic acid, iron salt, copper salt and manganese salt into N-dimethylformamide to obtain a mixed solution, then adding methanol and hydrofluoric acid, and carrying out heating reaction; and cooling the obtained mixture after reaction, performing centrifugal separation, washing and drying to obtain powder, namely the copper-manganese doped iron metal organic framework material. The catalyst disclosed by the invention is high in catalytic activity, short in catalytic time, good in durability, convenient to operate, and capable of having a higher degradation effect in a wider pH value range, and the activation effect is still good after repeated utilization for many times.
Description
Technical Field
The invention belongs to the technical field of water pollution control, and particularly relates to a copper-manganese doped iron metal organic framework material, a preparation method thereof and a method for treating organic wastewater by catalytically activating persulfate.
Background
Water pollution is one of the serious crises facing human beings at present, and the human beings are continuously developing in the aspect of treating water pollution. However, the treatment of toxic and harmful organic pollutants is always a technical difficulty in water treatment. Advanced oxidation technologies based on sulfate radicals (SO 4-), due to their high efficiency and cleanliness in degrading pollutants, are receiving increasing attention and interest from researchers in the field of degrading persistent organic pollutants. In the existing reports, the PS is generally activated by light, heat, ultrasound and metal ions, but the traditional catalytic activation method has the problems of low efficiency, large influence of pH value, easy secondary pollution and the like, so that the method is difficult to be widely applied in the actual industry. The metal organic framework is used as a heterogeneous catalyst to catalyze and activate PS to generate sulfate ions, so that the defects are overcome, and the catalyst has the advantages of reusability, high activity, good catalytic effect and the like, and becomes a hotspot for research of researchers at present.
Metal organic framework Materials (MOFs) are crystalline porous materials with regular pore channels or cavity structures, which are obtained by coordination self-assembly of metal nodes and organic ligands. The material has higher specific surface area, rich pore structure and higher physical and chemical stability, is easy to load other substances without changing the structure of the material, and has a large amount of unsaturated coordination metal nodes in a metal organic framework, so that the material has potential huge application value in a plurality of fields such as catalysis, separation, adsorption, gas storage, medical diagnosis and the like, and particularly shows huge application prospect in the aspect of removing water pollutants. Numerous researchers have prepared various heterogeneous catalysts with abundant metallic iron, but the catalytic ability has yet to be improved. Later, researchers have further prepared the iron-copper bimetallic MOFs (201610207408.5), and related patents have granted that the efficiency of degrading organic substances is improved to some extent compared with that of the single-metal iron MOFs, but two main defects exist. Firstly, the improvement of degradation efficiency is limited, and further improvement is needed; secondly, although the iron-copper bimetallic MOFs material improves the degradation efficiency on the basis of the single-metal iron MOFs material, the stability of the material is reduced, the structure is easy to collapse, more metal ions are separated out, the material is not beneficial to recycling, and secondary pollution to the environment is possibly caused.
Disclosure of Invention
Aiming at the problems that the degradation efficiency of the existing iron-copper bimetal MOFs material is improved to a limited extent, the material is poor in stability, the structure is easy to collapse, more metal ions can be separated out, and secondary pollution to the environment is possibly caused, the invention provides the iron-based tri-metal organic framework material capable of effectively solving the problems, the preparation method thereof and the method for applying the iron-copper bimetal MOFs material to persulfate activation treatment of organic wastewater. The invention adopts the copper-manganese doped iron metal organic framework material as the heterogeneous catalyst, fully utilizes the unsaturated coordinated iron active center in the material and the copper and manganese metal ions doped in the pores, leads persulfate to generate sulfate radicals with strong oxidability under the concerted catalysis of iron, copper and manganese, and carries out oxidative degradation on organic pollutants in water, thereby avoiding the loss of iron ions, copper ions and manganese ions in a homogeneous catalysis system.
The invention provides a method for activating persulfate more efficiently by taking a metal copper-manganese doped iron metal organic framework as a heterogeneous catalyst, achieves the purpose of degrading organic pollutants in water by utilizing the synergistic effect of iron, copper and manganese, and has stronger activation efficiency and higher stability compared with a bimetallic metal organic framework material under the same condition.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a copper-manganese doped iron metal organic framework material comprises the following steps:
(1) adding diaminoterephthalic acid, iron salt, copper salt and manganese salt into N-dimethylformamide to obtain a mixed solution, then adding methanol and hydrofluoric acid, and carrying out heating reaction;
(2) and (2) cooling the reacted mixture obtained in the step (1), and then centrifugally separating, washing and drying to obtain powder, namely the copper-manganese doped iron metal organic framework material.
Preferably, the molar ratio of the total amount of the iron salt, the copper salt and the manganese salt in the step (1) to the diamino terephthalic acid is 5: 7-7: 5; further preferably, the molar ratio of the total amount of the iron salt, the copper salt and the manganese salt to the diaminoterephthalic acid is 1: 1.
Preferably, the total concentration of the ferric salt, the cupric salt and the manganese salt in the mixed solution in the step (1) is 4-6 mM;
preferably, the volume ratio of the methanol to the mixed solution in the step (1) is 1: 10-1: 20;
preferably, the volume ratio of the hydrofluoric acid to the mixed solution in the step (1) is 1: 20-1: 40.
Preferably, in the step (1), the iron salt is at least one of a sulfate and a chloride of divalent or trivalent iron, the copper salt is at least one of a sulfate and a chloride of copper, and the manganese salt is at least one of a sulfate and a chloride of manganese.
Preferably, the heating reaction time in the step (1) is 12-16 h, and the heating reaction temperature is 140-160 ℃.
Preferably, the rotating speed of the centrifugation in the step (2) is 8000-10000 rpm, and the centrifugation time is 10-15 min;
preferably, the washing in step (2) is at least 3 times with methanol;
preferably, the drying temperature in the step (2) is 60-80 ℃, and the drying time is 12-24 h.
The copper-manganese doped iron metal organic framework material prepared by the preparation method comprises three metal elements of iron, copper and manganese.
The method for treating organic wastewater by catalytically activating persulfate through the copper-manganese doped iron metal organic framework material takes the metal organic framework material as a catalyst, utilizes the characteristics of high active site and strong activity of the metal organic framework, catalytically activates PS (polystyrene) at normal temperature to generate sulfate radicals with strong oxidizing property, and degrades organic pollutants in wastewater, and comprises the following steps of:
and adding the copper-manganese doped iron metal organic framework material and persulfate into organic pollutant wastewater, and reacting at normal temperature.
Preferably, the reaction is carried out in a shaking table, and the rotation speed of the shaking table is 150-250 rpm; the reaction time is 120-150 min; the pH value of the organic pollutant wastewater is 3-9.
Preferably, the persulfate is sodium persulfate or potassium persulfate.
Preferably, the molar ratio of persulfate to organic contaminant is 50: 1-200: 1;
preferably, the adding amount of the copper-manganese doped iron metal organic framework material is 0.1-0.6 g/L.
Preferably, the copper-manganese doped iron metal organic framework material is recycled for multiple times, so that the cyclic catalytic capability of the copper-manganese doped iron metal organic framework material is embodied.
Compared with the prior art, the invention has the following advantages and technical effects:
(1) the preparation method of the copper-manganese doped iron metal organic framework material provided by the invention is simple to operate, has no special requirements on the external environment, and is easy to realize;
(2) the iron metal organic framework has a high specific surface area, a plurality of pore structures and unsaturated metal active centers, the doping of copper and manganese ions increases the reaction points of the material in contact with persulfate, the combined action of iron, copper and manganese strengthens the effect of persulfate on generating sulfate radicals, and the catalyst has a good effect of removing pollutants;
(3) the heterogeneous catalyst has no selectivity to target pollutants, and has wide applicability;
(4) the catalyst can be repeatedly recycled, and is environment-friendly;
(5) the catalyst has wide application pH value range;
(6) compared with the original copper-manganese doped iron metal organic framework material and iron-copper bimetallic organic framework material, the invention has stronger activation efficiency under the same condition;
(7) the method does not need to consume extra energy including ultrasound, light and electricity, so that the cost is reduced; and the process flow is very simple, the operability is strong, the durability is good, the catalysis time is short, and the method has wide practical application prospect.
Drawings
FIG. 1 shows the Cu-Mn doped Fe-MOF material NH prepared in example 12Scanning Electron Micrograph (SEM) of MIL (Fe, Cu, Mn).
FIGS. 2, 3 and 4 show the Cu-Mn doped Fe-MOF material NH prepared in example 12-X-ray photoelectron spectroscopy (XPS) of MIL (Fe, Cu, Mn).
Detailed Description
The invention is further illustrated by the following examples, which illustrate the salient features and significant improvements of the invention, and which are intended to be illustrative of the invention and are in no way limited to the examples below. Sulfamethoxazole (SMZ) was chosen as the target contaminant in the examples.
Example 1
This example compares the removal rates of SMZ with copper manganese doped iron metal organic framework material activated sodium persulfate and with copper doped iron metal organic framework material alone and with sodium persulfate alone.
(1)NH2Preparation of MIL (Fe, Cu, Mn): respectively reacting diamino terephthalic acid (5mM) and FeCl2·4H2O，CuSO4·5H2O and MnCl2·4H2O (5mM of the three components in total) is added into 40mL of N-dimethylformamide, then 2mL of methanol and 1mL of hydrofluoric acid are added, and the mixed solution is transferred into a 100mL of reaction kettle with a polytetrafluoroethylene lining and is heated to 150 ℃ for reaction for 12 hours. The synthesis conditions were controlled to 3 kinds as follows: FeCl2·4H2O，CuSO4·5H2O and MnCl2·4H2The molar ratio of O to O is 1: 1:1,4: 1: 0,5: 0: 0, respectively named as NH2-MIL(Fe,Cu,Mn)，NH2-MIL(Fe,Cu)，NH2-mil (fe). After the reaction is finished, the reaction is carried outTransferring the mixture to a centrifuge tube, and centrifuging for 10min under the condition of 10000rpm to obtain a solid; washing with methanol for at least 3 times, placing the obtained solid in a vacuum drying oven, and drying at 60 deg.C for 12 hr to obtain powder.
(2) Preparing 0.0197mmol/L of SMZ solution for later use;
(3) using a conical flask as a reactor, 2.961mmol of Na was added into the reactor2S2O8And 0.0197mmol/L SMZ100 mL (nNa)2S2O8150/nSMZ) and 0.04g of NH material is added to the reactor2-MIL(Fe,Cu,Mn)，NH2-MIL(Fe,Cu)，NH2MIL (Fe), placing the flask on a shaker at 180rpm, reacting at ambient temperature (25 ℃), sampling and analyzing at fixed points, and taking a flask and adding only NH as a material2MIL (Fe, Cu, Mn), without Na addition2S2O8As a control. The SMZ removal rates for the different materials are shown in table 1.
TABLE 1
The results in Table 1 show that the catalyst NH alone is used2The removal effect of-MIL (Fe, Cu, Mn) on SMZ is weak. However, when the catalyst and the sodium persulfate are added simultaneously, the removal rate of the SMZ is obviously improved. We have found that the trimetallic material NH is in the presence of sodium persulfate2The removal rate of MIL (Fe, Cu, Mn) to SMZ is obviously higher than that of a bimetallic material NH under the same condition2MIL (Fe, Cn) and a monometallic material NH2-MIL(Fe)。
Example 2
This example compares the stability of a copper manganese doped iron metal organic framework material, a copper doped iron metal organic framework material and an iron metal organic framework material.
(1)NH2-MIL(Fe,Cu,Mn)、NH2-MIL(Fe,Cu)、NH2MIL (Fe) was prepared in the same manner as in step (1) of example 1;
(2) preparing 0.0197mmol/L of SMZ solution for later use;
(3) using a conical flask as a reactor, 2.961mmol of Na was added into the reactor2S2O8And 0.0197mmol/L SMZ100 mL (nNa)2S2O8150/nSMZ) and 0.04g of NH material is added to the reactor2-MIL(Fe,Cu,Mn)，NH2-MIL(Fe,Cu)，NH2MIL (Fe), placing the conical flask in a shaking table at 180rpm, carrying out reaction under the condition of normal temperature (25 ℃), carrying out fixed-point sampling analysis, and characterizing the stability of the material by measuring the concentration of metal ions in a degradation reaction system.
The stability of the different materials is shown in table 2.
TABLE 2
As can be seen from Table 2: bimetallic material NH in the presence of sodium persulfate2MIL (Fe, Cn) dissolves significantly more metal ions than NH, a single metal material2Mil (fe), the stability of the material becomes poor. Trimetallic material NH2MIL (Fe, Cu, Mn) overcomes this drawback, with minimal elution of metal ions and greater stability.
Example 3
This example compares different pH values to NH2Effect of MIL (Fe, Cu, Mn) on the degradation of SMZ by activated PS.
(1)NH2Preparation of MIL (Fe, Cu, Mn): respectively reacting diamino terephthalic acid (5mM) and FeCl2·4H2O，CuSO4·5H2O and MnCl2·4H2O (5mM of the three components in total) is added into 40mL of N-dimethylformamide, then 2mL of methanol and 1mL of hydrofluoric acid are added, and the mixed solution is transferred into a 100mL of reaction kettle with a polytetrafluoroethylene lining and is heated to 150 ℃ for reaction for 12 hours. Controlling FeCl2·4H2O，CuSO4·5H2O and MnCl2·4H2The molar ratio of O to O is 1: 1:1, material name NH2MIL (Fe, Cu, Mn). After the reaction is finished, transferring the mixture after the reaction to a centrifuge tube, and separating at 10000rpmSeparating in heart for 10min to obtain solid; washing with methanol for at least 3 times, placing the obtained solid in a vacuum drying oven, and drying at 60 deg.C for 12 hr to obtain powder.
(2) Preparing 0.0197mmol/L of SMZ solution for later use;
(3) using a conical flask as a reactor, 2.961mmol of Na was added into the reactor2S2O8And 0.0197mmol/L SMZ100 mL (nNa)2S2O8150/nSMZ) and 0.04g of NH material is added to the reactor2MIL (Fe, Cu, Mn), adjusting different pH values, placing the conical flask in a shaking table at 180rpm, carrying out reaction under the condition of normal temperature (25 ℃), and carrying out fixed-point sampling analysis;
the removal rate of SMZ at different pH values is shown in table 3.
TABLE 3
As can be seen from Table 3: at different pH values, NH2The removal effect of MIL (Fe, Cu, Mn) catalyzing and activating PS to degrade SMZ is different, the degradation efficiency of the SMZ is reduced along with the increase of the pH value, and the removal rate of the SMZ can still reach 77.87% when the pH value is 9, so that NH is used for removing the SMZ2the-MIL (Fe, Cu, Mn) catalytic activated PS can effectively remove the persistent organic pollutant SMZ under the condition of wide pH value (3-9).
Example 4
This example compares the difference in the molar ratio of PS to SMZ (nNa)2S2O8/nSMZ 50, 100, 150, 200, 250) to NH2Influence of MIL (Fe, Cu, Mn) on the catalytic activation reaction.
(1)NH2MIL (Fe, Cu, Mn) was prepared in the same manner as in step (1) of example 3;
(2)0.0197mmol/L of SMZ solution for later use;
(3) using a conical flask as a reactor, and respectively adding 0.985, 1.97, 2.961, 3.94 and 4.925mmol of Na into the reactor2S2O8And 0.0197mmol/L SMZ100 mL, and 0.04g of metal organic is added into the reactor at the same timeA framework material, placing the conical flask in a shaking table at 180rpm, reacting at normal temperature (25 ℃), and sampling and analyzing at fixed points;
NH at different molar ratios of PS and SMZ2The SMZ removal rate of the catalytically activated PS degradation by MIL (Fe, Cu, Mn) is shown in Table 4.
TABLE 4
As can be seen from Table 4: with nNa2S2O8the/nSMZ ratio is increased, the SMZ removal rate shows a first rising trend, when the ratio is increased from 50 to 150, the removal rate is increased from 64.52 percent to 85.40 percent after the reaction is carried out for 120min, and when the ratio is increased from 150 to 250, although the removal rate is further increased, the increase degree is not large. nNa from the standpoint of reaction efficiency and cost2S2O8The best choice is/nSMZ 150.
Example 5
This example compares NH2The effect of the addition of MIL (Fe, Cu, Mn) (0.02g, 0.03g, 0.04g, 0.05g, 0.06g) on the catalytic activation of the degradation SMZ reaction.
(1)NH2MIL (Fe, Cu, Mn) production method reference example 3, step (1);
(2)0.0197mmol/L of SMZ solution for later use;
(3) using a conical flask as a reactor, 2.961mmol of Na was added into the reactor2S2O8And 0.0197mmol/L SMZ100 mL (nNa)2S2O8150/nSMZ), simultaneously respectively adding 0.02g, 0.03g, 0.04g, 0.05g and 0.06g of metal organic framework materials into the reactor, placing the conical flask into a shaking table at 180rpm, carrying out reaction at normal temperature (25 ℃), and carrying out fixed-point sampling analysis;
the effect of different dosing on SMZ removal is shown in table 5 below.
TABLE 5
As can be seen from Table 5: with NH2The increase in the amount of MIL (Fe, Cu, Mn) added shows a tendency of increasing the SMZ removal rate first, and when the amount of addition is increased from 0.02g to 0.04g, the removal rate is increased from 74.63% to 85.40% after 120min of reaction, and when the amount of addition is increased from 0.04g to 0.06g, although the removal rate is further increased, the degree of increase is not great. NH from the viewpoint of reaction efficiency and cost2The amount of-MIL (Fe, Cu, Mn) added is preferably 0.04 g.
Example 6
This example compares NH2Recycling condition of reaction for catalytic activation and degradation of SMZ by MIL (Fe, Cu, Mn).
(1)NH2MIL (Fe, Cu, Mn) production method reference example 3, step (1);
(2)0.0197mmol/L of SMZ solution for later use;
(3) using a conical flask as a reactor, 2.961mmol of Na was added into the reactor2S2O8And 0.0197mmol/L SMZ100 mL (nNa)2S2O8150% of/nSMZ), simultaneously adding 0.04g of metal organic framework material into the reactor, placing the conical flask into a shaking table at 180rpm, reacting at the normal temperature (25 ℃), and sampling and analyzing at fixed points;
(4) filtering NH in the reaction solution of (3) with a 0.22um water washing filter membrane2MIL (Fe, Cu, Mn), fed into a conical flask reactor, under otherwise the same conditions as (3);
(5) filtering NH in the reaction solution of (4) with a 0.22um water washing filter membrane2MIL (Fe, Cu, Mn), fed into a conical flask reactor, under otherwise the same conditions as (3);
(6) filtering NH in the reaction solution of (5) with a 0.22um water washing filter membrane2MIL (Fe, Cu, Mn), fed into a conical flask reactor, under otherwise the same conditions as (3);
(7) the NH in the reaction solution of (6) was filtered through a 0.22um water-washing filter2MIL (Fe, Cu, Mn), fed into a conical flask reactor, under otherwise the same conditions as (3);
the removal rates of SMZ obtained by the five processes are shown in table 6.
TABLE 6
As can be seen from Table 6: NH (NH)2In a cyclic degradation experiment of degrading persistent organic matter SMZ by catalyzing and activating PS through MIL (Fe, Cu, Mn), it can be obviously found that the removal rate of the SMZ is reduced to a certain extent along with the increase of the cycle number, but the total removal rate still reaches over 75 percent. Thus NH2The MIL (Fe, Cu, Mn) catalyst can still effectively catalyze and activate PS to degrade SMZ after multiple cycles.
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. A preparation method of a copper-manganese doped iron metal organic framework material is characterized by comprising the following steps:
(1) adding diaminoterephthalic acid, iron salt, copper salt and manganese salt into N-dimethylformamide to obtain a mixed solution, then adding methanol and hydrofluoric acid, and carrying out heating reaction;
(2) and (2) cooling the reacted mixture obtained in the step (1), and then centrifugally separating, washing and drying to obtain powder, namely the copper-manganese doped iron metal organic framework material.
2. The preparation method according to claim 1, wherein the molar ratio of the total amount of the iron salt, the copper salt and the manganese salt in the step (1) to the diaminoterephthalic acid is 5: 7-7: 5; the total concentration of ferric salt, cupric salt and manganese salt in the mixed solution is 4-6 mM; the volume ratio of the methanol to the mixed solution is 1: 10-1: 20; the volume ratio of the hydrofluoric acid to the mixed solution is 1: 20-1: 40.
3. The preparation method according to claim 1, wherein the iron salt in step (1) is at least one of a sulfate and a chloride of divalent or trivalent iron, the copper salt is at least one of a sulfate and a chloride of copper, and the manganese salt is at least one of a sulfate and a chloride of manganese.
4. The preparation method according to claim 1, wherein the heating reaction time in the step (1) is 12-16 h, and the heating reaction temperature is 140-160 ℃.
5. The method according to claim 1, wherein the rotation speed of the centrifugation in the step (2) is 8000-10000 rpm, and the time of the centrifugation is 10-15 min; the washing is at least 3 times with methanol; the drying temperature is 60-80 ℃, and the drying time is 12-24 h.
6. A Cu-Mn doped Fe-MOF material obtained by the process according to any one of claims 1 to 5, wherein the Cu-Mn doped Fe-MOF material contains three metal elements of Fe, Cu and Mn.
7. The method for treating organic wastewater by using the copper-manganese doped iron metal organic framework material to catalyze and activate persulfate, which is characterized by comprising the following steps of:
and adding the copper-manganese doped iron metal organic framework material and persulfate into organic pollutant wastewater, and reacting at normal temperature.
8. The method of claim 7, wherein the reaction is carried out in a shaker at a speed of 150 to 250 rpm; the reaction time is 120-150 min; the pH value of the organic pollutant wastewater is 3-9.
9. The method according to claim 7, wherein the persulfate is sodium persulfate or potassium persulfate.
10. The method of claim 7, wherein the molar ratio of persulfate to organic contaminant is 50: 1-200: 1; the dosage of the copper-manganese doped iron metal organic framework material is 0.1-0.6 g/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110651265.8A CN113351254B (en) | 2021-06-10 | 2021-06-10 | Copper-manganese doped iron metal organic framework material, preparation method thereof and method for treating organic wastewater by catalytically activating persulfate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110651265.8A CN113351254B (en) | 2021-06-10 | 2021-06-10 | Copper-manganese doped iron metal organic framework material, preparation method thereof and method for treating organic wastewater by catalytically activating persulfate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113351254A true CN113351254A (en) | 2021-09-07 |
| CN113351254B CN113351254B (en) | 2022-07-26 |
Family
ID=77533723
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110651265.8A Active CN113351254B (en) | 2021-06-10 | 2021-06-10 | Copper-manganese doped iron metal organic framework material, preparation method thereof and method for treating organic wastewater by catalytically activating persulfate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113351254B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114931978A (en) * | 2022-05-31 | 2022-08-23 | 华南理工大学 | Defect metal organic framework material and preparation method and application thereof |
| CN115970761A (en) * | 2022-12-14 | 2023-04-18 | 中国五冶集团有限公司 | Synthesis method and test method of catalytic material of alumina reactor |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2804313A1 (en) * | 2010-07-20 | 2012-01-26 | The Regents Of The University Of California | Functionalization of organic molecules using metal-organic frameworks (mofs) as catalysts |
| CN104992848A (en) * | 2015-06-30 | 2015-10-21 | 中国地质大学（武汉） | Binary metal organic framework material applied to super capacitor and preparation method for binary metal organic framework material |
| CN105854944A (en) * | 2016-03-31 | 2016-08-17 | 华南理工大学 | Copper doped ferrous metal organic framework material as well as preparation method and method for activating persulfate to treat organic wastewater by using same |
| US20180274013A1 (en) * | 2015-09-23 | 2018-09-27 | Nanyang Technological University | Metal-organic framework nanosheet |
| CN111533237A (en) * | 2020-05-12 | 2020-08-14 | 湖南鑫恒环境科技有限公司 | Method for treating antibiotic wastewater by using manganese ion doped metal organic framework material |
-
2021
- 2021-06-10 CN CN202110651265.8A patent/CN113351254B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2804313A1 (en) * | 2010-07-20 | 2012-01-26 | The Regents Of The University Of California | Functionalization of organic molecules using metal-organic frameworks (mofs) as catalysts |
| CN104992848A (en) * | 2015-06-30 | 2015-10-21 | 中国地质大学（武汉） | Binary metal organic framework material applied to super capacitor and preparation method for binary metal organic framework material |
| US20180274013A1 (en) * | 2015-09-23 | 2018-09-27 | Nanyang Technological University | Metal-organic framework nanosheet |
| CN105854944A (en) * | 2016-03-31 | 2016-08-17 | 华南理工大学 | Copper doped ferrous metal organic framework material as well as preparation method and method for activating persulfate to treat organic wastewater by using same |
| CN111533237A (en) * | 2020-05-12 | 2020-08-14 | 湖南鑫恒环境科技有限公司 | Method for treating antibiotic wastewater by using manganese ion doped metal organic framework material |
Non-Patent Citations (2)
| Title |
|---|
| QIU, SY，ET AL.: "Enhancing water stability of MIL-101(Cr) by doping Ni(II)", 《APPLIED SURFACE SCIENCE》 * |
| 王晨曦等: "负载型颗粒活性炭催化过硫酸钠氧化降解橙黄G", 《环境工程学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114931978A (en) * | 2022-05-31 | 2022-08-23 | 华南理工大学 | Defect metal organic framework material and preparation method and application thereof |
| CN114931978B (en) * | 2022-05-31 | 2023-09-26 | 华南理工大学 | Defective metal organic framework material and preparation method and application thereof |
| CN115970761A (en) * | 2022-12-14 | 2023-04-18 | 中国五冶集团有限公司 | Synthesis method and test method of catalytic material of alumina reactor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113351254B (en) | 2022-07-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113351254B (en) | Copper-manganese doped iron metal organic framework material, preparation method thereof and method for treating organic wastewater by catalytically activating persulfate | |
| CN108722497B (en) | TiO 22-MOFs photocatalyst, preparation method and application thereof | |
| CN109054033B (en) | Iron/cobalt bimetal organic framework material and preparation method and application thereof | |
| CN107285452B (en) | Method for rapidly degrading antibiotics | |
| CN109482233B (en) | Ferrous metal organic framework material, normal-pressure synthesis method thereof and method for treating organic pollutants by catalytically activating persulfate | |
| CN107744806B (en) | Preparation method of catalyst for catalytically decomposing ozone by taking expanded graphite as carrier | |
| CN102249395B (en) | Water ozonization treatment method by taking cerium oxide nanomaterial as catalyst | |
| CN109759110A (en) | A kind of N doping porous carbon loaded titanium dioxide photocatalyst and the preparation method and application thereof | |
| CN105080526B (en) | A kind of titanium dioxide-diatom ooze composite process of indoor formaldehyde degradation by photocatalytic oxidation process prepared by biological template | |
| CN103736515A (en) | High-property absorption and wave absorption type catalyst for VOCs (Volatile Organic Chemicals) catalytic oxidation and preparation of catalyst | |
| CN109054034B (en) | Bimetallic copper/cobalt metal-organic framework material and preparation method and application thereof | |
| CN109622005A (en) | A kind of preparation method and its electrochemical applications of porous carbon-supported nitrogenous bimetallic catalyst | |
| CN111420708B (en) | Graphene covalent grafted aminobenzene terpyridine-iron complex Fenton catalyst and preparation method thereof | |
| CN110404544A (en) | A kind of bimetallic catalytic material and its preparation method and application method | |
| CN104841441A (en) | Preparation method and application of catalyst for purifying HCN through hydrolysis-oxidation coupling technology | |
| CN110280277B (en) | Carbon dioxide electrochemical reduction catalyst and preparation method thereof | |
| CN112973744B (en) | Photoelectric catalyst and preparation method thereof | |
| US20210394164A1 (en) | MILLIMETER-SCALE PEROXYMONOSULFATE ACTIVATOR ZSM-5-(C@Fe) AND PREPARATION METHOD AND APPLICATION THEREOF | |
| CN111569904A (en) | Hollow sphere photocatalyst and preparation method and application thereof | |
| CN107469818A (en) | CaZrO3The preparation method of carrier and by noble-metal-supported in supported catalyst and preparation method and application | |
| CN114042448B (en) | Preparation method and application of Mn-MOF-based two-dimensional sheet manganese oxide/mesoporous carbon catalyst | |
| CN110947403A (en) | Ag3PO4-BiVO4Heterojunction-supported porous carbon photocatalytic degradation material and preparation method thereof | |
| CN114950437A (en) | Preparation of supported Cu-Co bimetallic group ZIF derived Cu/Co-C ozone catalyst, product and application | |
| CN111974372B (en) | Photocatalyst and preparation method and application thereof | |
| CN107754859A (en) | Catalyst and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |