CN112521622A - Preparation method of MOFs derivatives for catalytically activating peroxymonosulfate - Google Patents

Preparation method of MOFs derivatives for catalytically activating peroxymonosulfate Download PDF

Info

Publication number
CN112521622A
CN112521622A CN202011478813.3A CN202011478813A CN112521622A CN 112521622 A CN112521622 A CN 112521622A CN 202011478813 A CN202011478813 A CN 202011478813A CN 112521622 A CN112521622 A CN 112521622A
Authority
CN
China
Prior art keywords
mofs
treated
treatment
mixed solution
preparation
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.)
Pending
Application number
CN202011478813.3A
Other languages
Chinese (zh)
Inventor
魏健
敖蒙蒙
宋永会
熊兆锟
赖波
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chinese Research Academy of Environmental Sciences
Original Assignee
Chinese Research Academy of Environmental Sciences
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Chinese Research Academy of Environmental Sciences filed Critical Chinese Research Academy of Environmental Sciences
Priority to CN202011478813.3A priority Critical patent/CN112521622A/en
Publication of CN112521622A publication Critical patent/CN112521622A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • 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
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • 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
    • 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
    • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • B01J2531/26—Zinc
    • 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
    • C02F2101/34—Organic compounds containing oxygen
    • 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
    • C02F2101/38—Organic compounds containing nitrogen
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a preparation method of MOFs derivatives for catalytically activating peroxymonosulfate, which specifically comprises the following steps: preparing materials; adding Zn (NO)3)2·6H2O、FeSO4·7H2Dissolving the mixed O in methanol to obtain a first mixed solution to be treated; dissolving 2-MeIM in methanol to obtain a second mixed solution to be treated; respectively carrying out ultrasonic treatment on the first mixed solution to be treated and the second mixed solution to be treated, then mixing, carrying out magnetic stirring, and then sealing the mixture solution and standing for 24-30 h at room temperature; centrifuging, washing, and vacuum drying to obtain the final productPowder is removed; calcining, cooling, acid washing, washing pH to neutrality, and vacuum drying to obtain the catalyst-MOFs derivative; the preparation method has higher safety by adopting a standing method, and has simpler and more convenient integral process and lower cost; the addition amount of the iron element in the adopted raw materials is less, and no secondary pollution is caused in the later water treatment.

Description

Preparation method of MOFs derivatives for catalytically activating peroxymonosulfate
Technical Field
The invention belongs to the technical field of preparation of wastewater catalysts, and particularly relates to a preparation method of MOFs derivatives for catalytically activating peroxymonosulfate.
Background
The catalytic activation of Peroxymonosulfate (PMS) is one of the important directions of the current advanced oxidation water treatment technology development, and the development of a high-performance PMS activated catalyst is the core of the direction.
PMS has a standard oxidation-reduction potential of 1.82V and PDS has a standard oxidation potential of 2.01V, and thus is oxidizing. However, under the condition of normal temperature, the oxidation rate is slow, SO the persulfate has little oxidation effect on organic pollutants, and SO is generated by activating PS4-So that the organic pollutants can be efficiently oxidized and degraded. Common activation methods include photoactivation, thermal activation, transition metal activation, and activation of iron or iron-modified catalysts.
Because the existing pharmaceutical industry is an important supporting industry in national economy in China, compared with other consumer products, the pharmaceutical product has lower price elasticity, the consumer needs are more stable, and the pharmaceutical product is increased along with the development of economy and is not easily influenced by sudden and accidental factors, the pharmaceutical industry is a steadily growing sunward industry. As a basic medicament, the antibiotic has wide clinical application and is a large-scale product in various medicament markets in China at present. The ministry of environmental protection, the first national pollution sources census bulletin, shows that the annual chemical oxygen demand emission value of the pharmaceutical industry accounts for 3.07% of the total point source emission of the national industry. Because pharmaceutical enterprises need to make production plans according to market demands, adjust the types and the quantities of produced products, and raw materials and production processes required by different essential products are different, the water quality and the water quantity of pharmaceutical wastewater fluctuate greatly, and water pollution caused by the pharmaceutical wastewater brings a serious challenge to industrial development. The situation occurs in China, and antibiotics are detected in farmland soil, rivers, lakes and underground water bodies in Europe, America and other countries at present. The national environmental protection agency detects various drug residue components including antibiotics in drinking water of 4100 ten thousand population in 24 major cities.
At present, the detection frequency of sulfonamides is the highest among the antibiotic drugs detected in the existing water environment. The sulfonamide is an antibacterial drug which is widely used, and the concentration of the sulfonamide in the water body is obviously increased due to the wide use of the sulfonamide. Therefore, research on the treatment of sulfamethoxazole drugs in water environment is necessary.
Disclosure of Invention
Aiming at the technical problems, the invention provides a preparation method of MOFs derivatives for catalyzing and activating peroxymonosulfate; the MOFs provided by the invention has a good frame structure, can be modified and calcined into a porous carbon material with a large specific surface area, and can be used as a good adsorption material for removing pollutants in water. N-coordinate bonds existing in the structure of the MOFs material can also be converted into heteroatom N to be doped in the carbon material through thermal activation, so that the catalytic capability of the carbon material is greatly improved. Meanwhile, metal cations existing in the MOFs material can be converted into metal or metal oxide, so that the catalytic capability of the carbon material can be further improved, and the metal cation can be effectively applied to the removal of drug pollutants in water by activating persulfate oxidation.
The technical scheme of the invention is as follows: preparation method of MOFs derivatives for catalytically activating peroxymonosulfate, wherein the MOFs derivatives specifically comprise Zn (NO)3)2·6H2O、FeSO4·7H2O、2-MeIM；
The preparation method of the MOFs derivative specifically comprises the following steps:
the method comprises the following steps: adding Zn (NO)3)2·6H2O、FeSO4·7H2O, 2-MeIM, wherein the molar ratio of O to 2-MeIM is 10-40: 0-2: preparing materials according to the proportion of 320-360;
step two: zn (NO) prepared in the first step3)2·6H2O、FeSO4·7H2Dissolving the mixed O in methanol according to the proportion of 1-2 g/80ml to obtain a first mixed solution to be treated; dissolving the 2-MeIM prepared in the step one in methanol according to the proportion of 3-4 g/80ml to obtain a second solutionMixed liquid to be treated;
respectively carrying out ultrasonic treatment on the first mixed solution to be treated and the second mixed solution to be treated, then mixing the first mixed solution to be treated and the second mixed solution to be treated after the ultrasonic treatment, and carrying out magnetic stirring to obtain a mixture solution; then sealing the mixture solution and standing for 24-30 h at room temperature;
step three: performing centrifugal separation on the mixture solution after standing treatment to obtain nano crystals, fully washing the nano crystals for 2-3 times by using methanol, and performing vacuum drying treatment to obtain precursor powder;
step four: placing the precursor powder obtained in the step three in a tube furnace, heating to 900-1000 ℃, keeping for 3-5 h, and then naturally cooling to room temperature; then carrying out acid washing treatment in a water bath, washing the pH value to be neutral, and carrying out vacuum drying treatment to obtain the catalyst, namely the MOFs derivative.
Further, the ultrasonic treatment condition in the second step is 50-70 KHZ, and the treatment time is 2-5 min; ultrasonic treatment can be used for assisting in accelerating dissolution, so that the raw materials can be quickly dissolved into the methanol.
Further, the rotating speed condition of the magnetic stirring in the step two is 400-500 rpm, and the stirring time is 3-8 min; the magnetic stirrer placed in the container is pushed by the magnetic field to perform circumferential operation, so that the aim of stirring liquid is fulfilled, and the liquid is guaranteed to be mixed to meet the required requirements.
Further, the rotation speed condition of the centrifugal separation treatment in the third step is 8000rpm, and the treatment time is 4-6 min.
Further, the temperature condition of the vacuum drying in the third step is 70-85 ℃, and the treatment time is 7-8 hours; the vacuum environment can effectively reduce the boiling point of water and can effectively avoid the problem of oxidation of the nano crystal caused by high temperature.
Further, the specific steps of the fourth step are as follows: placing the precursor powder obtained in the step three in a tube furnace, heating to 900-1000 ℃ at a heating rate of 5-10 ℃/min, keeping for 3-5 h, and then naturally cooling to room temperature; and finally, pickling the material in a water bath kettle by using 2mM sulfuric acid at the temperature of 80-85 ℃ for 4-5 h, washing the material by using ultrapure water until the pH is 7, and then drying the material in vacuum at the temperature of 70-85 ℃ for 7-8 h to obtain the catalyst, namely the MOFs derivative.
Further, after the temperature in the fourth step is increased to 900-1000 ℃, keeping the temperature for 3-5 hours under a flowing nitrogen atmosphere; the calcination under the nitrogen atmosphere is increased, so that the oxidation of Fe element in the calcination can be effectively avoided.
Further, the specific steps of the fourth step are as follows: placing the precursor powder obtained in the step three in a tubular furnace, heating to 300-500 ℃ at a heating rate of 5-10 ℃/min, introducing flowing nitrogen into the tubular furnace, heating to 900-1000 ℃ at a heating rate of 10-15 ℃/min, keeping for 3-4 h, and naturally cooling to room temperature; finally, pickling the material for 4-5 h at 80-85 ℃ in a water bath kettle by using 2mM sulfuric acid, washing the material by using ultrapure water until the pH value is 7, and then drying the material for 7-8 h in vacuum at 70-85 ℃ to obtain a catalyst, namely MOFs derivative; flowing nitrogen is introduced into the tubular furnace at 300-500 ℃ by utilizing a gradient heating mode, and N-coordinate bonds existing in the MOFs material structure can be effectively converted into heteroatom N to be doped in the carbon material through thermal activation under the premise of effectively controlling cost and reducing the use of nitrogen, so that the catalytic capacity of the carbon material is greatly improved.
Further, the specific steps of the fourth step are as follows: placing the precursor powder obtained in the step three in a tubular furnace, heating to 200-300 ℃ at a heating rate of 50 ℃/min, introducing flowing nitrogen into the tubular furnace, heating to 900-1000 ℃ at a heating rate of 5-10 ℃/min, keeping for 3-4 h, and naturally cooling to room temperature; finally, pickling the material for 4-5 h at 80-85 ℃ in a water bath kettle by using 2mM sulfuric acid, washing the material by using ultrapure water until the pH value is 7, and then drying the material for 7-8 h in vacuum at 70-85 ℃ to obtain a catalyst, namely MOFs derivative; the flowing nitrogen in the tubular furnace is kept for a long time, so that the oxidation of Fe element in the calcination can be effectively avoided in the absence of oxygen, and the generation of calcined substances is promoted.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method has higher safety by adopting a standing method, and has simpler and more convenient integral process and lower cost;
2. the addition amount of iron element in the adopted raw materials is less, and no secondary pollution is caused in the later water treatment;
3. the prepared catalyst, MOFs derivative, can effectively degrade sulfamethoxazole drug wastewater in a short time, and the degradation effect is obvious, when the ratio of Zn to Fe is 40: can completely degrade sulfamethoxazole drug wastewater in 1 hour.
Detailed Description
Example 1: a process for preparing MOFs derivatives for catalytic activation of peroxymonosulfate, the MOFs derivatives specifically include Zn (NO)3)2·6H2O、2-MeIM；
The preparation method of the MOFs derivative specifically comprises the following steps:
the method comprises the following steps: adding Zn (NO)3)2·6H2O, 2-MeIM in a molar ratio of 10: preparing 320 parts of raw materials;
step two: zn (NO) prepared in the first step3)2·6H2Dissolving O in methanol according to the proportion of 1g/80ml to obtain a first mixed solution to be treated; dissolving the 2-MeIM prepared in the step one in methanol according to the proportion of 3g/80ml to obtain a second mixed solution to be treated;
respectively carrying out ultrasonic treatment on the first mixed solution to be treated and the second mixed solution to be treated for 2min under the condition of 50KHZ, mixing, and magnetically stirring for 3min under the condition of the rotating speed of 400rpm to obtain a mixture solution; then sealing the mixture solution and standing for 24 hours at room temperature;
step three: performing centrifugal separation on the mixture solution after standing treatment to obtain nano crystals, fully washing the nano crystals for 2 times by using methanol, and performing vacuum drying treatment to obtain precursor powder; wherein, the rotation speed condition of the centrifugal separation treatment is 8000rpm, and the treatment time is 4 min; the temperature condition of vacuum drying is 70 ℃, and the processing time is 7 h;
step four: placing the precursor powder obtained in the step three in a tube furnace, heating to 900 ℃ at a heating rate of 5 ℃/min, keeping for 3h under a flowing nitrogen atmosphere, and then naturally cooling to room temperature; and finally, pickling the material for 4 hours at 80 ℃ in a water bath by using 2mM sulfuric acid, washing the material by using ultrapure water until the pH value is 7, and then drying the material for 7 hours in vacuum at 70 ℃ to obtain the catalyst, namely the MOFs derivative.
Example 2: a process for preparing MOFs derivatives for catalytic activation of peroxymonosulfate, the MOFs derivatives specifically include Zn (NO)3)2·6H2O、FeSO4·7H2O、2-MeIM；
The preparation method of the MOFs derivative specifically comprises the following steps:
the method comprises the following steps: adding Zn (NO)3)2·6H2O、FeSO4·7H2O, 2-MeIM in a molar ratio of 20: 1: preparing 340 parts;
step two: zn (NO) prepared in the first step3)2·6H2O、FeSO4·7H2Dissolving the mixed O in methanol according to the proportion of 1.5g/80ml to obtain a first mixed solution to be treated; dissolving the 2-MeIM prepared in the step one in methanol according to the proportion of 3-4 g/80ml to obtain a second mixed solution to be treated;
respectively carrying out ultrasonic treatment on the first mixed solution to be treated and the second mixed solution to be treated for 3min under the condition of 60KHZ, mixing, and magnetically stirring for 5min under the condition of the rotation speed of 450rpm to obtain a mixture solution; then sealing the mixture solution and standing for 28 hours at room temperature;
step three: performing centrifugal separation on the mixture solution after standing treatment to obtain nano crystals, fully washing the nano crystals for 2 times by using methanol, and performing vacuum drying treatment to obtain precursor powder; wherein, the rotation speed condition of the centrifugal separation treatment is 8000rpm, and the treatment time is 5 min; the temperature condition of vacuum drying is 80 ℃, and the processing time is 8 h;
step four: placing the precursor powder obtained in the step three in a tube furnace, heating to 960 ℃ at a heating rate of 8 ℃/min, keeping for 4h under a flowing nitrogen atmosphere, and then naturally cooling to room temperature; and finally, pickling the material for 5 hours at 83 ℃ in a water bath by using 2mM sulfuric acid, washing the material by using ultrapure water until the pH value is 7, and then drying the material for 8 hours in vacuum at 80 ℃ to obtain the catalyst, namely the MOFs derivative.
Example 3: a process for preparing MOFs derivatives for catalytic activation of peroxymonosulfate, the MOFs derivatives specifically include Zn (NO)3)2·6H2O、FeSO4·7H2O、2-MeIM；
The preparation method of the MOFs derivative specifically comprises the following steps:
the method comprises the following steps: adding Zn (NO)3)2·6H2O、FeSO4·7H2O, 2-MeIM in a molar ratio of 40: 1: preparing 340 parts;
step two: zn (NO) prepared in the first step3)2·6H2O、FeSO4·7H2Dissolving the mixed O in methanol according to the proportion of 2g/80ml to obtain a first mixed solution to be treated; dissolving the 2-MeIM prepared in the step one in methanol according to the proportion of 4g/80ml to obtain a second mixed solution to be treated;
respectively carrying out ultrasonic treatment on the first mixed solution to be treated and the second mixed solution to be treated for 5min under the condition of 70KHZ, then mixing, and carrying out magnetic stirring for 8min under the condition of the rotating speed of 400-500 rpm to obtain a mixture solution; then sealing the mixture solution and standing for 30 hours at room temperature;
step three: performing centrifugal separation on the mixture solution after standing treatment to obtain nano crystals, fully washing the nano crystals for 3 times by using methanol, and performing vacuum drying treatment to obtain precursor powder; wherein, the rotation speed condition of the centrifugal separation treatment is 8000rpm, and the treatment time is 6 min; the temperature condition of vacuum drying is 85 ℃, and the processing time is 8 h;
step four: placing the precursor powder obtained in the step three in a tube furnace, heating to 1000 ℃ at a heating rate of 10 ℃/min, keeping for 5 hours under a flowing nitrogen atmosphere, and then naturally cooling to room temperature; and finally, pickling the material for 5 hours at 85 ℃ in a water bath by using 2mM sulfuric acid, washing the material by using ultrapure water until the pH value is 7, and then drying the material for 7-8 hours in vacuum at 85 ℃ under the temperature condition to obtain the catalyst, namely the MOFs derivative.
Example 4: a process for preparing MOFs derivatives for catalytic activation of peroxymonosulfate, the MOFs derivatives specifically include Zn (NO)3)2·6H2O、2-MeIM；
The preparation method of the MOFs derivative specifically comprises the following steps:
the method comprises the following steps: adding Zn (NO)3)2·6H2O, 2-MeIM in a molar ratio of 40: preparing 340 parts;
step two: zn (NO) prepared in the first step3)2·6H2Dissolving O in methanol according to the proportion of 1.7g/80ml to obtain a first mixed solution to be treated; dissolving the 2-MeIM prepared in the step one in methanol according to the proportion of 3g/80ml to obtain a second mixed solution to be treated;
respectively carrying out ultrasonic treatment on the first mixed solution to be treated and the second mixed solution to be treated for 2min under the condition of 60KHZ, mixing, and magnetically stirring for 3min under the condition of 500rpm to obtain a mixture solution; then sealing the mixture solution and standing for 24 hours at room temperature;
step three: performing centrifugal separation on the mixture solution after standing treatment to obtain nano crystals, fully washing the nano crystals for 3 times by using methanol, and performing vacuum drying treatment to obtain precursor powder; wherein, the rotation speed condition of the centrifugal separation treatment is 8000rpm, and the treatment time is 4 min; the temperature condition of vacuum drying is 70 ℃, and the processing time is 7 h;
step four: placing the precursor powder obtained in the step three in a tubular furnace, heating to 300 ℃ at the heating rate of 5 ℃/min, introducing flowing nitrogen into the tubular furnace, heating to 900 ℃ at the heating rate of 10 ℃/min, keeping for 3h, and naturally cooling to room temperature; and finally, pickling the material for 4 hours at 80 ℃ in a water bath by using 2mM sulfuric acid, washing the material by using ultrapure water until the pH value is 7, and then drying the material for 7 hours in vacuum at 70 ℃ to obtain the catalyst, namely the MOFs derivative.
Example 5: a process for preparing MOFs derivatives for catalytic activation of peroxymonosulfate, the MOFs derivatives specifically include Zn (NO)3)2·6H2O、FeSO4·7H2O、2-MeIM；
The preparation method of the MOFs derivative specifically comprises the following steps:
the method comprises the following steps: adding Zn (NO)3)2·6H2O、FeSO4·7H2O, 2-MeIM in a molar ratio of 10: 1: 340 ratio ofPreparing materials;
step two: zn (NO) prepared in the first step3)2·6H2O、FeSO4·7H2Dissolving the mixed O in methanol according to the proportion of 1g/80ml to obtain a first mixed solution to be treated; dissolving the 2-MeIM prepared in the step one in methanol according to the proportion of 3g/80ml to obtain a second mixed solution to be treated;
respectively carrying out ultrasonic treatment on the first mixed solution to be treated and the second mixed solution to be treated for 2min under the condition of 60KHZ, mixing, and magnetically stirring for 3min under the condition of 500rpm to obtain a mixture solution; then sealing the mixture solution and standing for 24 hours at room temperature;
step three: performing centrifugal separation on the mixture solution after standing treatment to obtain nano crystals, fully washing the nano crystals for 3 times by using methanol, and performing vacuum drying treatment to obtain precursor powder; wherein, the rotation speed condition of the centrifugal separation treatment is 8000rpm, and the treatment time is 6 min; the temperature condition of vacuum drying is 80 ℃, and the processing time is 7 h;
step four: placing the precursor powder obtained in the step three in a tubular furnace, heating to 400 ℃ at the heating rate of 10 ℃/min, introducing flowing nitrogen into the tubular furnace, heating to 950 ℃ at the heating rate of 15 ℃/min, keeping for 4h, and naturally cooling to room temperature; and finally, pickling the material for 4 hours at 85 ℃ in a water bath by using 2mM sulfuric acid, washing the material by using ultrapure water until the pH value is 7, and then drying the material for 7 hours in vacuum at 80 ℃ to obtain the catalyst, namely the MOFs derivative.
Example 6: a process for preparing MOFs derivatives for catalytic activation of peroxymonosulfate, the MOFs derivatives specifically include Zn (NO)3)2·6H2O、FeSO4·7H2O、2-MeIM；
The preparation method of the MOFs derivative specifically comprises the following steps:
the method comprises the following steps: adding Zn (NO)3)2·6H2O、FeSO4·7H2O, 2-MeIM in a molar ratio of 40: 1: preparing 340 parts;
step two: zn (NO) prepared in the first step3)2·6H2O、FeSO4·7H2Dissolving the mixed O in methanol according to the proportion of 2g/80ml to obtain a first mixed solution to be treated; dissolving the 2-MeIM prepared in the step one in methanol according to the proportion of 4g/80ml to obtain a second mixed solution to be treated;
respectively carrying out ultrasonic treatment on the first mixed solution to be treated and the second mixed solution to be treated for 5min under the condition of 70KHZ, then mixing, and carrying out magnetic stirring for 8min under the condition of the rotating speed of 500rpm to obtain a mixture solution; then sealing the mixture solution and standing for 30 hours at room temperature;
step three: performing centrifugal separation on the mixture solution after standing treatment to obtain nano crystals, fully washing the nano crystals for 3 times by using methanol, and performing vacuum drying treatment to obtain precursor powder; wherein, the rotation speed condition of the centrifugal separation treatment is 8000rpm, and the treatment time is 6 min; the temperature condition of vacuum drying is 85 ℃, and the processing time is 8 h;
step four: placing the precursor powder obtained in the step three in a tubular furnace, heating to 500 ℃ at the heating rate of 10 ℃/min, introducing flowing nitrogen into the tubular furnace, heating to 1000 ℃ at the heating rate of 15 ℃/min, keeping for 4h, and naturally cooling to room temperature; and finally, pickling the material for 5 hours at 85 ℃ in a water bath by using 2mM sulfuric acid, washing the material by using ultrapure water until the pH value is 7, and then drying the material for 8 hours in vacuum at 85 ℃ under the temperature condition to obtain the catalyst, namely the MOFs derivative.
Example 7: a process for preparing MOFs derivatives for catalytic activation of peroxymonosulfate, the MOFs derivatives specifically include Zn (NO)3)2·6H2O、FeSO4·7H2O、2-MeIM；
The preparation method of the MOFs derivative specifically comprises the following steps:
the method comprises the following steps: adding Zn (NO)3)2·6H2O、FeSO4·7H2O, 2-MeIM in a molar ratio of 40: 1: preparing 340 parts;
step two: zn (NO) prepared in the first step3)2·6H2O、FeSO4·7H2Dissolving the mixed O in methanol according to the proportion of 1g/80ml to obtain a first mixed solution to be treated; dissolving the 2-MeIM prepared in the first step in a ratio of 3g/80mlObtaining a second mixed solution to be treated in the methanol;
respectively carrying out ultrasonic treatment on the first mixed solution to be treated and the second mixed solution to be treated for 2min under the condition of 50KHZ, mixing, and magnetically stirring for 3min under the condition of the rotating speed of 400rpm to obtain a mixture solution; then sealing the mixture solution and standing for 24 hours at room temperature;
step three: performing centrifugal separation on the mixture solution after standing treatment to obtain nano crystals, fully washing the nano crystals for 2 times by using methanol, and performing vacuum drying treatment to obtain precursor powder; wherein, the rotation speed condition of the centrifugal separation treatment is 8000rpm, and the treatment time is 4 min; the temperature condition of vacuum drying is 70 ℃, and the processing time is 7 h;
step four: placing the precursor powder obtained in the step three in a tubular furnace, heating to 200 ℃ at the heating rate of 50 ℃/min, introducing flowing nitrogen into the tubular furnace, heating to 900 ℃ at the heating rate of 5 ℃/min, keeping for 3h, and naturally cooling to room temperature; and finally, pickling the material for 4 hours at 80 ℃ in a water bath by using 2mM sulfuric acid, washing the material by using ultrapure water until the pH value is 7, and then drying the material for 7 hours in vacuum at 70 ℃ to obtain the catalyst, namely the MOFs derivative.
Example 8: a process for preparing MOFs derivatives for catalytic activation of peroxymonosulfate, the MOFs derivatives specifically include Zn (NO)3)2·6H2O、FeSO4·7H2O、2-MeIM；
The preparation method of the MOFs derivative specifically comprises the following steps:
the method comprises the following steps: adding Zn (NO)3)2·6H2O、FeSO4·7H2O, 2-MeIM in a molar ratio of 20: 1: preparing 340 parts;
step two: zn (NO) prepared in the first step3)2·6H2O、FeSO4·7H2Dissolving the mixed O in methanol according to the proportion of 1.7g/80ml to obtain a first mixed solution to be treated; dissolving the 2-MeIM prepared in the step one in methanol according to the proportion of 3.5g/80ml to obtain a second mixed solution to be treated;
respectively carrying out ultrasonic treatment on the first mixed solution to be treated and the second mixed solution to be treated for 3min under the condition of 60KHZ, mixing, and magnetically stirring for 5min under the condition of the rotation speed of 450rpm to obtain a mixture solution; then sealing the mixture solution and standing for 28 hours at room temperature;
step three: performing centrifugal separation on the mixture solution after standing treatment to obtain nano crystals, fully washing the nano crystals for 3 times by using methanol, and performing vacuum drying treatment to obtain precursor powder; wherein, the rotation speed condition of the centrifugal separation treatment is 8000rpm, and the treatment time is 5 min; the temperature condition of vacuum drying is 80 ℃, and the processing time is 8 h;
step four: placing the precursor powder obtained in the step three in a tubular furnace, heating to 250 ℃ at the heating rate of 50 ℃/min, introducing flowing nitrogen into the tubular furnace, heating to 900 ℃ at the heating rate of 5 ℃/min, keeping for 4h, and naturally cooling to room temperature; and finally, pickling the material for 5 hours at 80 ℃ in a water bath by using 2mM sulfuric acid, washing the material by using ultrapure water until the pH value is 7, and then drying the material for 8 hours in vacuum at 80 ℃ under the temperature condition to obtain the catalyst, namely the MOFs derivative.
Example 9: a process for preparing MOFs derivatives for catalytic activation of peroxymonosulfate, the MOFs derivatives specifically include Zn (NO)3)2·6H2O、FeSO4·7H2O、2-MeIM；
The preparation method of the MOFs derivative specifically comprises the following steps:
the method comprises the following steps: adding Zn (NO)3)2·6H2O、FeSO4·7H2O, 2-MeIM in a molar ratio of 10: 1: preparing 340 parts;
step two: zn (NO) prepared in the first step3)2·6H2O、FeSO4·7H2Dissolving the mixed O in methanol according to the proportion of 2g/80ml to obtain a first mixed solution to be treated; dissolving the 2-MeIM prepared in the step one in methanol according to the proportion of 4g/80ml to obtain a second mixed solution to be treated;
respectively carrying out ultrasonic treatment on the first mixed solution to be treated and the second mixed solution to be treated for 5min under the condition of 70KHZ, then mixing, and carrying out magnetic stirring for 8min under the condition of rotating speed of 4500rpm to obtain a mixture solution; then sealing the mixture solution and standing for 30 hours at room temperature;
step three: performing centrifugal separation on the mixture solution after standing treatment to obtain nano crystals, fully washing the nano crystals for 3 times by using methanol, and performing vacuum drying treatment to obtain precursor powder; wherein, the rotation speed condition of the centrifugal separation treatment is 8000rpm, and the treatment time is 6 min; the temperature condition of vacuum drying is 85 ℃, and the processing time is 8 h;
step four: placing the precursor powder obtained in the step three in a tubular furnace, heating to 300 ℃ at the heating rate of 50 ℃/min, introducing flowing nitrogen into the tubular furnace, heating to 1000 ℃ at the heating rate of 10 ℃/min, keeping for 4h, and naturally cooling to room temperature; and finally, pickling the material for 5 hours at 85 ℃ in a water bath by using 2mM sulfuric acid, washing the material by using ultrapure water until the pH value is 7, and then drying the material for 8 hours in vacuum at 85 ℃ under the temperature condition to obtain the catalyst, namely the MOFs derivative.
Experimental example: 100mL sulfamethoxazole with the concentration of 5ppm is prepared and placed in a 250mL beaker, the reaction process is carried out in a water bath kettle at the temperature of 30 ℃, the frequency of mechanical stirring is 300rpm, 0.5mM peroxomonosulfate and 150mg/L of the catalyst prepared in example 1 are added to start the reaction, samples are taken at regular intervals after the reaction is started, 1mL is taken each time, and 50 mu L of 0.1mol/LNa is added immediately after the sampling2S2O3Stopping the reaction of the solution, filtering and collecting the solution by using a 0.22 mu mPTE filter membrane to be detected; after the reaction, 10ml of sample is taken and the dissolution of the iron element is measured by a flame atomic absorption method. Similarly, the catalysts prepared in examples 2 to 9 were tested, and the specific structures are as follows:
Figure BDA0002836741490000111
the experimental results are as follows: when the ratio of Zn to Fe is 40: 1, the sulfamethoxazole can be completely degraded after reaction for 10min, and the dissolution of Fe element is not detected in the experimental process.

Claims (10)

1. A process for the preparation of MOFs derivatives for the catalytic activation of peroxymonosulfate, characterized in that said MOFs derivatives are specifiedComprising Zn (NO)3)2·6H2O、FeSO4·7H2O、2-MeIM；
The preparation method of the MOFs derivative specifically comprises the following steps:
the method comprises the following steps: adding Zn (NO)3)2·6H2O、FeSO4·7H2O, 2-MeIM, wherein the molar ratio of O to 2-MeIM is 10-40: 0-2: preparing materials according to the proportion of 320-360;
step two: zn (NO) prepared in the first step3)2·6H2O、FeSO4·7H2Dissolving the mixed O in methanol according to the proportion of 1-2 g/80ml to obtain a first mixed solution to be treated; dissolving the 2-MeIM prepared in the step one in methanol according to the proportion of 3-4 g/80ml to obtain a second mixed solution to be treated;
respectively carrying out ultrasonic treatment on the first mixed solution to be treated and the second mixed solution to be treated, then mixing the first mixed solution to be treated and the second mixed solution to be treated after the ultrasonic treatment, and carrying out magnetic stirring to obtain a mixture solution; then sealing the mixture solution and standing for 24-30 h at room temperature;
step three: performing centrifugal separation on the mixture solution after standing treatment to obtain nano crystals, fully washing the nano crystals for 2-3 times by using methanol, and performing vacuum drying treatment to obtain precursor powder;
step four: placing the precursor powder obtained in the step three in a tube furnace, heating to 900-1000 ℃, keeping for 3-5 h, and then naturally cooling to room temperature; then carrying out acid washing treatment in a water bath, washing the pH value to be neutral, and carrying out vacuum drying treatment to obtain the catalyst, namely the MOFs derivative.
2. The process according to claim 1, wherein the ultrasonic treatment in step two is carried out at 50-70 KHZ for 2-5 min.
3. The method for preparing MOFs derivatives for the catalytic activation of peroxymonosulfate according to claim 1, wherein the rotation speed of the magnetic stirring in the second step is 400-500 rpm, and the stirring time is 3-8 min.
4. The method for preparing MOFs derivatives for the catalytic activation of peroxymonosulfate according to claim 1, wherein the rotation speed condition of the centrifugal separation treatment in the third step is 8000rpm, and the treatment time is 4-6 min.
5. The method for preparing MOFs derivatives for the catalytic activation of peroxymonosulfate according to claim 1, wherein the temperature condition of the vacuum drying in the third step is 70-85 ℃ and the treatment time is 7-8 h.
6. The process for the preparation of MOFs derivatives for the catalytic activation of peroxymonosulfate according to claim 1, wherein the nanocrystals are washed with methanol in step three.
7. The process for the preparation of MOFs derivatives for the catalytic activation of peroxymonosulfates according to claim 1, wherein the specific steps of step four are: placing the precursor powder obtained in the step three in a tube furnace, heating to 900-1000 ℃ at a heating rate of 5-10 ℃/min, keeping for 3-5 h, and then naturally cooling to room temperature; and finally, pickling the material in a water bath kettle by using 2mM sulfuric acid at the temperature of 80-85 ℃ for 4-5 h, washing the material by using ultrapure water until the pH is 7, and then drying the material in vacuum at the temperature of 70-85 ℃ for 7-8 h to obtain the catalyst, namely the MOFs derivative.
8. The preparation method of the MOFs derivatives for the catalytic activation of the peroxymonosulfate according to claim 7, wherein the temperature in the fourth step is kept for 3-5 hours under a flowing nitrogen atmosphere after being raised to 900-1000 ℃.
9. The process for the preparation of MOFs derivatives for the catalytic activation of peroxymonosulfates according to claim 1, wherein the specific steps of step four are: placing the precursor powder obtained in the step three in a tubular furnace, heating to 300-500 ℃ at a heating rate of 5-10 ℃/min, introducing flowing nitrogen into the tubular furnace, heating to 900-1000 ℃ at a heating rate of 10-15 ℃/min, keeping for 3-4 h, and naturally cooling to room temperature; and finally, pickling the material in a water bath kettle by using 2mM sulfuric acid at the temperature of 80-85 ℃ for 4-5 h, washing the material by using ultrapure water until the pH is 7, and then drying the material in vacuum at the temperature of 70-85 ℃ for 7-8 h to obtain the catalyst, namely the MOFs derivative.
10. The preparation method of the MOFs derivatives for the catalytic activation of peroxymonosulfate according to claim 1, wherein the MOFs derivatives are applied to the treatment of wastewater from the degradation of sulfamethoxazole drugs.
CN202011478813.3A 2020-12-15 2020-12-15 Preparation method of MOFs derivatives for catalytically activating peroxymonosulfate Pending CN112521622A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011478813.3A CN112521622A (en) 2020-12-15 2020-12-15 Preparation method of MOFs derivatives for catalytically activating peroxymonosulfate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011478813.3A CN112521622A (en) 2020-12-15 2020-12-15 Preparation method of MOFs derivatives for catalytically activating peroxymonosulfate

Publications (1)

Publication Number Publication Date
CN112521622A true CN112521622A (en) 2021-03-19

Family

ID=75000196

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011478813.3A Pending CN112521622A (en) 2020-12-15 2020-12-15 Preparation method of MOFs derivatives for catalytically activating peroxymonosulfate

Country Status (1)

Country Link
CN (1) CN112521622A (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110828830A (en) * 2019-11-01 2020-02-21 北京化工大学 Self-growing carbon tube composite ZIF-8 oxygen reduction electrocatalyst
CN110947385A (en) * 2019-11-30 2020-04-03 华南理工大学 Carbon-encapsulated defective iron nano catalyst, preparation method thereof and application thereof in catalyzing peroxymonosulfate to degrade emerging pollutants

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110828830A (en) * 2019-11-01 2020-02-21 北京化工大学 Self-growing carbon tube composite ZIF-8 oxygen reduction electrocatalyst
CN110947385A (en) * 2019-11-30 2020-04-03 华南理工大学 Carbon-encapsulated defective iron nano catalyst, preparation method thereof and application thereof in catalyzing peroxymonosulfate to degrade emerging pollutants

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JI, YUEFEI等: ""Degradation of ciprofloxacin and sulfamethoxazole by ferrous-activated persulfate: Implications for remediation of groundwater contaminated by antibiotics"", 《SCIENCE OF THE TOTAL ENVIRONMENT》 *
WU, SHAOHUA等: ""High-performance porous carbon catalysts doped by iron and nitrogen for degradation of bisphenol F via peroxymonosulfate activation"", 《CHEMICAL ENGINEERING JOURNAL》 *
ZHUO SHEN等: ""Fe-based carbonitride as Fenton-like catalyst for the elimination of organic contaminants"", 《ENVIRONMENTAL RESEARCH》 *

Similar Documents

Publication Publication Date Title
CN111790422B (en) Graphitized nitrogen-complexed Fe (III) -Fe0Catalyst, and synthesis method and application thereof
CN109603883A (en) A kind of@nanometers of phosphatization cobalt composite catalysts of N doping porous carbon polyhedron and preparation method thereof that can efficiently activate persulfate
US11760673B2 (en) Treatment method of wastewater containing heterocyclic organics and adsorbing material obtained therefrom
CN105668759A (en) Method for recycling Fenton iron mud
CN105381797A (en) Preparation of catalytic ozonation supported catalyst used for treating sewage and doped with dual rare earth elements
CN109364924B (en) Magnetic nano ozone catalyst CoFe2O4And preparation method and application thereof
CN114487048B (en) Evaluation method for reaction efficiency of perovskite metal oxide material and peroxomonosulfate
CN109621974B (en) CuMn2O4Method for treating polluted water by ozone catalytic oxidation and removal of pollutants through rGO composite material
CN114192146B (en) Magnetic microporous carbon-based cobalt catalyst based on space confinement effect and preparation method and application thereof
CN103495428A (en) Preparation method of carbon nano-tube based Fenton-like catalyst for advanced oxidation system
CN109317151A (en) A kind of preparation method of the catalyst for ultraviolet catalytic wet oxidation
CN114308113A (en) Preparation method of modified 13X molecular sieve/activated carbon carrier loaded metal oxide ozone catalyst
CN113713855A (en) Ferric alginate-ascorbic acid gel ball and preparation method and application thereof
CN112521622A (en) Preparation method of MOFs derivatives for catalytically activating peroxymonosulfate
CN109316956B (en) Reaction system and purification method for purifying VOCs in industrial waste gas
CN106111105A (en) A kind of for composite catalyst processing antibiotic waste water and its preparation method and application
CN102372378A (en) Treatment method of waste water produced by adopting castor oil to prepare decanedioic acid
CN115715980A (en) Mn 3 O 4 CNTs Fenton catalyst, preparation method and application thereof
CN113117698B (en) Preparation method of magnetic nano iron-molybdenum composite catalyst and application of catalyst
CN114797874A (en) Spinel ferrite catalyst doped with metallic copper, preparation method and application
CN107442141B (en) A kind of solid super-strong acid is for being catalyzed hydrogen peroxide/ozone purposes and method
CN114534726A (en) Iron/oxygen doped carbon-based filter type electro-Fenton cathode and preparation method and application thereof
CN209583860U (en) A kind of hybrid apparatus for treating carbonized waste water
CN102757146A (en) Method for treating coal pressure gasification wastewater by employing coagulation-photocatalytic degradation
CN114917937B (en) Catalyst for activating peroxymonosulfate to degrade organic waste liquid and preparation method thereof

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