CN114797933B - Nano-cage composite catalyst and preparation method and application thereof - Google Patents
Nano-cage composite catalyst and preparation method and application thereof Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- 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
-
- 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
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Abstract
Nanometer cage composite catalyst, its preparation and application, and the nanometer cage composite catalyst is prepared with active sludge, ferrous oxalate and absolute alcohol and through mixing in N 2 Pyrolyzing in atmosphere, cooling to room temperature, sequentially cleaning the obtained solid with absolute ethyl alcohol, concentrated hydrochloric acid and deionized water, and drying to obtain the nitrogen-doped biomass carbon nanocage; uniformly mixing the nitrogen-doped biomass carbon nanocages with ammonium chloride, and N 2 After the heat treatment of protection and heat preservation is finished, air cooling is carried out to room temperature, water and ethanol are used for cleaning and filtering, and finally drying is carried out; mixing Cu salt and Co salt according to any mole ratio, adding the mixture into a mixed solution of DMF, methanol and water together with the product, adding DHTA, carrying out ultrasonic treatment to fully dissolve the mixture into the mixed solution, sealing, and then placing the mixture into an oven for reaction to obtain a Cu-Co-MOF-74@NCNC material; cu-Co-MOF74@NCNC material is coated on N 2 Carbonizing in the atmosphere to obtain the Cu-CO@NCNC catalyst.
Description
Technical Field
The invention relates to the field of water pollutant treatment, in particular to a MOF derivative material @ nitrogen doped biomass carbon nano-cage composite catalyst, and a preparation method and application thereof.
Background
The human being pollutes the environment through the ways of discharging domestic sewage and industrial wastewater, leaking solid waste and landfill leachate, environmental emergency and the like in production activities, and causes the universal pollution of environmental media such as drinking water sources, rainwater, underground water, river water bodies, reclaimed water, lake water, seawater, soil and the like through the global hydrologic cycle effect, threatens ecological safety and human health, and needs to develop a safe, efficient and stable treatment technology to effectively control organic pollutants of sources such as sewage, wastewater, solid waste, landfill leachate and the like, effectively remove pollutants in mediums such as surface water, underground water, seawater, soil and the like in the environment, deeply treat drinking water, reclaimed water, rainwater and the like, and ensure ecological environmental safety and public health.
Currently, major concerns are raised about serious risks and some toxic organic contaminants such as drugs, antibiotics, endocrine disruptors, pesticides, persistent organic contaminants, etc. The current common methods such as microbial degradation, activated carbon adsorption, membrane filtration and the like still have the defects of low efficiency, large influence on water quality, limited application range, higher running cost, weaker stability and the like.
Advanced oxidation processes, represented by Fenton and Fenton-like oxidation, have a good treatment effect on organic pollutants by generating high-activity free radicals (such as hydroxyl free radicals), and are used as advanced treatment technologies in the fields of treatment and repair of drinking water, sewage, wastewater, groundwater and the like in a large scale, but are still limited in many ways. Fenton oxidation is suitable for treating pollutants in acidic water (pH=3.5), a large amount of acid and alkali are often needed to be added for regulating the pH of water to be treated, and the consumption of the medicament is very large; fenton and Fenton-like oxidation require a large amount of ferrous ions, a large amount of iron mud can be generated, the iron mud is required to be further treated subsequently, and the treatment difficulty and cost are obviously increased; oxidizing agent H 2 O 2 The dosage is large, the effective use efficiency is low, a large amount of oxidant remains in the treated water, the further accurate treatment is needed, the operation management difficulty is increased, and the H of the liquid 2 O 2 Is a dangerous article, cannot be prepared on site in large scale at present, and has obvious potential safety hazard in long-distance transportation. Current improvements to Fenton and Fenton-like oxidation mainly include new oxidants, catalysts, and the like.
The hydroxyl radical is a non-selective high-activity species, so that the efficiency of oxidizing and removing pollutants is obviously influenced by water quality factors, and the application range is limited and the practical use effect is poor. The sulfate radical has extremely high oxidation activity, and the rate constant of the sulfate radical reacting with most of organic matters is close to or even exceeds that of hydroxyl radical, so that the sulfate radical has the greatest advantage of good reaction selectivity, is obviously less influenced by water quality, and has higher actual pollutant treatment efficiency. The safe, efficient, stable and economical production of sulfate radicals has been the focus of attention and the heart of technical development in the academia and industry. Persulfates such as peroxodisulfates and peroxomonosulfates can generate sulfate radicals by activation of ultraviolet light, transition metals, catalysts.
Separable solid catalysts are an effective means of strengthening Fenton and Fenton-like systems (including hydrogen peroxide, persulfates). Although partial catalysts have better catalytic effects, the activity and stability of the catalysts are insufficient, the activity is difficult to stabilize for a long time, and the catalysts cannot be applied in large scale practically; high-efficiency catalysts often require precious metals (such as Au, ag, pt and the like), and are expensive, but have insufficient stability and high treatment cost; the catalyst is easy to be polluted and has unstable activity, the stability of the method is poor, and the practical application is limited; the catalyst is easy to deactivate, easy to run off, difficult to recycle and difficult to reuse, and has a certain potential risk.
In view of the foregoing, fenton treatment of pollutants in drinking water, domestic sewage, industrial wastewater, rainwater, groundwater, surface water, seawater, soil, landfill leachate and solid waste remains a great challenge in the field of environmental pollution control and water treatment at present, and development of a safe, efficient, stable and economical catalyst for catalyzing persulfate oxidation to remove pollutants is highly desirable.
Disclosure of Invention
The technical problems to be solved are as follows: although the catalyst has better catalytic effect on part of the catalyst, the activity and stability of the catalyst are insufficient, the activity is difficult to stabilize for a long time, and the catalyst cannot be applied in large scale practically; high-efficiency catalysts often require precious metals (such as Au, ag, pt and the like), and are expensive, but have insufficient stability and high treatment cost; the invention provides a nano-cage composite catalyst, and a preparation method and application thereof, wherein the catalyst is easy to be polluted and unstable in activity, has poor stability and limited practical application and the like.
The technical scheme is as follows: the preparation method of the nano cage composite catalyst comprises the following steps: 1) Mixing 10g of activated sludge, 10g of ferrous oxalate and 50mL of absolute ethyl alcohol uniformly, and adding the mixture into N 2 Pyrolyzing at 600 ℃ for 5 hours in the atmosphere, cooling to room temperature, sequentially cleaning the obtained solid with absolute ethyl alcohol, concentrated hydrochloric acid and deionized water, and drying to obtain the nitrogen-doped biomass carbon nanocage; 2) Uniformly mixing the nitrogen-doped biomass carbon nanocages with 20g of ammonium chloride and N 2 After heat treatment is finished after the heat preservation at 500 ℃ for 30min, air cooling is carried out to room temperature, water and ethanol are used for cleaning and filtering, and finally drying is carried out; 3) Mixing 1.5g of Cu salt and Co salt according to any molar ratio, adding the mixture into 210mL of mixed solution of DMF, methanol and water together with 2g of the product obtained in the step 2), adding 0.5g of DHTA, carrying out ultrasonic treatment to fully dissolve the mixed solution into the mixed solution, sealing, and then placing the mixture in an oven to react for 24 hours at 120 ℃ to obtain a Cu-Co-MOF-74@NCNC material; 4) The Cu-Co-MOF74@NCNC material obtained in the step 3) is added in N 2 Carbonizing for 1h at 500-700 ℃ in the atmosphere to obtain the Cu-CO@NCNC catalyst.
Preferably, the Cu salt is Cu (NO 3 ) 2 。
Preferably, the Co salt is Co (NO 3 ) 2 •6H 2 O。
Preferably, the volume ratio of the mixed solution of DMF, methanol and water is 1:1:1.
Preferably, the molar ratio of Co to the total Cu+Co is 30% -70%.
The nano-cage composite catalyst prepared by the preparation method.
The application of the nano-cage composite catalyst in preparing products for degrading organic matters in water by activating sulfate radical.
The beneficial effects are that: compared with the traditional carbon source, the activated sludge utilized by the carbon nanocage synthesis method realizes the recycling of resources to a certain extent, and compared with other toxic organic matters, the activated sludge has lower risk. Compared with the traditional catalyst taking carbon black as a carrier, the catalyst prepared by taking the nitrogen doped biomass carbon nanocage as a catalyst carrier has better catalytic activity and stability, and the main reasons are the hollow and graphitized shell structure of the carbon nanocage. In addition, compared with a carbon nano tube carrier with high graphitization degree, the special spherical structure of the carbon nano cage contains five-membered rings and seven-membered rings of carbon, which is favorable for nucleation of MOF on the surface of the carbon nano tube carrier, and the problem of winding agglomeration and uneven dispersion of the carbon nano tube due to too long length is avoided. Compared with other metal catalysts, the catalyst loaded on the carbon nanocage has a hollow structure, so that the MOF carbonized derivative has large specific surface area and more catalytic active sites; the common MOF derivative has the advantages that particles are not uniformly dispersed and are easy to aggregate, so that the catalytic activity is reduced, and when the nitrogen doped biomass carbon nanocages are used as carriers of the MOF derivative, the nitrogen doped biomass carbon nanocages can be uniformly deposited on the surfaces of the carbon nanocages, and good particle dispersibility can be maintained. Because of its good crystallinity, it has good corrosion resistance and strong durability. Cu and Co in Cu-Co@NCNC have good conductivity, and can be used as a catalyst to enhance electron transfer in a Fenton system and accelerate removal of organic matters. In addition, cu-Nx and Co-Nx as effective active sites can also promote the activation of free radicals. In general, cu—co@ncnc has excellent organic removal catalytic performance due to having cu—nx and co—nx bi-metal active sites, a high N doping level, a large specific surface area, and a special structure, as compared to other catalysts. The preparation method has simple thought and simple and convenient operation, is more efficient in degrading organic matters in the water body by using the Fenton system, and can be widely applied to the field of catalyzing and degrading organic pollutants by using the activated persulfate advanced oxidation system.
Drawings
FIG. 1 is a graph of the catalytic degradation of pollutants by Cu-Co@NCNC materials prepared in examples 1-5 of the invention (control group Cu-Co-MOF-74-600 ℃ C., example 1, example 2, example 3, example 4, example 5 in order from bottom to top).
Detailed Description
Example 1
In the embodiment, the specific preparation method of the MOF derivative material @ nitrogen doped biomass carbon nanocage composite catalyst comprises the following steps:
(1) Mixing 10g of activated sludge, 10g of ferrous oxalate and 50mL of absolute ethyl alcohol uniformly in a beaker, then placing the mixture in a clean quartz tube, and using N 2 The air in the discharge tube was thermally decomposed for 5 hours at 600 c. The quartz tube was then removed and air cooled to room temperature. And (3) adding the solid obtained after the reaction into absolute ethyl alcohol, hydrochloric acid and deionized water for cleaning, and finally drying the obtained powder to obtain the nitrogen-doped biomass carbon nanocage (NCNC).
(2) Uniformly mixing the nitrogen-doped biomass carbon nanocage prepared in the previous step with 20g of ammonium chloride, placing the mixture in a quartz tube, and filling N into the quartz tube 2 And (3) after the heat treatment is carried out for 30min at the temperature of 500 ℃, air cooling is carried out to room temperature, a heat treatment sample is collected, filtered by water and ethanol, and then dried, so that the purified NCNC is obtained.
(3) 2g NCNC, 0.45g Co (NO) 3 ) 2 •6H 2 O and 1.05g Cu (NO) 3 ) 2 Dissolving in a mixed solution consisting of 70mL of DMF, 70mL of absolute methanol and 70mL of water, adding 0.5g of DHTA, carrying out ultrasonic treatment to enable the DHTA to be fully dissolved in the mixed solution, and then placing a sealed bottle filled with the mixed solution in a 100 ℃ oven to react for 24 hours to obtain the 30% -Cu-Co-MOF-74@NCNC material, wherein the molar ratio of Co to the total amount of Cu+Co is 30%.
(4) Placing 30% -Cu-Co-MOF-74@NCNC material in a crucible, and adding N 2 Carbonizing at 600 ℃ in the atmosphere of (2) to obtain 30% -Cu-Co@NCNC-600 ℃.
The prepared 30% -Cu-Co@NCNC-600 ℃ is used for oxidative degradation of organic pollutants in water in a persulfate system, and COD in water is 5000 mg/L.
The catalyst is added in the following manner: taking 0.5g of 30% -Cu-Co@NCNC-600 ℃, putting the mixture into a reactor, adding 1L of organic wastewater with COD content of 5000 mg/L into the reactor, adding 0.5g of potassium persulfate, reacting for 60min, taking out a water sample, and detecting the residual COD content; the degradation effect is shown by a curve of 30% -Cu-Co@NCNC-600 ℃ in figure 1.
Example 2
In the embodiment, the specific preparation method of the MOF derivative material @ nitrogen doped biomass carbon nanocage composite catalyst comprises the following steps:
(1) Mixing 10g of activated sludge, 10g of ferrous oxalate and 50mL of absolute ethyl alcohol uniformly in a beaker, then placing the mixture in a clean quartz tube, and using N 2 The air in the discharge tube was thermally decomposed for 5 hours at 600 c. The quartz tube was then removed and air cooled to room temperature. And (3) adding the solid obtained after the reaction into absolute ethyl alcohol, hydrochloric acid and deionized water for cleaning, and finally drying the obtained powder to obtain the nitrogen-doped biomass carbon nanocage (NCNC).
(2) Uniformly mixing the nitrogen-doped biomass carbon nanocage prepared in the previous step with 20g of ammonium chloride, placing the mixture in a quartz tube, and filling N into the quartz tube 2 And (3) after the heat treatment is carried out for 30min at the temperature of 500 ℃, air cooling is carried out to room temperature, a heat treatment sample is collected, filtered by water and ethanol, and then dried, so that the purified NCNC is obtained.
(3) 2g NCNC, 0.75g Co (NO) 3 ) 2 •6H 2 O and 0.75g Cu (NO) 3 ) 2 Dissolving in a mixed solution consisting of 70mL of DMF, 70mL of absolute methanol and 70mL of water, adding 0.5g of DHTA, carrying out ultrasonic treatment to ensure that the DHTA is fully dissolved in the mixed solution, and then placing a sealed bottle filled with the mixed solution in a 100 ℃ oven for reaction for 24 hours to obtain a 50% -Cu-Co-MOF-74@NCNC material, wherein the molar ratio of Co to the total amount of Cu+Co is 50%.
(4) Placing 50% -Cu-Co-MOF-74@NCNC material in a crucible, and adding N 2 Carbonizing at 600 ℃ in the atmosphere of (2) to obtain 50% -Cu-Co@NCNC-600 ℃.
The prepared 50% -Cu-Co@NCNC-600 ℃ is used for oxidative degradation of organic pollutants in water in a persulfate system, and COD in water is 5000 mg/L.
The catalyst is added in the following manner: taking 0.5g of 50% -Cu-Co@NCNC-600 ℃, putting the mixture into a reactor, adding 1L of organic wastewater with COD content of 5000 mg/L into the reactor, adding 0.5g of potassium persulfate, reacting for 60min, taking out a water sample, and detecting the residual COD content; the degradation effect is shown by a curve of 50% -Cu-Co@NCNC-600 ℃ in figure 1.
Example 3
In the embodiment, the specific preparation method of the MOF derivative material @ nitrogen doped biomass carbon nanocage composite catalyst comprises the following steps:
(1) Mixing 10g of activated sludge, 10g of ferrous oxalate and 50mL of absolute ethyl alcohol uniformly in a beaker, then placing the mixture in a clean quartz tube, and using N 2 The air in the discharge tube was thermally decomposed for 5 hours at 600 c. The quartz tube was then removed and air cooled to room temperature. And (3) adding the solid obtained after the reaction into absolute ethyl alcohol, hydrochloric acid and deionized water for cleaning, and finally drying the obtained powder to obtain the nitrogen-doped biomass carbon nanocage (NCNC).
(2) Uniformly mixing the nitrogen-doped biomass carbon nanocage prepared in the previous step with 20g of ammonium chloride, placing the mixture in a quartz tube, and filling N into the quartz tube 2 And (3) after the heat treatment is carried out for 30min at the temperature of 500 ℃, air cooling is carried out to room temperature, a heat treatment sample is collected, filtered by water and ethanol, and then dried, so that the purified NCNC is obtained.
(3) 2g of NCNC, 1.05g of Co (NO 3 ) 2 •6H 2 O and 0.45g Cu (NO) 3 ) 2 Dissolving in a mixed solution consisting of 70mL of DMF, 70mL of absolute methanol and 70mL of water, adding 0.5g of DHTA, carrying out ultrasonic treatment to ensure that the DHTA is fully dissolved in the mixed solution, and then placing a sealed bottle filled with the mixed solution in a 100 ℃ oven to react for 24 hours to obtain the 70% -Cu-Co-MOF-74@NCNC material, namely, the molar ratio of Co to the total amount of Cu+Co is 70%.
(4) Placing 70% -Cu-Co-MOF-74@NCNC material in a crucible, and adding N 2 Carbonizing at 600 ℃ in the atmosphere of (2) to obtain 70% -Cu-CO@NCNC-600 ℃.
The prepared 70% -Cu-Co@NCNC-600 ℃ is used for oxidative degradation of organic pollutants in water in a persulfate system, and COD in water is 5000 mg/L.
The catalyst is added in the following manner: taking 0.5g of 70% -Cu-Co@NCNC-600 ℃, putting the mixture into a reactor, adding 1L of organic wastewater with the COD content of 5000 mg/L into the reactor, adding 0.5g of potassium persulfate, reacting for 60min, taking out a water sample, and detecting the residual COD content; the degradation effect is shown by a curve of 70% -Cu-Co@NCNC-600 ℃ in figure 1.
Example 4
In the embodiment, the specific preparation method of the MOF derivative material @ nitrogen doped biomass carbon nanocage composite catalyst comprises the following steps:
(1) Mixing 10g of activated sludge, 10g of ferrous oxalate and 50mL of absolute ethyl alcohol uniformly in a beaker, then placing the mixture in a clean quartz tube, and using N 2 The air in the discharge tube was thermally decomposed for 5 hours at 600 c. The quartz tube was then removed and air cooled to room temperature. And (3) adding the solid obtained after the reaction into absolute ethyl alcohol, hydrochloric acid and deionized water for cleaning, and finally drying the obtained powder to obtain the nitrogen-doped biomass carbon nanocage (NCNC).
(2) Uniformly mixing the nitrogen-doped biomass carbon nanocage prepared in the previous step with 20g of ammonium chloride, placing the mixture in a quartz tube, and filling N into the quartz tube 2 And (3) after the heat treatment is carried out for 30min at the temperature of 500 ℃, air cooling is carried out to room temperature, a heat treatment sample is collected, filtered by water and ethanol, and then dried, so that the purified NCNC is obtained.
(3) 2g NCNC, 0.75g Co (NO) 3 ) 2 •6H 2 O and 0.75g Cu (NO) 3 ) 2 Dissolving in a mixed solution consisting of 70mL of DMF, 70mL of absolute methanol and 70mL of water, adding 0.5g of DHTA, carrying out ultrasonic treatment to ensure that the DHTA is fully dissolved in the mixed solution, and then placing a sealed bottle filled with the mixed solution in a 100 ℃ oven for reaction for 24 hours to obtain a 50% -Cu-Co-MOF-74@NCNC material, wherein the molar ratio of Co to the total amount of Cu+Co is 50%.
(4) Placing 50% -Cu-Co-MOF-74@NCNC material in a crucible, and adding N 2 Carbonizing at 500 ℃ in the atmosphere of (2) to obtain 50% -Cu-Co@NCNC-500 ℃.
The prepared 50% -Cu-Co@NCNC-500 ℃ is used for oxidative degradation of organic pollutants in water in a persulfate system, and COD in water is 5000 mg/L.
The catalyst is added in the following manner: taking 0.5g of 50% -Cu-Co@NCNC-500 ℃, putting the mixture into a reactor, adding 1L of organic wastewater with COD content of 5000 mg/L into the reactor, adding 0.5g of potassium persulfate, reacting for 60min, taking out a water sample, and detecting the residual COD content; the degradation effect is shown by a curve of 50% -Cu-Co@NCNC-500 ℃ in figure 1.
Example 5
In the embodiment, the specific preparation method of the MOF derivative material @ nitrogen doped biomass carbon nanocage composite catalyst comprises the following steps:
(1) Mixing 10g of activated sludge, 10g of ferrous oxalate and 50mL of absolute ethyl alcohol uniformly in a beaker, then placing the mixture in a clean quartz tube, and using N 2 The air in the discharge tube was thermally decomposed for 5 hours at 600 c. The quartz tube was then removed and air cooled to room temperature. And (3) adding the solid obtained after the reaction into absolute ethyl alcohol, hydrochloric acid and deionized water for cleaning, and finally drying the obtained powder to obtain the nitrogen-doped biomass carbon nanocage (NCNC).
(2) Uniformly mixing the nitrogen-doped biomass carbon nanocage prepared in the previous step with 20g of ammonium chloride, placing the mixture in a quartz tube, and filling N into the quartz tube 2 And (3) after the heat treatment is carried out for 30min at the temperature of 500 ℃, air cooling is carried out to room temperature, a heat treatment sample is collected, filtered by water and ethanol, and then dried, so that the purified NCNC is obtained.
(3) 2gNCNC, 0.75g Co (NO) 3 ) 2 •6H 2 O and 0.75g Cu (NO) 3 ) 2 Dissolving in a mixed solution consisting of 70mL of DMF, 70mL of absolute methanol and 70mL of water, adding 0.5g of DHTA, carrying out ultrasonic treatment to ensure that the DHTA is fully dissolved in the mixed solution, and then placing a sealed bottle filled with the mixed solution in a 100 ℃ oven for reaction for 24 hours to obtain a 50% -Cu-Co-MOF-74@NCNC material, wherein the molar ratio of Co to the total amount of Cu+Co is 50%.
(4) Placing 50% -Cu-Co-MOF-74@NCNC material in a crucible, and adding N 2 Carbonizing at 700 ℃ in the atmosphere of (2) to obtain 50% -Cu-Co@NCNC-700 ℃.
The prepared 50% -Cu-Co@NCNC-700 ℃ is used for oxidative degradation of organic pollutants in water in a persulfate system, and COD in water is 5000 mg/L.
The catalyst is added in the following manner: taking 0.5g of 50% -Cu-Co@NCNC-700 ℃, putting the mixture into a reactor, adding 1L of organic wastewater with COD content of 5000 mg/L into the reactor, adding 0.5g of potassium persulfate, reacting for 60min, taking out a water sample, and detecting the residual COD content; the degradation effect is shown by a curve of 50% -Cu-Co@NCNC-700 ℃ in figure 1.
In the control group, the specific preparation method of the MOF derivative material catalyst is as follows:
(1) 0.75g Co (NO) 3 ) 2 •6H 2 O and 0.75g Cu (NO) 3 ) 2 Dissolving in a mixed solution consisting of 70mL of DMF, 70mL of absolute methanol and 70mL of water, adding 0.5g of DHTA, fully dissolving in the mixed solution by ultrasonic treatment, and then placing a sealed bottle filled with the mixed solution in a 100 ℃ oven for reaction for 24 hours to obtain the Cu-Co-MOF-74 material.
(2) Placing Cu-Co-MOF-74 material in crucible, and adding N 2 Carbonizing at 600 ℃ in the atmosphere of (2) to obtain Cu-Co-MOF-74-600 ℃.
The prepared Cu-Co-MOF-74-600 ℃ is used for oxidative degradation of organic pollutants in water in a persulfate system, and COD in water is 5000 mg/L.
The catalyst is added in the following manner: taking 0.5g of Cu-Co-MOF-74-600 ℃, putting the mixture into a reactor, adding 1L of organic wastewater with COD content of 5000 mg/L into the reactor, adding 0.5g of potassium persulfate, reacting for 60min, taking out a water sample, and detecting the residual COD content; the degradation effect is shown as a Cu-Co-MOF-74 curve in figure 1.
The Cu-Co@NCNC prepared by the method has better catalytic degradation effect than Cu-Co-MOF-74 in experiments, and because Cu and Co have good conductivity, the Cu-Co@NCNC can be used as a catalyst to enhance electron transfer in a Fenton system and accelerate removal of organic matters; in addition, cu-Nx and Co-Nx as effective active sites can also promote the activation of free radicals.
The Cu-Co@NCNC prepared by the method disclosed by the invention has the advantages that by adjusting the molar ratio of metal nodes of different CuCo, the two metal nodes are uniformly distributed on the MOF-74 framework according to a proportion, so that the characteristics of various types and continuously adjustable structural component sizes are realized, the Cu-Co@NCNC has different catalytic efficiencies, and the highest catalytic efficiency of 50% -Cu-Co@NCNC-600 ℃ can better degrade COD under the conditions of the embodiment.
The present invention is not limited to the above-described embodiments, and it should be understood by those skilled in the art that several equivalent changes and substitutions may be made thereto without departing from the principles of the present invention, and such equivalent changes and substitutions should also be considered to be within the scope of the present invention.
Claims (6)
1. The preparation method of the nano-cage composite catalyst is characterized by comprising the following steps of: 1) Mixing 10g of activated sludge, 10g of ferrous oxalate and 50mL of absolute ethyl alcohol uniformly, and adding the mixture into N 2 Pyrolyzing at 600 ℃ for 5 hours in the atmosphere, cooling to room temperature, sequentially cleaning the obtained solid with absolute ethyl alcohol, concentrated hydrochloric acid and deionized water, and drying to obtain the nitrogen-doped biomass carbon nanocage; 2) Uniformly mixing the nitrogen-doped biomass carbon nanocages with 20g of ammonium chloride and N 2 After heat treatment is finished after the heat preservation at 500 ℃ for 30min, air cooling is carried out to room temperature, water and ethanol are used for cleaning and filtering, and finally drying is carried out; 3) Mixing 1.5g of Cu salt and Co salt according to any molar ratio, adding the mixture into 210mL of mixed solution of DMF, methanol and water together with 2g of the product obtained in the step 2), adding 0.5g of DHTA, carrying out ultrasonic treatment to fully dissolve the mixed solution into the mixed solution, sealing, and then placing the mixture in an oven to react for 24 hours at 120 ℃ to obtain a Cu-Co-MOF-74@NCNC material; 4) The Cu-Co-MOF74@NCNC material obtained in the step 3) is added in N 2 Carbonizing for 1h at 500-700 ℃ in the atmosphere to obtain the Cu-Co@NCNC catalyst.
2. The method for preparing a nanocage composite catalyst according to claim 1, wherein the Cu salt in step 3) is Cu (NO 3 ) 2 。
3. The method for preparing a nanocage composite catalyst according to claim 1, wherein in step 3) the Co salt is Co (NO 3 ) 2 •6H 2 O。
4. The method for preparing the nanocage composite catalyst according to claim 1, wherein the volume ratio of the three in the mixed solution of DMF, methanol and water in the step 3) is 1:1:1.
5. The nanocage composite catalyst prepared by the method of any of claims 1-4.
6. The use of the nanocage composite catalyst of claim 5 to activate sulfate radicals to degrade organics in water.
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