CN113713816A - Preparation and application of copper-cobalt/carbon catalyst derived from metal organic framework material - Google Patents
Preparation and application of copper-cobalt/carbon catalyst derived from metal organic framework material Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 45
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 22
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims description 13
- 239000000463 material Substances 0.000 title description 14
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims abstract description 90
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
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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
- 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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- B01J35/23—
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- B01J35/39—
-
- B01J35/394—
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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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
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a copper-cobalt/carbon catalyst which is high in efficiency and easy to recover and is synthesized by a one-step carbonization method by taking Cu @ Co-MOF as a precursor. The carbon-based material derived from the MOFs organic ligand can prevent the aggregation of copper/cobalt nanoparticles and promote the highly uniform distribution of active metals, and the conductivity of the carbon-based material can promote the transfer of electrons to potassium hydrogen Persulfate (PMS), so that the copper/cobalt nanoparticles in the catalyst can jointly act to promote the improvement of the catalytic efficiency. The degradation rate of the prepared copper-cobalt/carbon catalyst on Ciprofloxacin (CIP) can reach 90%, the CIP removal rate can reach more than 85% after 4 cycles, and the catalyst is easy to separate from a solution through a magnet and has good stability and reusability.
Description
Technical Field
The invention belongs to the technical field of advanced oxidation, and mainly relates to preparation and application of a copper-cobalt/carbon catalyst derived from a metal organic framework material.
Background
Ciprofloxacin (CIP), a fluoroquinolone antibiotic (FQs), is widely used for the prevention and treatment of bacterial infectious diseases due to its broad-spectrum antibacterial activity. However, due to overuse and poor biodegradability, we can often detect CIP contaminants in aquatic environments. Research shows that even if the concentration of CIP in aqueous solution is low, the CIP still induces the organisms to generate drug resistance to antibiotics, and finally causes harm to human health. CIP entering the water environment can also lead to physiological abnormalities in plants/algae, as well as genotoxicity and carcinogenicity to organisms. Conventional treatment methods such as physical (adsorption) and chemical (precipitation, flocculation) methods have very limited efficiency in degrading CIP and may generate by-products during the treatment process to cause secondary pollution. Therefore, there is a strong need to develop an effective method for removing CIP in an aqueous environment to prevent the CIP from causing greater harm to the environment and human health.
MOFs are crystalline porous materials with periodic network structures assembled by coordination of multifunctional organic ligands with metal ions/clusters. Due to the differences in composition and structure, MOFs are considered as ideal precursors for the preparation of new materials consisting of metal nanoparticles and carbon matrix by pyrolysis. Compared to the use of biochar or carbon nanotubes as raw materials, the direct pyrolysis of MOFs to form carbon matrices is a more convenient and feasible method. In the high-temperature pyrolysis process, organic ligands in the MOFs are carbonized into carbon matrixes, and metal nodes are aggregated into metal nanoparticles. The formed metal nano particles are uniformly distributed on the surface of the carbon matrix and partially coated in the carbon matrix, so that the stability of the catalyst is further improved. And the carbon matrix is used as a dispersing agent, so that the aggregation of copper and cobalt can be effectively limited, and the highly uniform distribution of active metal is promoted. In recent years, cobalt-based carbon materials derived from MOFs have attracted considerable attention from researchers. Research shows that the cobalt-based bimetallic catalyst has better catalytic activity compared with a single metal catalyst. In fact, the addition of the second metal not only provides a new active site, but also promotes the catalytic effect by creating some specific properties through the interaction between the two metals. Of these, Cu/Co bimetallic catalysts are of particular interest because of their unique PMS activating catalytic activity.
Disclosure of Invention
In order to overcome the defects of the prior art and improve the defects, a Cu @ Co-MOF precursor is synthesized by adopting a one-step hydrothermal method, then the Cu @ Co-MOF precursor is pyrolyzed at 900 ℃ in a nitrogen atmosphere to generate a copper-cobalt/carbon (CuCo/C) nano composite catalyst, and the copper-cobalt/carbon nano composite catalyst is applied to activating persulfate to degrade ciprofloxacin pollutants.
In order to solve the problems, the invention is realized by the following technical scheme:
the synthesis method of the Cu @ Co-MOF precursor comprises the following steps:
s1, mixing 6mmol of cobalt nitrate (Co (NO)3)2.6H2O) and 6mmol of copper nitrate (Cu (NO)3)2.3H2O) and 12mmol of terephthalic acid (H)2BDC) was added to a beaker containing 60mL of N, N-Dimethylformamide (DMF) and stirred at room temperature for 20-30 min;
s2, transferring the mixed solution into a stainless steel autoclave with a 100mL polytetrafluoroethylene lining after stirring, and adding 0.8mL hydrofluoric acid;
s3, transferring the polytetrafluoroethylene-lined stainless steel autoclave filled with the uniformly mixed solution into an oven, heating at 150 ℃ for 72 hours, and naturally cooling to room temperature after the reaction is finished;
s4, washing the solid product with DMF, ethanol and water twice respectively, vacuum-drying at 70 ℃ for 12h, and collecting the Cu @ Co-MOF.
S5, preparing the carbon/cobalt/copper (CuCo/C) nano composite catalyst as follows:
charging the solid collected in S4 into a ceramic boat, placing into a tube furnace, heating to 900 deg.C at a rate of 5 deg.C/min, and adding N2Carbonizing for 2h under the atmosphere. After completion, the furnace was allowed to cool naturally to room temperature to obtain a CuCo/C catalyst.
In order to compare the catalytic performances of the catalyst under different copper-cobalt ratios, Cu (NO) is not added in the previous step3)2.3H2O catalysts were prepared with Co/C and copper to cobalt ratios of 2:3 and 3: 2.
According to the preparation scheme designed by the invention, a simple hydrothermal reaction is firstly carried out to obtain a Cu @ Co-MOF precursor, then a high-temperature calcination process is carried out, the related raw materials are easy to obtain, the experimental operation is simple, the conditions are easy to control, and the important point is that the synthesized material is stable, green, environment-friendly and pollution-free.
As a general technical concept, the invention also provides the practical application of the catalytic material in degrading antibiotics in wastewater, wherein the antibiotics are ciprofloxacin, and the preferable process is as follows:
(1) putting the prepared CuCo/C catalyst into 100mL of 10mg/L ciprofloxacin solution, and stirring and adsorbing for 30min at room temperature under the condition of not adding PMS;
(2) and (3) adding PMS under the same conditions as in the step (1) to realize the degradation of pollutants by activating PMS.
The addition amount of the prepared CuCo/C catalyst is that 0.25g/L of catalytic material is added in each liter of the wastewater containing the antibiotics; the concentration of the ciprofloxacin in the wastewater is 10 mg/L; the prepared CuCo/C catalyst is stirred for 0.5h in the application of activating PMS to degrade antibiotics in wastewater; the amount of PMS added is 0.25g/L added in each liter of the wastewater containing the antibiotics; the catalytic degradation time is 30 min.
The invention adopts a simple process to prepare the MOFs-derived metal carbon-based catalyst with good stability and excellent catalytic performance, and aims to overcome the defects of poor stability, high cost, poor catalytic performance and the like caused by the traditional method of using biochar or carbon nanotubes as raw materials to load metal nanoparticles. According to the invention, a Cu @ Co-MOF precursor is synthesized by adopting a one-step hydrothermal method, then the precursor is pyrolyzed at 900 ℃ in a nitrogen atmosphere to generate a copper-cobalt/carbon (CuCo/C) nano composite catalyst, in the high-temperature pyrolysis process, an organic ligand in MOFs is carbonized into a carbon matrix, and metal nodes are aggregated into metal nano particles. The formed metal nano particles are uniformly distributed on the surface of the carbon matrix and partially coated in the carbon matrix, so that the stability of the catalyst is further improved. And the carbon matrix is used as a dispersing agent, so that the aggregation of cobalt can be effectively limited, and the highly uniform distribution of active metal is promoted. In addition, the organic ligand carbon group in the MOF not only plays a role of a dispersing agent, prevents the aggregation of Cu/Co nano particles and promotes the highly uniform distribution of active metals, but also promotes the transfer of electrons from the catalyst to the PMS due to the conductivity of the organic ligand carbon group; furthermore, the Cu/Co double-nanoparticle interaction activates PMS to provideHigh catalytic efficiency. During the catalytic degradation, free radicals (SO)4 ·-,OH·and O2 ·-) And non-free radicals (1O2) The combined action mineralizes the contaminants into carbon dioxide and water.
Compared with the traditional technology, the invention has the advantages that:
the invention provides a MOFs-derived metal carbon-based catalyst, which is formed by assembling a multifunctional organic ligand and coordination of metal ions/clusters to form an MOFs precursor, and then a CuCo/C nano composite catalyst is obtained by a one-step pyrolysis method. In the high-temperature pyrolysis process, organic ligands in the MOFs are carbonized into carbon matrixes, and metal nodes are aggregated into metal nanoparticles. The formed metal nano particles are uniformly distributed on the surface of the carbon matrix and partially coated in the carbon matrix, so that the stability of the catalyst is further improved. And the carbon matrix is used as a dispersing agent, so that the aggregation of copper and cobalt can be effectively limited, and the highly uniform distribution of active metal is promoted. In addition, the organic ligand carbon group in the MOF not only plays a role of a dispersing agent, prevents the aggregation of Cu/Co nano particles and promotes the highly uniform distribution of active metals, but also promotes the transfer of electrons from the catalyst to the PMS due to the conductivity of the organic ligand carbon group; moreover, the Cu/Co double nanoparticles act synergistically to activate PMS, so that the catalytic efficiency is improved. It can be seen that the direct pyrolysis of MOFs to form carbon matrices is a more convenient and feasible method than the traditional use of biochar or carbon nanotubes as raw materials to support metal nano-ions. During the catalytic degradation, free radicals (SO)4 ·-,OH·and O2 ·-) And non-free radicals (1O2) The pollutants are mineralized into carbon dioxide and water under the combined action, and the degradation efficiency is improved compared with that of the traditional technology.
(2) The invention provides a preparation method of a CuCo/C catalyst, which has the advantages of easily obtained raw materials, high stability of synthetic materials, low energy consumption, high synthesis rate, simple process, easily controlled conditions, environmental friendliness, no secondary pollution and the like, and is suitable for continuous large-scale production.
(3) The invention also provides a method for degrading antibiotics in water, and the CuCo/C catalyst is used for degrading the antibiotics in water, has the advantages of simple operation, stable catalyst performance, high degradation efficiency and the like, and has good practical application value.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
Drawings
FIG. 1 is an XRD diffraction pattern of Cu @ Co-MOF of example 1 of the present invention, CuCo/C and Co/C of comparative example 1.
FIG. 2 is an XPS plot of Cu @ Co-MOF, CuCo/C of example 1 of the present invention. Wherein B, C and D are XPS plots of carbon atoms, copper atoms, and cobalt atoms, respectively.
FIG. 3 is an SEM and TEM electron micrograph of Cu @ Co-MOF, CuCo/C of example 1 according to the present invention.
FIG. 4 is a graph of adsorption-desorption isotherms for Cu @ Co-MOF of example 1 of the invention, CuCo/C and Co/C of comparative example 1. .
FIG. 5 is a CuCo/C magnetic test chart of example 1 of the present invention.
FIG. 6 is a graph of the time-degradation efficiency of Ciprofloxacin (CIP) for the Cu @ Co-MOF and CuCo/C catalysts prepared in example 1 of the present invention and the Co/C catalyst prepared in comparative example 1 with PMS added.
FIG. 7 is a graph of cycle number-degradation efficiency corresponding to the cyclic degradation of Ciprofloxacin (CIP) wastewater by the CuCo/C catalyst in example 3 of the present invention.
Detailed Description
The invention is described in more detail below with reference to examples and the accompanying drawings, but the invention is not limited thereto.
The materials and equipment used in the following examples are commercially available. In the examples of the present invention, unless otherwise specified, the adopted process is a conventional process, the adopted equipment is conventional equipment, and the obtained data are average values of three or more repeated experiments.
Example 1
The invention relates to a method for synthesizing a CuCo/C catalyst, which comprises the following steps:
(1) 6mmol of cobalt nitrate (Co (NO)3)2.6H2O) and 6mmol of copper nitrate (Cu (NO)3)2.3H2O) and 12mmol of terephthalic acid (H)2BDC) was added to a beaker containing 60mL of N, N-Dimethylformamide (DMF) and stirred at room temperature for 20-30 min;
(2) after stirring, transferring the mixed solution into a stainless steel autoclave with a 100mL polytetrafluoroethylene lining, and adding 0.8mL of hydrofluoric acid;
(3) transferring the polytetrafluoroethylene-lined stainless steel autoclave filled with the uniformly mixed solution into an oven, heating at 150 ℃ for 72 hours, and naturally cooling to room temperature after the reaction is finished;
(4) and respectively washing the solid product twice with DMF, ethanol and water, performing vacuum drying at 70 ℃ for 12h, and collecting the Cu @ Co-MOF.
(5) Putting the solid collected in the step (4) into a ceramic boat, putting the ceramic boat into a tube furnace, heating the ceramic boat to 900 ℃ at the speed of 5 ℃/min, and keeping the temperature in N2Carbonizing for 2h under the atmosphere. After completion, the furnace was allowed to cool naturally to room temperature to obtain a CuCo/C catalyst.
Comparative example 1
A method for producing a Co/C catalyst, which comprises the following steps, in the same manner as in steps (2) to (5), except that step (1) in example 1 is changed:
(1) 6mmol of cobalt nitrate (Co (NO)3)2.6H2O) and 12mmol of terephthalic acid (H)2BDC) was added to a beaker containing 60mL of N, N-Dimethylformamide (DMF) and stirred at room temperature for 20-30 min;
(2) after stirring, transferring the mixed solution into a 100mL stainless steel autoclave lined with polytetrafluoroethylene, and adding 0.8mL hydrofluoric acid;
(3) transferring the polytetrafluoroethylene-lined stainless steel autoclave filled with the uniformly mixed solution into an oven, sealing and heating at 150 ℃ for 72 hours, and naturally cooling to room temperature after the reaction is finished;
(4) and respectively washing the solid product twice with DMF, ethanol and water, performing vacuum drying at 70 ℃ for 12 hours, and collecting the Co-MOF.
(5) Putting the solid collected in the step (4) into a ceramic boat, putting the ceramic boat into a tube furnace, heating the ceramic boat to 900 ℃ at the speed of 5 ℃/min, and keeping the temperature in N2Carbonizing for 2h under the atmosphere. After completion, the furnace was allowed to cool naturally to room temperature to obtain a Co/C catalyst.
Experimental example 1
XRD analysis was performed on the Cu @ Co-MOF of example 1, CuCo/C and the Co/C of comparative example 1, and the results are shown in FIG. 1.
FIG. 1 is an XRD diffraction pattern of Cu @ Co-MOF of example 1 of the present invention, CuCo/C and Co/C of comparative example 1, respectively. As shown in figure 1, indexes (200), (220) and (440) corresponding to diffraction peaks of the Cu @ Co-MOF at 43.4 degrees, 50.4 degrees and 74.1 degrees represent zero-valent copper, which indicates that Cu in the solution is2+Most of which is converted to zero-valent copper. The above results indicate the success of Cu @ Co-MOF preparation. The XRD patterns of the carbonized CuCo/C and Co/C are shown in figure 1. At 26 deg., there was a weak peak in the (002) plane of the graphitic carbon, indicating that the organic ligands of Co-MOF formed a carbon matrix by pyrolysis. The diffraction peaks for CuCo/C and Co/C are at 44.5 °, 51.6 ° and 75.9 °, respectively, all in agreement with the indices (111), (200) and (220) of the Co metal phase. In addition, the XRD pattern of CuCo/C, three new peaks are located at 43.5 °, 50.6 ° and 74.2 °, which should correspond to the metallic Cu phase. These results indicate that Cu @ Co-MOF was successfully carbonized to a copper/cobalt/carbon-based material. FIG. 2 is an XPS plot of Cu @ Co-MOF, CuCo/C of example 1 of the present invention. B, C and D in FIG. 2 are carbon atoms, copper atoms, and cobalt atoms, respectively. As can be seen from fig. 2, the catalyst contains carbon, copper and cobalt elements, and forms C-C/C ═ C bonds, C ═ O bonds and C-O/C-O-C bonds. . As can be seen from FIGS. 1 and 2, the present invention has successfully synthesized CuCo/C catalyst.
Experimental example 2
The Cu @ Co-MOF, CuCo/C of example 1 were subjected to SEM and TEM electron microscopy. FIG. 3 is an SEM and TEM electron micrograph of Cu @ Co-MOF, CuCo/C of example 1 according to the present invention. From the figure, it can be seen that SEM shows that Cu @ Co-MOF has a spherical structure and a relatively smooth surface. Furthermore, from the TEM of Cu @ Co-MOFs, small particles are dispersed on the surface of the Co-MOFs, and the particles on the surface are copper, which indicates that copper is successfully added into the Cu @ Co-MOF. SEM images of CuCo/C show that the shape of the precursor is not damaged, spherical metal particles are formed, and the surface of the CuCo/C structure is rough. In addition, the TEM image further confirms that the nanoparticles are in a polyhedral structure, and the Cu/Co nanoparticles are uniformly distributed on the porous carbon.
Experimental example 3
The Cu @ Co-MOF, CuCo/C of example 1 and the Co/C of comparative example 1 were subjected to specific surface area and pore size measurements.
FIG. 4 is a graph of adsorption-desorption isotherms for Cu @ Co-MOF of example 1 of the invention, CuCo/C and Co/C of comparative example 1. As can be seen from the figure, the specific surface areas and the total pore volumes of Cu @ Co-MOF, CuCo/C and Co/C are 11.9187m, respectively2G and 0.52cm3/g、4.2869m2G and 0.0159cm3/g、8.3940m2G and 0.0246cm3(ii) in terms of/g. The specific surface area and pore volume of CuCo/C are lower than Cu @ Co-MOF, which may be related to the collapse of some of the nanopores during calcination. In addition, the specific surface area of CuCo/C is slightly smaller than that of Co/C after Cu doping, which is probably caused by the blockage of the pores of CuCo/C by part of copper. .
Experimental example 4
The CuCo/C of inventive example 1 was subjected to a magnetic test.
FIG. 5 is a magnetic test chart of CuCo/C according to example 1 of the present invention, and it can be seen that the saturation magnetization of CuCo/C is about 61.625emu g-1. Actually, although the saturation magnetization data of the CuCo/C catalyst is small, the CuCo/C catalyst can be separated after a few minutes under the action of an external magnetic field and is easy to recover.
Example 2
The application of the prepared CuCo/C catalyst activated PMS to the degradation of antibiotics in wastewater mainly comprises the following steps:
weighing 0.025g of each of Cu @ Co-MOF (example 1), CuCo/C (example 1) and Co/C (comparative example 1), adding the weighed materials into 100mL of 10mg/L Ciprofloxacin (CIP) wastewater, and magnetically stirring for 30min under the condition of not adding PMS to achieve adsorption balance; under the same condition, PMS is added, and the mixture is magnetically stirred to react for 30min, so that the aim of degrading the antibiotics in the wastewater is fulfilled.
In the process of catalytic reaction, ciprofloxacin liquid is extracted into a centrifuge tube filled with 1mL of methanol at certain intervals, the characteristic peak value of CIP in the solution is measured by an ultraviolet-visible spectrophotometer, and the degradation efficiency is calculated. The prepared catalytic materials were subjected to the same procedure, and the degradation efficiency was calculated. Meanwhile, the optimal CuCo/C catalyst dosage is selected to carry out four cycles according to the same test method, so that the stability of the catalytic material is conveniently inspected.
FIG. 6 is a graph of the time-degradation efficiency of Ciprofloxacin (CIP) for the Cu @ Co-MOF and CuCo/C catalysts prepared in example 1 of the present invention and the Co/C catalyst prepared in comparative example 1 with PMS added. In FIG. 6, CtRepresenting CIP concentration after degradation, C0The initial concentration of CIP is indicated. As can be seen from fig. 6:
the degradation efficiency of the Cu @ Co-MOF prepared in the embodiment 1 of the invention to CIP after 30min of catalytic reaction is 60%.
The degradation efficiency of the CuCo/C catalytic material prepared in the embodiment 1 of the invention to CIP after 30min of catalytic reaction is 90%.
The Co/C catalyst catalytic material prepared in the comparative example 1 of the invention has the degradation efficiency of 76% to CIP after the catalytic reaction is carried out for 30 min.
Therefore, the CuCo/C catalytic material prepared in the embodiment 1 of the invention has the best degradation effect on CIP, the degradation efficiency on CIP after 30min of photocatalytic reaction can reach 90%, and the efficient removal of CIP is realized. However, the degradation efficiency of Cu @ Co-MOF is only 60%, and the degradation efficiency of Co/C catalyst is only 76%. It can be concluded that: the CuCo/C catalyst has the property of quickly and effectively degrading ciprofloxacin, and has the advantages of good stability, low and simple preparation cost and excellent catalytic performance. In addition, the preparation method adopted by the invention has the advantages of simple process, easy operation, low cost, no pollution and the like, and the prepared catalyst or the preparation method has better application prospect in the field of advanced oxidation water treatment.
Example 3
The method for investigating the recycling property and stability of the CuCo/C catalyst in the process of activating PMS to degrade CIP comprises the following steps:
(1) 0.025g of the CuCo/C catalyst prepared in example 1 was weighed and added to 100mL of ciprofloxacin wastewater having an initial concentration of 10mg/L to obtain a reaction system.
(2) Placing the reaction system obtained in the step (1) on a magnetic stirrer, and taking the concentration of the original solution measured by an ultraviolet-visible spectrophotometer as C0Adding PMS and catalyst, stirring, adding 2mL of solution at certain time intervals into a centrifuge tube filled with 1mL of methanol, and measuring CIP residual concentration in supernatant with ultraviolet-visible spectrophotometer as Ct。
(3) And (3) centrifugally separating the solution reacted in the step (2), pouring off a supernatant, collecting the reacted CuCo/C, washing the CuCo/C with ethanol for a plurality of times (aiming at desorbing CIP by using ethanol), centrifuging, filtering, drying, weighing, and adding the CuCo/C into 100mL ciprofloxacin wastewater with the initial concentration of 10mg/L again.
(4) And (4) continuously repeating the steps (2) to (3) for four times.
(5) FIG. 7 is a graph of cycle number-degradation efficiency corresponding to the cyclic degradation of Ciprofloxacin (CIP) wastewater by the CuCo/C catalyst in example 3 of the present invention. In fig. 7, the degradation efficiency of CIP is plotted on the ordinate, wherein 1, 2, 3, and 4 correspond to the photocatalytic degradation efficiency of the first reaction, the second reaction, the third reaction, and the fourth reaction, respectively. From the figure, the CuCo/C catalyst still shows high-efficiency photocatalytic performance after four cycles, and the degradation efficiency still reaches 85% after four cycles, which shows that the CuCo/C catalyst has the advantages of high stability, cyclic utilization and high degradation efficiency on ciprofloxacin, and is a novel catalyst with good reutilization property.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples. All technical solutions that fall within the spirit and principle of the present invention are included in the scope of the present invention.
Claims (9)
1. According to the invention, a Cu @ Co-MOF precursor is synthesized by adopting a one-step hydrothermal method, then the precursor is pyrolyzed at 900 ℃ in a nitrogen atmosphere to generate a copper-cobalt/carbon (CuCo/C) nano composite catalyst, in the high-temperature pyrolysis process, an organic ligand in MOFs is carbonized into a carbon matrix, and metal nodes are aggregated into metal nano particles. The formed metal nano particles are uniformly distributed on the surface of the carbon matrix and partially coated in the carbon matrix, so that the stability of the catalyst is further improved. And the carbon matrix is used as a dispersing agent, so that the aggregation of copper and cobalt can be effectively limited, and the highly uniform distribution of active metal is promoted. In addition, carbon radicals generated by organic ligands in the MOF not only play a role of a dispersing agent, prevent the aggregation of Cu/Co nanoparticles and promote the highly uniform distribution of active metals, but also promote the transfer of electrons from the catalyst to the PMS due to the conductivity of the active metals; the Cu/Co double-nanoparticle interaction activates PMS so as to improve the catalytic efficiency.
2. The mocs-derived CuCo/C catalyst for activating PMS catalytic degradation antibiotics according to claim 1, characterized in that: the formed metal nano particles are uniformly distributed on the surface of the carbon matrix and partially coated in the carbon matrix, so that the stability of the catalyst is further improved.
3. The process for the preparation of the mocs-derived CuCo/C catalyst for activating PMS catalytic degradation antibiotics, as claimed in claim 1 or 2, comprising the steps of:
the synthesis method of the Cu @ Co-MOF precursor comprises the following steps:
s1, mixing 6mmol of cobalt nitrate (Co (NO)3)2.6H2O) and 6mmol of copper nitrate (Cu (NO)3)2.3H2O) and 12mmol of terephthalic acid (H)2BDC) was added to a beaker containing N, N-Dimethylformamide (DMF) and stirred at room temperature;
s2, transferring the mixed solution into a stainless steel autoclave with a 100mL polytetrafluoroethylene lining after stirring, and adding hydrofluoric acid;
s3, transferring the sealed polytetrafluoroethylene-lined stainless steel autoclave filled with the uniformly mixed solution into an oven, heating at 150 ℃ for 72 hours, and naturally cooling to room temperature after the reaction is finished;
s4, washing the solid product with DMF, ethanol and water twice respectively, vacuum-drying at 70 ℃ for 12h, and collecting the Cu @ Co-MOF.
S5, preparing the carbon/cobalt/copper (CuCo/C) nano composite catalyst as follows:
charging the solid collected in S4 into a ceramic boat, placing into a tube furnace, heating to 900 deg.C at a rate of 5 deg.C/min, and adding N2Carbonizing for 2h under the atmosphere. After completion, the furnace was allowed to cool naturally to room temperature to obtain a CuCo/C catalyst.
4. The process for the preparation of the MOFs-derived CuCo/C catalyst for activating PMS catalytic degradation antibiotics according to claim 3, wherein in steps S1 and S2: the DMF solution is 60 mL; the stirring is carried out under the condition that the rotating speed is 600 r/min-1000 r/min; the stirring time is about 20-30 min; the amount of the hydrofluoric acid is 0.8 mL; .
5. The process for the preparation of the MOFs-derived CuCo/C catalyst for activating PMS catalytic degradation antibiotics according to claim 3, wherein in steps S3 and S4: the reaction temperature is 150 ℃, and the reaction time is 72 hours; the drying time is 12h, and the temperature is 70 ℃.
6. Use of the mocs-derived CuCo/C catalyst of claim 1 or 2 for the catalytic degradation of antibiotics with activated PMS for the degradation of antibiotic wastewater.
7. The use of claim 6, wherein the antibiotic is ciprofloxacin.
8. The application according to claim 6, characterized in that it comprises the following steps: adding the prepared catalyst into wastewater containing antibiotics to obtain mixed liquor, and stirring for 30min under the condition of not adding PMS to obtain the adsorption efficiency of the catalyst; then, adding PMS to react for 30min under the same condition to finish the degradation of antibiotics in the water body; the addition amount of the catalyst is 0.25g of CuCo/C catalyst derived from MOFs added in each liter of antibiotic wastewater.
9. The use according to claim 8, wherein the concentration of antibiotics in the wastewater is 10 mg/L; the stirring treatment time under the condition without adding PMS is 30 min; the catalytic reaction time of the activated PMS is 30 min; the stirring treatment is carried out at the rotating speed of 550-600 r/min; the time for the catalytic reaction treatment of the activated PMS is 30 min.
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| CN114177911A (en) * | 2021-12-10 | 2022-03-15 | 湖南大学 | Carbon-supported multi-metal oxide catalyst and preparation method and application thereof |
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