CN116174005A - Preparation method and application of cobalt/nitrogen-carbon composite material with double carbon layers - Google Patents
Preparation method and application of cobalt/nitrogen-carbon composite material with double carbon layers Download PDFInfo
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- CN116174005A CN116174005A CN202310079364.2A CN202310079364A CN116174005A CN 116174005 A CN116174005 A CN 116174005A CN 202310079364 A CN202310079364 A CN 202310079364A CN 116174005 A CN116174005 A CN 116174005A
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 53
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- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
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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 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
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- 229960001763 zinc sulfate Drugs 0.000 claims description 2
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- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002243 precursor Substances 0.000 abstract description 4
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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
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
-
- 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
- C02F2305/08—Nanoparticles or nanotubes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
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Abstract
The invention relates to the technical field of removal of novel pollutants in nano materials and wastewater, in particular to a preparation method and application of a cobalt/nitrogen-carbon composite material with a double carbon layer. The cobalt/nitrogen-carbon composite material with a double carbon layer is prepared by stirring at room temperature, taking water as a solvent, reacting to prepare a cobalt-zinc bimetal organic framework, mechanically mixing with melamine to prepare a precursor of a derivative carbon material, and calcining. Zn evaporates during calcination, and the introduction of Zn can form a molecular fence effect to enlarge the distance between Co atoms, thereby inhibiting Co agglomeration during calcination. Melamine can generate ammonia during calcination, which will facilitate Co nanoparticles migration to the surface of the derivatized carbon material, exposing more active sites. The invention can provide a new thought for preparing MOFs derived cobalt-carbon composite materials, and can also open up a new way for the application of MOFs derived carbon-supported metal catalysts in pollutant degradation.
Description
Technical Field
The invention relates to the technical field of removal of novel pollutants in nano materials and wastewater, in particular to a preparation method and application of a cobalt/nitrogen-carbon composite material with a double carbon layer.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
Antibiotics play an important role in human medicine and aquaculture as one of the most important medical findings in the 20 th century. However, the abuse and non-monitored release of antibiotics has led to the generation, proliferation and spread of resistant bacteria and antibiotic resistance genes in the environment, not only creating a crisis for the use of antibiotics, but also the appearance of "super resistant bacteria" has once again created a serious threat to human health. In recent years, antibiotic contamination has also attracted great national importance and is listed in the national strategy. In order to effectively prevent, control and treat environmental pollution caused by new pollutants such as persistent organic pollutants, endocrine disruptors and antibiotics which are widely concerned at home and abroad and are managed and controlled by international convention. Among the numerous antibiotics, sulfonamides are identified as the most commonly used antibiotics in livestock farming, especially Sulfamethoxazole (SMX) is frequently detected from aquaculture wastewater. However, traditional wastewater treatment techniques have low SMX removal efficiency due to their inherent antimicrobial properties and recalcitrance. Thus, developing an effective SMX degradation method is a viable strategy to reduce the risk of SMX environments. The advanced oxidation technology of the Peroxomonosulfate (PMS) can generate sulfate radical with strong oxidation capability, and the pH application range is wider, so that the Peroxomonosulfate (PMS) is widely used for removing stubborn organic pollutants.
Among the numerous persulfate catalysts, metal organic framework Materials (MOFs) are widely used in activated persulfate to remove organic contaminants due to their large specific surface area, high porosity, rich functional groups, and their pore size and structure being controllable and functional groups being replaceable. However, the pore size of most MOFs is in the microporous region, which places a large limit on the diffusion of macromolecules within the pore material. Some MOFs may even collapse under humid air, in aqueous solutions or at elevated temperatures. Thus, the inherent instability and microporous structure of MOFs limit their further use in contaminant removal. The research results show that the catalytic performance can be remarkably improved by converting the conventional bulk MOFs crystals into two-dimensional nano-sheets, because the two-dimensional nano-materials have higher exposed active atomic ratio to ensure higher catalytic activity, and large nano-thickness to ensure rapid mass transfer and charge transfer in the reaction process. Meanwhile, MOFs are pyrolyzed to optimize the distribution and uniformity of pore diameters, so that the derived carbon material generally has the characteristics of higher porosity, uniform pore diameters and adjustable active site dispersion. In addition, adjusting the thermal decomposition temperature of MOFs precursors can control the morphology of the derivatized carbon composite. Therefore, MOFs-derived carbon materials have recently attracted considerable attention in persulfate activation to remove new contaminants. However, during pyrolysis of MOFs, metal particles tend to agglomerate. A large amount of metal is embedded in the carbon substrate or microporous channels during synthesis and is deactivated during catalysis due to mass transfer limitations. In addition, most MOFs are generally environmentally unfriendly in the synthesis process with volatile and toxic methanol and N, N-dimethylformamide as solvents. Meanwhile, the preparation process also needs to be carried out at high temperature and high pressure for a long time, i.e. the preparation process is unsafe and time-consuming.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a preparation method and application of a cobalt/nitrogen-carbon composite material with a double carbon layer. The cobalt/nitrogen-carbon composite material with a double carbon layer is prepared by stirring at room temperature, taking water as a solvent, reacting to prepare a cobalt-zinc bimetal organic framework, mechanically mixing with melamine to prepare a precursor of a derivative carbon material, and calcining. The invention can provide a new thought for preparing MOFs derived cobalt-carbon composite materials, and can also open up a new way for the application of MOFs derived carbon-supported metal catalysts in pollutant degradation.
In order to achieve the above object, the present invention is realized by the following technical scheme:
in a first aspect, the present invention provides a method for preparing a cobalt/nitrogen carbon composite material having a dual carbon layer, comprising the steps of:
s1, dripping aqueous solutions of cobalt salt, zinc salt and hexadecyl trimethyl ammonium bromide into an aqueous solution of 2-methylimidazole, stirring, centrifuging, washing and drying to obtain CoZn-ZIF;
s2, mixing and grinding CoZn-ZIF and melamine to obtain a mixture;
s3, placing the mixture in a tube furnace under the protection of inert atmosphere, and carbonizing by adopting gradient heating to obtain the cobalt/nitrogen-carbon composite material with the double carbon layers.
In a second aspect, the invention provides a cobalt/nitrogen-carbon composite material with a double-carbon layer, which is obtained by the preparation method of the cobalt/nitrogen-carbon composite material with the double-carbon layer in the first aspect.
In a third aspect, the present invention provides the use of a cobalt/nitrogen carbon composite material having a dual carbon layer according to the second aspect for contaminant removal.
The beneficial effects obtained by one or more of the technical schemes of the invention are as follows:
(1) The preparation method of the cobalt/nitrogen-carbon composite material with the double carbon layers can effectively solve the problem of agglomeration in the pyrolysis process of cobalt nanoparticles, and the prepared cobalt/nitrogen-carbon composite material with the double carbon layers has good treatment effect on new pollutants, can be directly put into waste water for use, and reduces time and economic cost.
(2) The cobalt/nitrogen-carbon composite material with the double carbon layers has the advantages of little addition amount when degrading emerging pollutants, simple operation, low cost, low energy consumption and the like, can effectively remove the emerging pollutants in surface water and underground water, and has good potential and advantages in the aspect of practical engineering application.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is an XRD pattern of Co-N@NC prepared in example 1, co@NC prepared in comparative example 1, N@NC prepared in comparative example 2, NC prepared in comparative example 3 of the present invention;
FIG. 2 is a Transmission Electron Microscope (TEM) image of Co-N@NC prepared in example 1 of the present invention;
FIG. 3 is a graph of energy dispersive X-ray elements of a large-angle annular dark field spherical aberration electron microscope of Co-N@NC prepared in example 1 of the invention;
FIG. 4 (a) is a graph showing the effect of the catalyst removal of sulfamethoxazole by the catalysis of peroxomonosulfate, wherein no catalyst group (PMS alone) was added, co-N@NC prepared in example 1 was added as a catalyst (Co-N@NC+PMS), co@NC prepared in comparative example 1 was added as a catalyst (Co@NC+PMS), N@NC prepared in comparative example 2 was added as a catalyst (N@NC+PMS), and NC prepared in comparative example 3 was added as a catalyst (NC+PMS); (b) Comparative graphs of the sulfamethoxazole removal effect of the catalytic peroxymonosulfates of Co-N@NC, co-N@NC-2, co-N@NC-5 and Co-N@NC-10 prepared in examples 1-4 of the invention; c (C) t /C 0 Representing the ratio of the concentration at different reaction times to the initial concentration;
FIG. 5 is a graph showing the comparative effect of Co-N@NC prepared in example 1 of the present invention on catalyzing the degradation of sulfamethoxazole by peroxymonosulfate at different pH values, C t /C 0 Representing the ratio of the concentration at different reaction times to the initial concentration;
FIG. 6 is an XRD pattern of Co-N@NC prepared in example 1 of the present invention before and after removal of sulfamethoxazole by catalytic peroxymonosulfate.
Detailed Description
In a first exemplary embodiment of the present invention, a method for preparing a cobalt/nitrogen carbon composite material having a dual carbon layer includes the steps of:
s1, dripping aqueous solutions of cobalt salt, zinc salt and Cetyl Trimethyl Ammonium Bromide (CTAB) into an aqueous solution of 2-methylimidazole, stirring, centrifuging, washing and drying to obtain CoZn-ZIF;
s2, mixing and grinding CoZn-ZIF and melamine to obtain a mixture;
s3, placing the mixture in a tube furnace under the protection of inert atmosphere, and carbonizing by adopting gradient heating to obtain the cobalt/nitrogen-carbon composite material with the double carbon layers.
In one or more embodiments of this embodiment, in step S1, the cobalt salt is one of cobalt chloride, cobalt nitrate and cobalt sulfate, the zinc salt is one of zinc chloride, zinc sulfate and zinc nitrate, the molar ratio of the cobalt salt to the zinc salt is 1:15-20, and the molar amount of the cobalt salt is 0.1-0.2 mmol;
the molar weight of the cetyl trimethyl ammonium bromide is 0.027-0.03mmol;
the molar ratio of the 2-methylimidazole to the cobalt salt is 300-500:1.
In one or more embodiments of this embodiment, the stirring time in step S1 is 1.5-2.5 hours, the stirring temperature is room temperature, and the stirring rate is 400-600 rpm;
the washing was performed using methanol.
In one or more examples of this embodiment, the mass ratio of CoZn-ZIF to melamine in step S2 is 1:1-10.
In one or more embodiments of this embodiment, the inert atmosphere in step S3 is one of argon or nitrogen;
the gradient temperature rise calcination procedure is as follows: firstly, heating to 500-600 ℃ at a heating rate of 10 ℃/min, preserving heat for 1-2 h, then heating to 900-1000 ℃ at a continuous heating rate of 5 ℃/min, and preserving heat for 2-3 h.
Since Zn can be reduced to metallic Zn by the support carbon material at high temperature, and the boiling point of metallic Zn (908 ℃) is low, zn species is evaporated around 900 ℃, and Co introduction also promotes Zn evaporation. Therefore, the introduction of Zn can form a molecular fence effect, and the distance between Co atoms is increased, so that the agglomeration of Co in the calcination process is inhibited. Melamine can generate ammonia during calcination, which will facilitate Co nanoparticles migration to the surface of the derivatized carbon material, exposing more active sites. Because ammonia gas is generated in situ and is closely adjacent to metal, the reduction of metal is easier to carry out, and the reduction products are only water and nitrogen, so that pollution is reduced.
A second exemplary embodiment of the present invention, a cobalt/nitrogen-carbon composite material having a dual carbon layer, is obtained by the method for preparing a cobalt/nitrogen-carbon composite material having a dual carbon layer according to the first exemplary embodiment of the present invention.
In one or more examples of this embodiment, the inner carbon of the cobalt/nitrogen carbon composite material having a dual carbon layer is a CoZn-ZIF-derived carbon, the outer carbon is a melamine-derived carbon layer, and the cobalt is dispersed in the form of nanoparticles or nanoclusters.
In a third exemplary embodiment of the present invention, the use of the cobalt/nitrogen carbon composite material with a dual carbon layer according to the second exemplary embodiment of the present invention for removing contaminants includes activating a peroxymonosulfate to remove sulfamethoxazole, a new contaminant in wastewater.
In one or more examples of this embodiment, activating the peroxymonosulfate to remove the new contaminant sulfamethoxazole from the wastewater includes the steps of:
preparing sulfamethoxazole solution, and regulating the pH to 3-11;
the cobalt/nitrogen carbon composite material with the double carbon layer according to the second exemplary embodiment of the invention is put into sulfamethoxazole solution, and then the persulfate is added to carry out the reaction;
1mL of the mixture was removed from the beaker at specific time intervals, filtered through a 0.22 μm polytetrafluoroethylene filter into 0.5mL of methanol, quenched to terminate the reaction, then transferred to a liquid phase vial, and the SMX concentration was detected by high performance liquid chromatography.
In one or more examples of this embodiment, the concentration of sulfamethoxazole in the sulfamethoxazole solution is 10-40 mg/L;
the reaction is carried out in a constant temperature water bath with the temperature of 15-35 ℃ and with the mechanical stirring of 300-500 rmp;
the input amount of the cobalt/nitrogen-carbon composite material with the double carbon layers is 0.01-0.03 g, and the concentration of the peroxymonosulfate is 0.05-0.2 g/L.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail below with reference to specific examples and comparative examples.
Example 1
0.0437g Co (NO) 3 ) 2 ·6H 2 O、0.8478g Zn(NO 3 ) 2 ·6H 2 O and 10mg CTAB were dissolved in 20mL of water, 4.9263g of 2-methylimidazole was weighed out and dissolved in 130mL of water, and Co (NO) was stirred at 500rpm at room temperature 3 ) 2 ·6H 2 O、Zn(NO 3 ) 2 ·6H 2 Dripping the mixed aqueous solution of O and CTAB into the aqueous solution of 2-methylimidazole, stirring for 2 hours, centrifugally washing with methanol for three times, and drying at 60 ℃ for 12 hours to obtain CoZn-ZIF;
mixing and grinding CoZn-ZIF and melamine according to a mass ratio of 1:1 to obtain a mixture of CoZn-ZIF and melamine;
and (3) placing the mixture in a tubular furnace under the protection of argon, heating to 550 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, continuously heating to 1000 ℃ at a heating rate of 5 ℃/min, and preserving heat for 2.5h to obtain the cobalt/nitrogen-carbon composite material with the double carbon layer, which is denoted as Co-N@NC.
Example 2
Unlike example 1, the CoZn-ZIF and melamine were mixed and ground in a mass ratio of 1:2, and the finally obtained cobalt/nitrogen-carbon composite material having a double carbon layer was designated as Co-N@NC-2.
Example 3
Unlike example 1, the CoZn-ZIF and melamine were mixed and ground in a mass ratio of 1:5, and the finally obtained cobalt/nitrogen-carbon composite material having a double carbon layer was designated as Co-N@NC-5.
Example 4
Unlike example 1, coZn-ZIF and melamine were mixed and ground in a mass ratio of 1:10, and the finally obtained cobalt/nitrogen-carbon composite material having a double carbon layer was designated as Co-N@NC-10.
Comparative example 1
Unlike example 1, no melamine was added, and a cobalt-loaded monolayer of nitrogen-doped carbon was obtained, designated co@nc.
Comparative example 2
Unlike example 1, co (NO 3 ) 2 ·6H 2 O, obtaining the double-carbon layer nitrogen doped carbon, which is marked as N@NC.
Comparative example 3
Unlike example 1, melamine and Co (NO 3 ) 2 ·6H 2 O, a single layer of nitrogen doped carbon was obtained, designated NC.
First, the above prepared Co-N@NC, co@NC, N@NC and NC were subjected to X-ray powder diffraction (XRD) characterization, and as a result, as shown in FIG. 1, there were two diffraction peaks at-25℃and-44.5℃in all the samples, attributable to the (002) and (101) crystal planes of graphitic carbon, respectively. Three metallic cobalt phase diffraction peaks in Co-n@nc can be found to belong to the (111), (200) and (220) crystal planes, respectively. However, due to the poor effect of carbon coating and cobalt migration, three diffraction peaks were not found in the XRD pattern of co@nc. To further verify that the Co-N@NC materials were all successfully prepared. The morphology and the component element results of the synthesized Co-N@NC sample are shown in fig. 2 and 3. FIG. 2 shows that no self-aggregation of Co nanoparticles was found in the Co-N@NC Transmission Electron Microscope (TEM), which is attributed to the large specific surface area of NC and the provision of rich cobalt loading sites. Meanwhile, it can be found that the material edges comprise a bilayer carbon layer, the inner carbon being due to MOF-derived carbon and the outer carbon being due to melamine-derived carbon layer. The presence of the graphitic carbon layer may facilitate electron transfer during contaminant removal. The large angle annular dark field spherical aberration electron microscope energy dispersive X-ray element spectrum (HAADF-STEM-EDX-map 1ngs, FIG. 3) of Co-N@NC shows that the C and N elements are regularly dispersed on the surface of the material. The Co element is dispersed throughout the material in the form of Co nanoparticles and in the form of small Co clusters. The above results demonstrate that cobalt/nitrogen carbon composite materials with a dual carbon layer were successfully prepared.
Example 5
The SMX removal experiment procedure is as follows: 200mL of the formulated SMX with an initial pH of 7.08 was first placed in a 250mL beaker. Then, the beaker was placed in a thermostat water bath, the temperature was kept at 25 ℃, 20mg of catalyst and 20mg of PMS were sequentially added to the SMX solution with stirring at a stirring rate of 400rpm, and the reaction was started immediately. 1mL of the mixture was removed from the beaker at specific time intervals, filtered through a 0.22 μm polytetrafluoroethylene filter into 0.5mL of methanol, quenched to terminate the reaction, then transferred to a liquid phase vial, and the SMX concentration was detected by high performance liquid chromatography. In the scheme, a Thermo HPLC system is adopted for high performance liquid analysis. A detector: an ultraviolet lamp; chromatographic column: BDS HYPERIL.C18, 150X4.6 mm; flow rate: 1mL/min; mobile phase: acetonitrile/water (0.2% formic acid) =40/60 (v/v); sample injection amount: 10. Mu.L; column temperature: 35 ℃; detection wavelength: 270nm.
As can be seen from fig. 4a, at an initial pH of 7.08, the removal rate of PMS alone was 28.46% for 120min for SMX, and the degradation effect of co@nc (41.48%) and Co-n@nc (97.09%) on SMX was better than NC (31.07%) and n@nc (28.02%) within 120 min. The results show that the addition of Co enhances the ability of NC and N@NC to catalyze PMS. At the same time, cobalt nanoparticles have also been demonstrated to be the primary active site catalyzing PMS degradation SMX. Compared with Co@NC, co-N@NC not only shows the highest removal rate of SMX, but also shows the best reactivity. The reason is that ammonia is generated in situ in the calcination process due to the addition of melamine, and promotes more cobalt nano particles to migrate to the surface of the derivative carbon, so that the active sites are exposed with a higher probability, and the degradation effect of SMX is enhanced. Furthermore, further increasing the mass ratio of melamine and cobalt zinc MOF precursor did not further promote SMX degradation (fig. 4 b). The reason is that the cobalt nano particles have reached the maximum exposure ratio in the mass ratio of 1 to 1, and the cobalt content is not different, so that the exposed cobalt sites are not further increased, and the SMX degradation effect is not further enhanced.
As shown in fig. 5. After 120min of reaction, at an initial pH of 3.48-9.25, SMX degradation rates were 96.67, 98.23, 97.09 and 97.88%, respectively. At a pH of 10.71, the degradation efficiency of SMX still reached 59.35%. The results show that the Co-N@NC not only has good catalytic activity, but also has a wide pH application range. In addition, the pH of the organic sewage is generally close to neutral, so the material prepared by the invention has good potential for efficiently treating the actual sewage.
To investigate the stability of Co-N@NC, the reacted Co-N@NC was centrifugally washed with ethanol and ultrapure water and dried, and then XRD characterization was performed. As a result, as shown in FIG. 6, the oxidation state of Co was not observed from the XRD spectrum of Co-N@NC after the reaction. The results show that Co-N@NC has good stability.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method and application of the cobalt/nitrogen-carbon composite material with the double carbon layers are characterized by comprising the following steps:
s1, dripping aqueous solutions of cobalt salt, zinc salt and hexadecyl trimethyl ammonium bromide into an aqueous solution of 2-methylimidazole, stirring, centrifuging, washing and drying to obtain CoZn-ZIF;
s2, mixing and grinding CoZn-ZIF and melamine to obtain a mixture;
s3, placing the mixture in a tube furnace under the protection of inert atmosphere, and carbonizing by adopting gradient heating to obtain the cobalt/nitrogen-carbon composite material with the double carbon layers.
2. The method for preparing the cobalt/nitrogen-carbon composite material with the double carbon layer according to claim 1, wherein in the step S1, the cobalt salt is one of cobalt chloride, cobalt nitrate and cobalt sulfate, the zinc salt is one of zinc chloride, zinc sulfate and zinc nitrate, the molar ratio of the cobalt salt to the zinc salt is 1:15-20, and the molar amount of the cobalt salt is 0.1-0.2 mmol;
the molar weight of the cetyl trimethyl ammonium bromide is 0.027-0.03mmol;
the molar ratio of the 2-methylimidazole to the cobalt salt is 300-500:1.
3. The method for preparing a cobalt/nitrogen-carbon composite material with a double carbon layer according to claim 1, wherein in the step S1, the stirring time is 1.5-2.5 h, the stirring temperature is room temperature, and the stirring speed is 400-600 rpm;
the washing was performed using methanol.
4. The method for preparing a cobalt/nitrogen-carbon composite material with a double carbon layer according to claim 1, wherein the mass ratio of CoZn-ZIF to melamine in the step S2 is 1:1-10.
5. The method for producing a cobalt/nitrogen-carbon composite material having a double carbon layer according to claim 1, wherein the inert atmosphere in step S3 is one of argon or nitrogen;
the gradient temperature rise calcination procedure is as follows: firstly, heating to 500-600 ℃ at a heating rate of 10 ℃/min, preserving heat for 1-2 h, then heating to 900-1000 ℃ at a continuous heating rate of 5 ℃/min, and preserving heat for 2-3 h.
6. A cobalt/nitrogen-carbon composite material having a double carbon layer, characterized by being obtained by the method for producing a cobalt/nitrogen-carbon composite material having a double carbon layer according to any one of claims 1 to 5.
7. The cobalt/nitrogen carbon composite with a dual carbon layer according to claim 6, wherein the inner carbon of the cobalt/nitrogen carbon composite with a dual carbon layer is CoZn-ZIF-derived carbon, the outer carbon is melamine-derived carbon layer, and cobalt is dispersed in the form of nanoparticles or nanoclusters.
8. Use of a cobalt/nitrogen carbon composite material with a double carbon layer according to any of claims 6-7 for the removal of new contaminants, characterized in that the use comprises the activation of peroxymonosulfate to remove new contaminant sulfamethoxazole in wastewater.
9. The use according to claim 8, wherein the activated peroxymonosulfate to remove sulfamethoxazole as a new contaminant in wastewater comprises the steps of:
preparing sulfamethoxazole solution, and regulating the pH to 3-11;
putting the cobalt/nitrogen-carbon composite material with the double carbon layer as claimed in any one of claims 6-7 into sulfamethoxazole solution, and then adding peroxymonosulfate to react;
1mL of the mixture was removed from the beaker at specific time intervals, filtered through a 0.22 μm polytetrafluoroethylene filter into 0.5mL of methanol, quenched to terminate the reaction, then transferred to a liquid phase vial, and the SMX concentration was detected by high performance liquid chromatography.
10. The use according to claim 9, wherein the concentration of sulfamethoxazole in the sulfamethoxazole solution is 10-40 mg/L;
the reaction is carried out in a constant temperature water bath with the temperature of 15-35 ℃ and with the mechanical stirring of 300-500 rmp; the input amount of the cobalt/nitrogen-carbon composite material with the double carbon layers is 0.01-0.03 g, and the concentration of the peroxymonosulfate is 0.05-0.2 g/L.
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