CN113292107B - Magnetic hollow cobalt oxide @ nitrogen-doped porous carbon, preparation method thereof and application thereof in antibiotic wastewater treatment - Google Patents
Magnetic hollow cobalt oxide @ nitrogen-doped porous carbon, preparation method thereof and application thereof in antibiotic wastewater treatment Download PDFInfo
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Abstract
The application discloses a magnetic hollow cobalt oxide @ nitrogen-doped porous carbon, a preparation method thereof and application thereof in antibiotic wastewater treatment, wherein the preparation method comprises the following steps: adding a mixed solution containing zinc nitrate hexahydrate and cobalt nitrate hexahydrate into graphene oxide dispersion liquid, mixing, adding a dimethyl imidazole solution, stirring, centrifuging, washing, drying to obtain purple powder, and adding the purple powder into N 2 Calcining in the atmosphere, and calcining in the air to obtain the magnetic hollow cobalt oxide @ nitrogen-doped porous carbon. The introduction of nitrogen improves the catalytic activity; the specific surface area is increased by the evaporation of Zn in the carbonization process; the reduced graphene oxide is used as a supporting substrate, so that the catalytic activity of the catalyst is improved, the aggregation of adjacent cobalt oxide particles is reduced, and Co in a catalytic system is reduced 2+ The leaching concentration of (a). The catalyst can activate the potassium monopersulfate composite salt to efficiently degrade sulfamethoxazole, and has the advantages of good reusability and stability and easy recycling.
Description
Technical Field
The invention belongs to the field of heterogeneous catalysts, and particularly relates to a magnetic hollow cobalt oxide @ nitrogen-doped porous carbon, a preparation method thereof and application thereof in antibiotic wastewater treatment.
Background
At present, the treatment technology of antibiotic wastewater comprises physicochemical technology, biotechnology and advanced oxidation technology. In recent years, based on sulfate radicals (SO) 4 ·– ) Also used for treating antibiotic wastewater. SO (SO) 4 ·– Can be generated by the activation of persulfate, and the activation mode is mainly divided into photoactivation, thermal activation, activation of transition metal ions and metal oxides, activation of non-metallic materials and the like. Of these, cobalt oxide has a high persulfate activation but has a relatively small surface area and tends to aggregate during the reaction, resulting in a reduction in catalytic activity, and Co 2+ Secondary pollution can be caused by leaching; the carbon material has adjustable surface property and relatively simple preparation, but is difficult to recycle. Therefore, there is a need to prepare a novel catalyst which can activate persulfate with high efficiency, and can be recycled without causing secondary pollution.
Disclosure of Invention
The technical problem to be solved is as follows: the application mainly provides a magnetic hollow cobalt oxide @ nitrogen-doped porous carbon, a preparation method thereof and application thereof in antibiotic wastewater treatment, and solves the technical problems of low catalyst degradation efficiency, difficulty in recycling, secondary pollution and the like in the prior art.
The technical scheme is as follows:
a preparation method of magnetic hollow cobalt oxide @ nitrogen-doped porous carbon comprises the following steps:
firstly, ultrasonically dispersing graphene oxide GO powder in water for 1h, adding methanol, and continuously dispersing for 1h to prepare a GO dispersion liquid;
the second step: zn (NO) 3 ) 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 Dissolving O and a dispersing agent in methanol to prepare a mixed solution;
the third step: dissolving dimethyl imidazole in methanol to prepare a solution;
the fourth step: adding the mixed solution in the second step into the GO dispersion liquid prepared in the first step, fully mixing for 2 hours, then adding the dimethyl imidazole solution prepared in the third step, continuously mixing for 24 hours, and centrifuging, washing and drying the obtained mixed solution to obtain purple powder;
the fifth step: the purple powder in the fourth step is firstly treated with N 2 Calcining in the atmosphere, and calcining in the air to obtain the magnetic hollow cobalt oxide @ nitrogen-doped porous carbon.
As a preferred technical scheme of the invention: in the first step, the mass parts of GO, water and methanol are as follows: 48.6-103.6mg GO: 20mL of water: 20mL of methanol.
As a preferred technical scheme of the invention: in the second step, the molar ratio of Zn to Co is 2:1-1: 3; the dispersant in the second step is polyvinylpyrrolidone with the mass of 1 g; the amount of methanol used in the second step was 30 mL.
As a preferred technical scheme of the invention: the mass of the dimethyl imidazole in the third step is 0.924-2.464 g; the amount of methanol used in the third step was 30 mL.
As a preferred technical scheme of the invention: the doping amount of GO in the purple powder obtained in the fourth step is 1.2-2.2 wt%; and in the fourth step, after the mixed solution is centrifuged, washing and centrifuging the mixed solution for 3 times by using anhydrous methanol, removing supernatant, and carrying out vacuum freeze drying on the precipitate for 12 hours to obtain the purple powder.
As a preferred technical scheme of the invention: magnetic stirring is adopted in the second step, the third step and the fourth step for preparing the mixed solution, and the rotating speed is 600 rpm; the first to third steps are all carried out at room temperature.
As a preferred technical scheme of the invention: in the fourth step, the purple powder is in N 2 The calcination condition in the atmosphere is 800 ℃ for 2h, and the calcination condition in the air is 250 ℃ for 1 h.
The magnetic hollow cobalt oxide @ nitrogen-doped porous carbon is prepared by any one of the preparation methods.
The application also discloses an application of the magnetic hollow cobalt oxide @ nitrogen-doped porous carbon in antibiotic wastewater treatment.
Has the beneficial effects that: compared with the prior art, the magnetic hollow cobalt oxide @ nitrogen-doped porous carbon, the preparation method thereof and the technical scheme adopted by the application in the antibiotic wastewater treatment have the following technical effects:
1. according to the invention, the introduction of nitrogen induces electrons to be transferred from the adjacent carbon atom to the nitrogen atom, and the generated active site effectively improves the catalytic activity of the catalyst.
2. The evaporation of Zn in the carbonization process enables the catalyst to generate rich pores, the specific surface area of the catalyst is improved, the catalytic performance is further improved, the catalyst shows high degradation efficiency in the degradation of antibiotics, and the complete degradation of sulfamethoxazole antibiotics can be realized within 2 min.
3. The invention takes the reduced graphene oxide as the supporting substrate, not only improves the catalytic activity of the catalyst, but also reduces the aggregation of adjacent metal particles and Co in a catalytic system 2+ The leaching concentration of (a).
4. The catalyst has magnetism, can be easily recycled under the action of an external magnetic field, has good reutilization property, and can still degrade 94.5 percent of sulfamethoxazole within 30min after being recycled for 5 times.
Description of the drawings:
fig. 1 is an X-ray photoelectron spectrum of the magnetic hollow cobalt oxide @ nitrogen-doped porous carbon provided in example 2 of the present application;
FIG. 2 is a TEM image of the magnetic hollow cobalt oxide @ nitrogen doped porous carbon provided in example 2 of the present application;
fig. 3 is a high resolution transmission electron microscope image of the magnetic hollow cobalt oxide @ nitrogen doped porous carbon provided in example 2 of the present application.
Detailed Description
The following description will explain embodiments of the present invention in further detail with reference to the accompanying drawings.
Example 1
A preparation method of magnetic hollow cobalt oxide @ nitrogen-doped porous carbon comprises the following steps:
the first step is as follows: ultrasonically dispersing 55.9mg GO powder in 20mL of water, adding 20mL of methanol, uniformly mixing, adding 30mL of water containing 0.595g Zn (NO) 3 ) 2 ·6H 2 O、1.164g Co(NO 3 ) 2 ·6H 2 Stirring O and 1g of methanol solution of polyvinylpyrrolidone for 2 hours; then adding 30mL of methanol solution containing 1.847g of dimethyl imidazole, and stirring at room temperature for 24 h; the mixed solution was centrifuged, washed 3 times with anhydrous methanol, and then vacuum freeze-dried for 12h to give a purple powder.
The second step is that: placing the purple powder in an atmosphere furnace, and firstly, adding N 2 Calcining for 2h at 800 ℃ in the atmosphere, and calcining for 1h at 250 ℃ in the air to obtain the magnetic hollow cobalt oxide @ nitrogen-doped porous carbon.
Example 2
A preparation method of magnetic hollow cobalt oxide @ nitrogen-doped porous carbon comprises the following steps:
the first step is as follows: ultrasonically dispersing 80.0mg GO in 20mL of water, adding 20mL of methanol, uniformly mixing, adding 30mL of water containing 0.595g Zn (NO) 3 ) 2 ·6H 2 O、1.164g Co(NO 3 ) 2 ·6H 2 Stirring O and 1g of methanol solution of polyvinylpyrrolidone for 2 hours; then adding 30mL of methanol solution containing 1.847g of dimethyl imidazole, and stirring at room temperature for 24 h; the mixed solution was centrifuged, washed 3 times with anhydrous methanol, and then lyophilized in vacuo for 12h to give a purple powder.
The second step: placing purple powder in an atmosphere furnace, firstly, adding N 2 Calcining for 2h at 800 ℃ in the atmosphere, and calcining for 1h at 250 ℃ in the air to obtain the magnetic hollow cobalt oxide @ nitrogen-doped porous carbon.
Example 3
A preparation method of magnetic hollow cobalt oxide @ nitrogen-doped porous carbon comprises the following steps:
the first step is as follows: dispersing 103.6mg GO in 20mL water by ultrasonic, adding 20mL methanol, mixing well, adding 30mL Zn (NO) containing 0.595g Zn 3 ) 2 ·6H 2 O、1.164g Co(NO 3 ) 2 ·6H 2 O and 1g of methanol solution of polyvinylpyrrolidone are stirred for 2 hours; then adding 30mL of methanol solution containing 1.847g of dimethyl imidazole, and stirring at room temperature for 24 h; centrifuging the mixed solution, washing with anhydrous methanol for 3 times, and vacuum freeze-drying for 12h to obtain purple powder;
the second step is that: placing purple powder in an atmosphere furnace, firstly, adding N 2 Calcining for 2h at 800 ℃ in the atmosphere, and calcining for 1h at 250 ℃ in the air to obtain the magnetic hollow cobalt oxide @ nitrogen-doped porous carbon.
Example 4
A preparation method of magnetic hollow cobalt oxide @ nitrogen-doped porous carbon comprises the following steps:
the first step is as follows: ultrasonically dispersing 48.6mg GO in 20mL of water, adding 20mL of methanol, uniformly mixing, adding 30mL of water containing 0.595g of Zn (NO) 3 ) 2 ·6H 2 O、0.291g Co(NO 3 ) 2 ·6H 2 Stirring O and 1g of methanol solution of polyvinylpyrrolidone for 2 hours; then, 30mL of a methanol solution containing 0.924g of dimethylimidazole was added thereto, and the mixture was stirred at room temperature for 24 hours; the mixed solution was centrifuged and washed with anhydrous methanolWashing for 3 times, and then carrying out vacuum freeze drying for 12 hours to obtain purple powder;
the second step is that: placing purple powder in an atmosphere furnace, firstly, adding N 2 Calcining for 2h at 800 ℃ in the atmosphere, and calcining for 1h at 250 ℃ in the air to obtain the magnetic hollow cobalt oxide @ nitrogen-doped porous carbon.
Example 5
A preparation method of magnetic hollow cobalt oxide @ nitrogen-doped porous carbon comprises the following steps:
the first step is as follows: dispersing 59.0mg GO in 20mL water by ultrasonic, adding 20mL methanol, mixing well, adding 30mL Zn (NO) containing 0.595g Zn 3 ) 2 ·6H 2 O、0.582g Co(NO 3 ) 2 ·6H 2 O and 1g of methanol solution of polyvinylpyrrolidone are stirred for 2 hours; then adding 30mL of methanol solution containing 1.232g of dimethyl imidazole, and stirring at room temperature for 24 h; centrifuging the mixed solution, washing with anhydrous methanol for 3 times, and vacuum freeze-drying for 12h to obtain purple powder;
the second step is that: placing the purple powder in an atmosphere furnace, and firstly, adding N 2 Calcining for 2h at 800 ℃ in the atmosphere, and calcining for 1h at 250 ℃ in the air to obtain the magnetic hollow cobalt oxide @ nitrogen-doped porous carbon.
Example 6
A preparation method of magnetic hollow cobalt oxide @ nitrogen-doped porous carbon comprises the following steps:
the first step is as follows: dispersing 100.4mg GO in 20mL water by ultrasonic, adding 20mL methanol, mixing well, adding 30mL Zn (NO) containing 0.595g Zn 3 ) 2 ·6H 2 O、1.746g Co(NO 3 ) 2 ·6H 2 O and 1g of methanol solution of polyvinylpyrrolidone are stirred for 2 hours; then adding 30mL of methanol solution containing 2.464g of dimethyl imidazole, and stirring at room temperature for 24 h; centrifuging the mixed solution, washing with anhydrous methanol for 3 times, and vacuum freeze-drying for 12h to obtain purple powder;
the second step is that: placing purple powder in an atmosphere furnace, firstly, adding N 2 Calcining at 800 deg.C for 2 hr in atmosphere, calcining at 250 deg.C in air for 1 hr,and obtaining the magnetic hollow cobalt oxide @ nitrogen-doped porous carbon.
Comparative example 1
A preparation method of magnetic hollow cobalt oxide @ carbon comprises the following steps:
the first step is as follows: ultrasonically dispersing 80.0mg GO in 20mL of water, adding 20mL of methanol, uniformly mixing, and adding 30mL of Co (NO) containing 1.746g 3 ) 2 ·6H 2 Stirring O and 1g of methanol solution of polyvinylpyrrolidone for 2 hours; then adding the mixture into a methanol solution containing 1.847g of dimethyl imidazole, and stirring the mixture for 24 hours at room temperature; centrifuging the mixed solution, washing with anhydrous methanol for 3 times, and then carrying out vacuum freeze drying for 12 hours to obtain ZIF-67/GO powder;
the second step is that: placing ZIF-67/GO powder in an atmosphere furnace, firstly adding N 2 Calcining for 2h at 800 ℃ in the atmosphere, and calcining for 1h at 250 ℃ in the air to obtain the magnetic hollow cobalt oxide @ carbon.
Comparative example 2
A preparation method of magnetic hollow cobalt oxide @ nitrogen-doped porous carbon comprises the following steps:
the first step is as follows: to 30mL of the solution, 0.595 (NO) 0.595gZn was added 3 ) 2 ·6H 2 O、1.164gCo(NO 3 ) 2 ·6H 2 Adding O and 1g of methanol solution of polyvinylpyrrolidone into methanol solution containing 1.847g of dimethyl imidazole, and stirring for 24 hours at room temperature; centrifuging the mixed solution, washing with anhydrous methanol for 3 times, and then carrying out vacuum freeze drying for 12 hours to obtain Zn-Co-ZIFs powder;
the second step is that: putting Zn-Co-ZIFs powder into an atmosphere furnace, and firstly, adding N 2 Calcining for 2h at 800 ℃ in the atmosphere, and calcining for 1h at 250 ℃ in the air to obtain the magnetic hollow cobalt oxide @ nitrogen-doped porous carbon.
The MOFs-derived magnetic hollow cobalt oxide @ nitrogen-doped porous carbon composite materials prepared by the methods described in examples 1-6 and comparative examples 1-2 are used for activating potassium peroxymonosulfate composite salt to degrade sulfamethoxazole, and the specific degradation process comprises the following steps:
2mg of catalyst was added to a 100mL25mg L package -1 In a beaker of SMX solution (initial pH 7),stirring was carried out on a magnetic stirrer (rotation speed 600rpm) for 10min to establish adsorption-desorption equilibrium, and then 12.3mg of potassium monopersulfate complex salt was added to initiate the reaction.
Fig. 1 is an X-ray photoelectron spectrum of the magnetic hollow cobalt oxide @ nitrogen-doped porous carbon provided in example 2, and it can be seen from the graph that the catalyst contains four elements of Co, O, N and C.
Fig. 2 is a transmission electron microscope image of the magnetic hollow cobalt oxide @ nitrogen doped porous carbon provided in example 2, from which it can be seen that the cobalt oxide is attached to reduced graphene oxide sheets and the particle size is less than 100 nm.
Fig. 3 is a high resolution tem image of the magnetic hollow cobalt oxide @ nitrogen doped porous carbon provided in example 2, from which it can be seen that a hollow cavity is present inside the cobalt oxide particle, demonstrating its hollow structure. Furthermore, it can be seen that the cobalt oxide is surrounded by a carbon shell, which proves to have a core-shell structure.
Catalytic degradation efficiency and Co in catalytic system of magnetic hollow cobalt oxide @ nitrogen-doped porous carbon obtained in examples 1-6 and comparative examples 1-2 2+ The leaching concentrations of (a) are shown in table 1 below:
as can be seen from comparative examples 1 to 3, increasing the mass fraction of reduced graphene oxide in the catalyst contributes to increasing the catalytic activity of the catalyst; as can be seen by comparing examples 2, 4, 5 and 6, the reduction of the Zn/Co molar ratio improves the catalytic degradation efficiency of the catalyst on sulfamethoxazole; comparing example 6 with comparative example 1, it can be seen that the evaporation of Zn during the carbonization process further improves the catalytic activity of the catalyst, so that the catalyst can realize complete degradation of sulfamethoxazole within 2 min.
As can be seen by comparing examples 1-3 with comparative example 2, the use of reduced graphene oxide as a support substrate reduces the amount of Co in the catalyst system 2+ The leaching concentration of the catalyst improves the stability of the catalyst and is beneficial to solving the problem of Co 2+ Secondary pollution caused by leaching.
The recycling effect of the magnetic hollow cobalt oxide @ nitrogen-doped porous carbon obtained in example 2 is shown in table 2 below:
| number of reaction times | Reaction time (min) | Degradation efficiency (%) |
| 1 | 5 | 100 |
| 2 | 10 | 100 |
| 3 | 15 | 100 |
| 4 | 20 | 100 |
| 5 | 30 | 94.5 |
As can be seen from Table 2, the catalyst can degrade 94.5% sulfamethoxazole within 30min after being recycled for 5 times, indicating that the catalyst has good recycling property.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and inventive concepts of the present invention are equivalent or changed and shall be covered by the scope of the present invention.
Claims (3)
1. The application of the magnetic hollow cobalt oxide @ nitrogen-doped porous carbon in antibiotic wastewater treatment is characterized by comprising the following steps of:
firstly, ultrasonically dispersing Graphene Oxide (GO) powder in water for 1h, adding methanol, and continuously dispersing for 1h to prepare a GO dispersion liquid; in the first step, the mass parts of GO, water and methanol are as follows: 48.6-103.6mg GO: 20mL of water: 20mL of methanol;
the second step is that: adding Zn (NO) 3 ) 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 Dissolving O and a dispersing agent in methanol to prepare a mixed solution; the molar ratio of Zn to Co in the second step is 2:1-1: 3; the dispersant in the second step is polyvinylpyrrolidone with the mass of 1 g; the amount of methanol used in the second step is 30 mL;
the third step: dissolving dimethyl imidazole in methanol to prepare a solution; the mass of the dimethyl imidazole in the third step is 0.924-2.464 g; in the third step, the using amount of the methanol is 30 mL;
the fourth step: adding the mixed solution in the second step into the GO dispersion liquid prepared in the first step, fully mixing for 2 hours, then adding the dimethyl imidazole solution prepared in the third step, continuously mixing for 24 hours, and centrifuging, washing and drying the obtained mixed solution to obtain purple powder; the doping amount of GO in the purple powder obtained in the fourth step is 1.2-2.2 wt%; fourthly, after centrifuging the mixed solution, washing and centrifuging the mixed solution for 3 times by using anhydrous methanol, removing supernate, and carrying out vacuum freeze drying on the precipitate for 12 hours to obtain purple powder;
the fifth step: the purple powder in the fourth step is firstly treated with N 2 Calcining in the atmosphere, and calcining in the air to prepare the magnetic hollow cobalt oxide @ nitrogen-doped porous carbon; will be magneticThe sexual hollow cobalt oxide @ nitrogen-doped porous carbon is used for activating potassium peroxymonosulfate composite salt to degrade sulfamethoxazole; in the fifth step, the purple powder is in N 2 The calcination condition in the atmosphere is 800 ℃ for 2h, and the calcination condition in the air is 250 ℃ for 1 h.
2. The use of the magnetic hollow cobalt oxide @ nitrogen doped porous carbon according to claim 1, wherein: magnetic stirring is adopted in the second step, the third step and the fourth step for preparing the mixed solution, and the rotating speed is 600 rpm; the first to fourth steps are all carried out at room temperature.
3. The application of the magnetic hollow cobalt oxide @ nitrogen-doped porous carbon in antibiotic wastewater treatment according to claim 1, wherein the application of the magnetic hollow cobalt oxide @ nitrogen-doped porous carbon in activating potassium peroxymonosulfate composite salt to degrade sulfamethoxazole specifically comprises the following steps: 2mg of magnetic hollow cobalt oxide @ nitrogen doped porous carbon was added to a sample containing 100mL of 25mg L −1 In a beaker of sulfamethoxazole solution with initial pH =7, stirred on a magnetic stirrer at 600rpm for 10min to establish adsorption-desorption equilibrium, and then 12.3mg of potassium monopersulfate complex salt was added to initiate the reaction.
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