CN114471443A - Manganese oxide @ nitrogen-doped block carbon aerogel material and preparation and application thereof - Google Patents

Manganese oxide @ nitrogen-doped block carbon aerogel material and preparation and application thereof Download PDF

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CN114471443A
CN114471443A CN202111632108.9A CN202111632108A CN114471443A CN 114471443 A CN114471443 A CN 114471443A CN 202111632108 A CN202111632108 A CN 202111632108A CN 114471443 A CN114471443 A CN 114471443A
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nitrogen
manganese
carbon aerogel
aerogel material
manganese oxide
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CN114471443B (en
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侯浩波
陈家骜
李嘉豪
曾天宇
曾庆媛
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Institute Of Resources And Environmental Technology Wuhan University Zhaoqing
Wuhan University WHU
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Wuhan University WHU
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Abstract

The invention belongs to the field of wastewater treatment, and particularly relates to a preparation method of a manganese oxide @ nitrogen-doped block carbon aerogel material, which comprises the following steps of mixing phenolic resin,
Figure DDA0003440550560000011
Performing gelation reaction in methanol before preparing blockDriving a body: and then loading a manganese source in the block precursor and carrying out calcination treatment to obtain the manganese oxide @ nitrogen-doped block carbon aerogel material. The invention also comprises the material prepared by the preparation method and the application of the material in tetracycline antibiotics. The invention innovatively discovers that the adsorption activity of the prepared material can be improved by adopting phenolic resin and the compound shown in the formula 1 to be further matched with manganese source roasting treatment in methanol internal gel, and the prepared material is beneficial to recovery and has excellent cycle stability.

Description

Manganese oxide @ nitrogen-doped block carbon aerogel material and preparation and application thereof
Technical Field
The invention relates to the field of wastewater treatment, in particular to the field of antibiotic wastewater adsorbing materials.
Background
In recent years, carbon aerogels have attracted attention from researchers due to their wide applicability in various fields, such as solar cells, supercapacitors, electrochemistry, and environmental sciences. The aerogel has a pore structure formed by connecting three-dimensional (3D) networks, can realize high water absorption, provides a large specific adsorption surface area, and makes the carbon aerogel attract more and more attention in the adsorption of heavy metals and organic pollutants. However, the adsorption capacity of carbon aerogel to pollutants in wastewater is still limited, so the physical and chemical properties of carbon aerogel must be improved to further remove pollutants in wastewater, and the doping modification of carbon aerogel to obtain unique excellent performance has become a research hotspot in recent years.
The modification mode is mainly focused on modifying the carbon aerogel by nitrogen and metal elements so as to make up the defects of poor hydrophilicity and low surface activity. The nitrogen is located adjacent to the carbon in the periodic table and, when incorporated into the carbon aerogel, may replace a carbon atom in the carbon aerogel, the nitrogen atom having an additional nuclear electron to donate an electron to the pi electron in the Sp2 mixed carbon framework. Research shows that the nitrogen-doped carbon material has partially unpaired electrons, so that the nitrogen-doped carbon material is widely applied to the fields of catalysis and adsorption. Some studies also suggest that nitrogen doping may reduce the surface area and pore volume of biochar, and thus, modification of carbon aerogel by nitrogen doping may greatly alter its adsorption properties. However, the carbon aerogel incorporating only nitrogen cannot provide more functional groups on the surface thereof, and further modification methods are required to increase the functional groups of the carbon aerogel. Meanwhile, the existing carbon aerogel materials generally have the technical problems of low synthesis efficiency, long preparation procedure, high cost, difficult recovery, unsatisfactory cyclic adsorption stability and the like.
Disclosure of Invention
Aiming at the problem that the adsorption performance and the regeneration stability of the existing antibiotic adsorption material are difficult to be considered at the same time, the invention provides a preparation method of a manganese oxide @ nitrogen-doped block carbon aerogel material, and aims to prepare a material which has both excellent adsorption performance and adsorption stability.
The second purpose of the invention is to provide the manganese oxide @ nitrogen-doped bulk carbon aerogel material prepared by the preparation method.
The third purpose of the invention is to provide the application of the manganese oxide @ nitrogen-doped bulk carbon aerogel material prepared by the preparation method in adsorption of antibiotics, especially tetracycline antibiotics.
The existing antibiotic adsorption material is mainly a powder material, which has good specific surface area and theoretically better adsorption performance, but has unsatisfactory wettability in aqueous solution, difficult recovery and regeneration and unsatisfactory regeneration adsorption stability. However, the formation of the adsorbent material as a block theoretically facilitates the recovery of the material, but may affect the adsorption capacity of the material to some extent. Aiming at the technical problem that the adsorption activity and the regeneration adsorption stability of the material are difficult to be considered at the same time, the invention innovatively discovers that the adsorption activity of the prepared material can be improved by adopting phenolic resin and the compound shown in the formula 1 to be further matched with manganese source roasting treatment in methanol inner gel, and the prepared material is not only favorable for recovery, but also excellent in cycle stability. The preparation method can prepare the material with both good adsorption activity and cyclic adsorption stability.
In the invention, the gelation of the phenolic resin, the compound shown in the formula 1 and a methanol system and the roasting treatment under the assistance of manganese are the key points for synergistically improving the adsorption capacity and the cyclic adsorption stability. The preparation method can prepare the nanoscale manganese-nitrogen-doped block carbon aerogel material which has large specific surface area, developed pore structure, more microporous structures and a large number of functional groups, and has the characteristics of large adsorption capacity, high adsorption efficiency, excellent cyclic adsorption stability and the like on organic pollutants.
The invention has no special requirement on the parameters of the phenolic resin, for example, the purity of the phenolic resin is BR.
In the invention, the mass ratio of the phenolic resin to the compound in the formula 1 is 2-8: 1; preferably 2.5-6: 1; further preferably 4-6: 1;
in the present invention, the concentration of the compound of formula 1 in the initial solution of the gelation reaction is 10 to 50 mL/g.
In the invention, the temperature of the gelation reaction is 50-80 ℃.
Preferably, after the gelation reaction forms gel, aging and drying treatment are carried out to prepare the block precursor;
preferably, the aging temperature is 40-60 ℃;
preferably, the aging time is 7-9 d;
preferably, the drying process comprises a first stage drying process and a second stage drying process, wherein the temperature of the first stage drying process is 15-25 ℃, and the time is 12-24 hours; the temperature of the second stage drying process is 50-65 ℃ and the time is 1-2 days.
In the invention, the manganese source is loaded in the bulk precursor by adopting an immersion method;
preferably, the bulk precursor is immersed in a manganese source solution, and then solid-liquid separation and drying treatment are carried out to obtain a bulk precursor loaded with a manganese source;
preferably, the solvent in the manganese source solution is water or a mixed solvent of water and an organic solvent; the organic solvent is at least one of C1-C4 alcohol and acetone;
preferably, the manganese source is a water soluble manganese compound, preferably a permanganate.
Preferably, the stirring and dipping time is 10-24 h;
preferably, the temperature of the stirring and dipping process is 25-40 ℃.
Preferably, the mass ratio of the manganese element in the manganese source to the N element in the formula 1 is 1-10: 1; further preferably 1-5: 1; more preferably 3 to 5:1, and most preferably 4 to 5: 1.
The solid-liquid separation means may be filtration, centrifugation or the like. Examples of the drying include freeze drying, vacuum drying, supercritical drying, and normal-temperature normal-pressure drying.
In the invention, the calcining process is carried out under the protection of inert gas;
preferably, the protective atmosphere is at least one of nitrogen or an inert atmosphere;
preferably, the calcining temperature is 300-1200 ℃; further preferably 500-900 ℃; more preferably 700 to 800 ℃.
Preferably, the calcining time is 1-24 h; further preferably 2 to 6 hours.
The invention also provides a manganese oxide @ nitrogen-doped block carbon aerogel material prepared by the preparation method;
preferably, the nitrogen-doped bulk gel carbon comprises a three-dimensional network structure and manganese oxide nanoparticles loaded on the surface of the nitrogen-doped bulk gel carbon;
preferably, the specific surface area of the manganese oxide @ nitrogen-doped bulk carbon aerogel material is 100-500 m2Per g, pore volume of 0.007cm3/g～0.3cm3The manganese content is 0.5 to 11 percent;
the particle size of the manganese oxide nano-particles is 50-300 nm.
The invention also provides application of the manganese oxide @ nitrogen-doped block carbon aerogel material prepared by the preparation method, and the manganese oxide @ nitrogen-doped block carbon aerogel material is used as an adsorption material of antibiotics.
The application of the invention is used as an adsorbent for adsorbing tetracycline antibiotics in water body by physical-chemical combination.
The research of the invention discovers that the material constructed by the special preparation method can improve the adsorption effect of tetracycline antibiotics based on the physical and special chemical synergistic effect.
Preferably, the antibiotic is at least one of tetracycline, oxytetracycline and chlortetracycline;
preferably, in the adsorption process, the dosage of the adsorbent is 0.8-1.2 g/L;
in a preferred application, the adsorbent is regenerated cyclically.
Has the advantages that:
1. the phenolic resin and the compound shown in the formula 1 are further matched with a manganese source for roasting treatment under methanol gelation, so that the adsorption activity of the prepared material can be improved, and the prepared material is beneficial to recovery and has excellent cycle stability. The preparation method can prepare the material with both good adsorption activity and cyclic adsorption stability.
The preparation method is simple, produces no toxic pollutants, has simple reaction conditions, and is suitable for large-scale production.
2. The material prepared by the preparation process disclosed by the invention has excellent physical and chemical synergistic adsorption activity on antibiotics, particularly tetracycline antibiotics, is beneficial to regeneration cycle, and has excellent cyclic adsorption stability.
Drawings
FIG. 1 is a scanning electron microscope characterization map of the manganese nitrogen-doped carbon aerogel material in example 1;
FIG. 2 is a scanning electron microscope characterization map of the manganese nitrogen-doped carbon aerogel material in example 2;
FIG. 3 is a scanning electron microscopy characterization map of the manganese nitrogen-doped carbon aerogel material in example 3;
FIG. 4 is a scanning electron microscope characterization map of the nitrogen-doped carbon aerogel material in comparative example 1;
FIG. 5 is a macroscopic view of the precursor aerogel material of example 1;
FIG. 6 is an XRD pattern of examples 1 to 3 and comparative example 1.
Detailed Description
In order to better explain the technical solutions and advantages of the present invention, the following detailed description of the present invention is provided with reference to the embodiments. It should be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as those skilled in the art will be able to make insubstantial modifications and variations of this invention in light of the above teachings, and will nevertheless fall within the scope of this invention.
In the present invention, the parameters of the phenolic resin are not particularly required, and in the following case, the phenolic resin used is a resin supplied by the company Aladdin. The above resins are only examples of the embodiments of the present invention and do not necessarily limit the embodiments of the present invention.
Example 1:
the preparation method of the manganese nitrogen doped carbon aerogel material specifically comprises the following steps:
(1) preparing an aerogel precursor: 15g of the phenolic resin and 3g of formula 1 are weighed out and dissolved in 100ml of anhydrous methanol and mixed with stirring until the solution is homogeneous. Sealing the mixed ethanol solution of the phenolic resin formula 1 in a regular container, placing the container in a constant-temperature water bath (60 ℃) at the gelling temperature for sol gelation reaction, aging the solution which is just prepared for 7 days at the water bath reaction (60 ℃) until the color becomes dark along with the increase of the concentration of reactants, and finally taking out the wet gel. Drying at normal temperature (25 ℃) and normal pressure for 1 day, and then placing in an oven for drying for 1 day (65 ℃) to obtain a phenolic resin based organic aerogel precursor;
(2) preparing a potassium permanganate solution: 0.57g of potassium permanganate powder is weighed and placed into a 500ml beaker, and deionized water is added until the mark reaches 300ml, thus obtaining a potassium permanganate solution.
(3) Preparing manganese nitrogen doped carbon aerogel: adding the prepared aerogel precursor into the potassium permanganate solution to ensure that the mass ratio of the manganese element to the nitrogen element in the formula 1 is 1:1 respectively. And (3) continuously stirring for 24 hours by adopting mechanical stirring, so that the gel precursor is completely soaked in the potassium permanganate solution. And centrifuging, filtering, drying at 65 ℃ under normal pressure, heating in a tube furnace at 700 ℃ for 2h under the atmosphere of nitrogen, cooling, taking out black solids to obtain manganese-nitrogen-doped carbon aerogel, and storing in a cool and dry place.
The manganese nitrogen-doped carbon aerogel material prepared by the preparation method. The specific surface area of the manganese-nitrogen-doped carbon aerogel material is 368m2G, average pore diameter of 2.82nm and pore volume of 0.025cm3/g。
The manganese-nitrogen-doped carbon aerogel material in the embodiment 1 is used as an adsorbent, tetracycline solutions with different concentration gradients (the concentration is from 10 mg/L to 200mg/L) are prepared, the manganese-nitrogen-doped carbon aerogel material is added in an amount of 1.2g/L, the manganese-nitrogen-doped carbon aerogel material is adsorbed for 48 hours at 25 ℃ at 200r/min, and a water sample after adsorption is analyzed by using high performance liquid chromatography, wherein the saturated adsorption capacity of the manganese-nitrogen-doped carbon aerogel material synthesized in the embodiment 1 is as follows: 730.8 mg/g.
Example 2:
the preparation method of the manganese nitrogen doped carbon aerogel material specifically comprises the following steps:
(1) preparing an aerogel precursor: 15g of phenolic resin and 3g of formula 1 are weighed out and dissolved in 100ml of anhydrous methanol and mixed with stirring until the solution is homogeneous. Sealing the mixed ethanol solution of the phenolic resin formula 1 in a regular container, placing the container in a constant-temperature water bath (60 ℃) at the gelling temperature for sol gelation reaction, wherein the solution just prepared is light yellow (the color depth is deepened along with the increase of the concentration of reactants), the water bath reaction is aged (60 ℃) for 7 days, the color is gradually deepened, and finally, taking out the gel. Drying at normal temperature (25 ℃) and normal pressure for 1 day, and then placing in an oven for drying for 1 day (65 ℃) to obtain a phenolic resin based organic aerogel precursor;
(2) preparing a potassium permanganate solution: 1.71g of potassium permanganate powder is weighed and placed into a 500ml beaker, deionized water is added until the mark of 300ml is reached, and a potassium permanganate solution is obtained.
(3) Preparing manganese nitrogen doped carbon aerogel: adding the prepared aerogel precursor into the potassium permanganate solution to ensure that the mass ratio of the manganese element to the nitrogen element is 3:1 respectively. And (3) continuously stirring for 24 hours by adopting mechanical stirring, so that the gel precursor is completely soaked in the potassium permanganate solution. And centrifuging, filtering, drying at 65 ℃ under normal pressure, heating in a tube furnace at 700 ℃ for 2h under the atmosphere of nitrogen, cooling, taking out black solids to obtain manganese-nitrogen-doped carbon aerogel, and storing in a cool and dry place.
The manganese nitrogen-doped carbon aerogel material prepared by the preparation method. The specific surface area of the manganese-nitrogen-doped carbon aerogel material is 292m2G, average pore diameter of 3.43nm, pore volumeIs 0.013cm3/g。
Taking the manganese nitrogen-doped carbon aerogel material in the embodiment 2 as an adsorbent, preparing tetracycline solutions with different concentration gradients (the concentration is from 10 mg/L to 200mg/L), adding the manganese nitrogen-doped carbon aerogel material in an addition amount of 1.2g/L, adsorbing for 48 hours at 25 ℃ at 200r/min, and analyzing a water sample after adsorption by using high performance liquid chromatography, wherein the saturated adsorption amount of the manganese nitrogen-doped carbon aerogel material synthesized in the embodiment 2 is as follows: 828.3 mg/g.
Example 3:
the preparation method of the manganese nitrogen doped carbon aerogel material specifically comprises the following steps:
(1) preparing an aerogel precursor: 15g of phenolic resin and 3g of formula 1 are weighed out and dissolved in 100ml of anhydrous methanol and mixed with stirring until the solution is homogeneous. Sealing the mixed ethanol solution of the phenolic resin formula 1 in a regular container, placing the container in a constant-temperature water bath (60 ℃) at the gelling temperature for sol gelation reaction, wherein the solution just prepared is light yellow (the color depth is deepened along with the increase of the concentration of reactants), the water bath reaction is aged (60 ℃) for 7 days, the color is gradually deepened, and finally, taking out the gel. Drying at normal temperature (25 ℃) and normal pressure for 1 day, and then placing in an oven for drying for 1 day (65 ℃) to obtain a phenolic resin based organic aerogel precursor;
(2) preparing a potassium permanganate solution: 2.86g of potassium permanganate powder is weighed and placed into a 500ml beaker, deionized water is added to reach the 300ml scale mark, and a potassium permanganate solution is obtained.
(3) Preparing manganese nitrogen doped carbon aerogel: adding the prepared aerogel precursor into a potassium permanganate solution to ensure that the mass ratio of manganese elements to nitrogen elements is 5:1 respectively; and (3) continuously stirring for 24 hours by adopting mechanical stirring, so that the gel precursor is completely soaked in the potassium permanganate solution. And (3) centrifuging, filtering, drying the modified solution at the normal pressure and the temperature of 65 ℃, heating the solution in a tubular furnace at the temperature of 700 ℃ for 2 hours in the nitrogen atmosphere, cooling, taking out black solids to obtain manganese-nitrogen-doped carbon aerogel, and storing the manganese-nitrogen-doped carbon aerogel in a cool and dry place.
The manganese nitrogen-doped carbon aerogel material prepared by the preparation method. The specific surface area of the manganese-nitrogen-doped carbon aerogel material is 125m2G, averageThe aperture is 3.85nm, and the pore volume is 0.008cm3/g。
Taking the manganese-nitrogen-doped carbon aerogel material in example 3 as an adsorbent, preparing tetracycline solutions with different concentration gradients (with a concentration of 10-200 mg/L), adding the manganese-nitrogen-doped carbon aerogel material in an amount of 1.2g/L, adsorbing at 25 ℃ and 200r/min for 48 hours, and analyzing the water sample after adsorption by using high performance liquid chromatography, wherein the saturated adsorption amount of the manganese-nitrogen-doped carbon aerogel material synthesized in example 3 is as follows: 917.2 mg/g.
Example 4:
compared with the embodiment 3, the difference is mainly that the proportion of the phenolic resin and the formula 1 is regulated and controlled, and the specific steps are as follows:
(1) preparing an aerogel precursor: 15g of the phenolic resin and 6g of formula 1 are weighed out and dissolved in 100ml of anhydrous methanol and mixed with stirring until the solution is homogeneous. Sealing the mixed ethanol solution of the phenolic resin formula 1 in a regular container, placing the container in a constant-temperature water bath (60 ℃) with the gel temperature to carry out sol-gel reaction, wherein the solution just prepared is light yellow (the color depth is deepened along with the increase of the concentration of reactants), the water bath reaction is aged (60 ℃) for 7 days, the color is deepened gradually, and finally, taking out the gel. Drying at normal temperature (25 ℃) and normal pressure for 1 day, and then placing in an oven for drying for 1 day (65 ℃) to obtain a phenolic resin based organic aerogel precursor;
(2) preparing a potassium permanganate solution: 2.86g of potassium permanganate powder is weighed and placed into a 500ml beaker, deionized water is added to reach the 300ml scale mark, and a potassium permanganate solution is obtained.
(3) Preparing manganese nitrogen doped carbon aerogel: and adding the prepared aerogel precursor into the potassium permanganate solution to ensure that the mass ratio of the manganese element to the nitrogen element is 5:1 respectively. And (3) continuously stirring for 24 hours by adopting mechanical stirring, so that the gel precursor is completely soaked in the potassium permanganate solution. And centrifuging, filtering, drying at 65 ℃ under normal pressure, heating in a tube furnace at 700 ℃ for 2h under the atmosphere of nitrogen, cooling, taking out black solids to obtain manganese-nitrogen-doped carbon aerogel, and storing in a cool and dry place.
The manganese nitrogen doped carbon aerogel material prepared by the preparation method. The specific surface area of the carbon aerogel material doped with manganese and nitrogenIs 187m2G, average pore diameter of 4.12nm, pore volume of 0.012cm3/g。
Taking the manganese-nitrogen-doped carbon aerogel material in example 4 as an adsorbent, preparing tetracycline solutions with different concentration gradients (with a concentration of 10-200 mg/L), adding the manganese-nitrogen-doped carbon aerogel material in an amount of 1.2g/L, adsorbing at 25 ℃ and 200r/min for 48 hours, and analyzing the water sample after adsorption by using high performance liquid chromatography, wherein the saturated adsorption amount of the manganese-nitrogen-doped carbon aerogel material synthesized in example 4 is as follows: 638.5 mg/g.
Example 5:
compared with the example 3, the difference is that the temperature of the calcination is 500 ℃, and the specific steps are as follows:
(1) preparing an aerogel precursor: 15g of phenolic resin and 3g of formula 1 are weighed out and dissolved in 100ml of anhydrous methanol and mixed with stirring until the solution is homogeneous. Sealing the mixed ethanol solution of the phenolic resin formula 1 in a regular container, placing the container in a constant-temperature water bath (60 ℃) at the gelling temperature for sol gelation reaction, wherein the solution just prepared is light yellow (the color depth is deepened along with the increase of the concentration of reactants), the water bath reaction is aged (60 ℃) for 7 days, the color is gradually deepened, and finally, taking out the gel. Drying at normal temperature (25 ℃) and normal pressure for 1 day, and then placing in an oven for drying for 1 day (65 ℃) to obtain a phenolic resin based organic aerogel precursor;
(2) preparing a potassium permanganate solution: 2.86g of potassium permanganate powder is weighed and placed into a 500ml beaker, deionized water is added to reach the 300ml scale mark, and a potassium permanganate solution is obtained.
(3) Preparing manganese nitrogen doped carbon aerogel: adding the prepared aerogel precursor into a potassium permanganate solution to ensure that the mass ratio of manganese elements to nitrogen elements is 5:1 respectively. And (3) continuously stirring for 24 hours by adopting mechanical stirring, so that the gel precursor is completely soaked in the potassium permanganate solution. And centrifuging, filtering, drying at 65 ℃ under normal pressure, heating in a tube furnace at 500 ℃ for 2h under the atmosphere of nitrogen, cooling, taking out black solids to obtain manganese-nitrogen-doped carbon aerogel, and storing in a cool and dry place.
The manganese nitrogen-doped carbon aerogel material prepared by the preparation method. The carbon aerogel doped with manganese and nitrogenThe specific surface area of the material is 110m2G, average pore diameter of 3.21nm and pore volume of 0.005cm3/g。
Taking the manganese-nitrogen-doped carbon aerogel material in example 5 as an adsorbent, preparing tetracycline solutions with different concentration gradients (with a concentration of 10-200 mg/L), adding the manganese-nitrogen-doped carbon aerogel material in an amount of 1.2g/L, adsorbing at 25 ℃ and 200r/min for 48 hours, and analyzing the water sample after adsorption by using high performance liquid chromatography, wherein the saturated adsorption amount of the manganese-nitrogen-doped carbon aerogel material synthesized in example 5 is as follows: 562.7 mg/g.
Example 6 circulation
The method for the cyclic adsorption stability of the manganese nitrogen-doped carbon aerogel material (prepared in example 3) specifically comprises the following steps:
(1) the manganese nitrogen doped carbon aerogel material adsorption method comprises the following steps: the manganese nitrogen-doped carbon aerogel material in the embodiment 3 is used as an adsorbent, tetracycline solutions with different concentration gradients (the concentration is from 10 mg/L to 200mg/L) are prepared, the manganese nitrogen-doped carbon aerogel material is added in an amount of 1.2g/L, and the manganese nitrogen-doped carbon aerogel material is adsorbed for 48 hours at the temperature of 25 ℃ and at the speed of 200 r/min.
(2) The desorption method of the manganese nitrogen doped carbon aerogel material comprises the following steps: the adsorbed manganese nitrogen-doped carbon aerogel is desorbed using a solvent elution process. The desorption reagent is H2And O, soaking the manganese nitrogen-doped carbon aerogel adsorbed with the tetracycline solution into a flask filled with distilled water. And then, cleaning by ultrasonic vibration, and repeating the step of cleaning the manganese nitrogen-doped carbon aerogel for three times. The cleaned manganese nitrogen-doped carbon aerogel is dried and then directly applied to the next adsorption cycle.
The adsorption and desorption experiment is repeated for 5 times, and the removal rate of the tetracycline solution by the manganese-nitrogen-doped carbon aerogel reaches 75% in the fifth time.
Comparative example 1:
compared with the embodiment, the difference is mainly that Mn is not compounded on the surface, and the steps are as follows:
(1) preparing an aerogel precursor: 15g of phenolic resin and 3g of formula 1 are weighed out and dissolved in 100ml of anhydrous methanol and mixed with stirring until the solution is homogeneous. Sealing the mixed ethanol solution of the phenolic resin formula 1 in a regular container, placing the container in a constant-temperature water bath (60 ℃) at the gelling temperature for sol gelation reaction, wherein the solution just prepared is light yellow (the color depth is deepened along with the increase of the concentration of reactants), the water bath reaction is aged (60 ℃) for 7 days, the color is gradually deepened, and finally, taking out the gel. Drying at normal temperature (25 ℃) and normal pressure for 1 day, and then placing in an oven for drying for 1 day (65 ℃) to obtain a phenolic resin based organic aerogel precursor;
(3) preparing nitrogen-doped carbon aerogel: and centrifuging, filtering, drying the prepared aerogel precursor at the normal pressure and the temperature of 65 ℃, heating the aerogel precursor in a tube furnace at the temperature of 700 ℃ for 2h in the atmosphere of nitrogen, cooling, taking out black solids to obtain the nitrogen-doped carbon aerogel, and storing the nitrogen-doped carbon aerogel in a cool and dry place.
The nitrogen-doped carbon aerogel material prepared by the preparation method. The specific surface area of the nitrogen-doped carbon aerogel material is 429m2G, average pore diameter of 2.19nm and pore volume of 0.3cm3/g。
Taking the nitrogen-doped carbon aerogel material in the comparative example 1 as an adsorbent, preparing tetracycline solutions with different concentration gradients (the concentration is from 10 mg/L to 200mg/L), adding the nitrogen-doped carbon aerogel material in an addition amount of 1.2g/L, adsorbing for 48 hours at 25 ℃ under 200r/min, and analyzing the water sample after adsorption by using high performance liquid chromatography, wherein the saturated adsorption capacity of the manganese-nitrogen-doped carbon aerogel material synthesized in the comparative example 1 is as follows: 234.7 mg/g.
Comparative example 2:
the only difference compared to example 3 is that equal mass of melamine is used instead of formula 1. As a result of measuring the adsorption performance by the method of example 3, the saturated adsorption capacity was 356.9 mg/g.
Comparative example 4:
compared with the example 3, the difference is only that the absolute methanol is replaced by the equal volume of absolute ethanol, and other parameters and adsorption modes are the same as the example 3. The saturated adsorption capacity was 425.7 mg/g. The performance is significantly worse than in example 3.

Claims (10)

1. The preparation method of the manganese oxide @ nitrogen-doped bulk carbon aerogel material is characterized by comprising the following steps of carrying out gelation reaction on phenolic resin and a compound shown in a formula 1 in methanol to prepare a bulk precursor: then loading a manganese source in the block precursor and carrying out calcination treatment to obtain the manganese oxide @ nitrogen-doped block carbon aerogel material;
Figure FDA0003440550530000011
2. the preparation method of the manganese oxide @ nitrogen-doped bulk carbon aerogel material as claimed in claim 1, wherein the mass ratio of the phenolic resin to the compound of formula 1 is 2-8: 1; preferably 2.5-6: 1.
3. The method of making a manganese oxide @ nitrogen doped bulk carbon aerogel material of claim 1, wherein the phenolic resin purity is BR;
preferably, the concentration of the compound of formula 1 in the initial solution of the gelation reaction is 10 to 50 mL/g.
4. The preparation method of the manganese oxide @ nitrogen-doped bulk carbon aerogel material as claimed in claim 1, wherein the temperature of the gelation reaction is 50-80 ℃;
preferably, aging and drying are carried out after the gelation reaction to prepare the block precursor;
preferably, the aging temperature is 40-60 ℃;
preferably, the aging time is 7-9 d;
preferably, the drying process comprises a first stage drying process and a second stage drying process, wherein the temperature of the first stage drying process is 15-25 ℃, and the time is 12-24 hours; the temperature of the second stage drying process is 50-65 ℃ and the time is 1-2 days.
5. The preparation method of manganese oxide @ nitrogen-doped bulk carbon aerogel material according to claim 1, wherein the manganese source is loaded in a bulk precursor by an impregnation method;
preferably, the bulk precursor is immersed in a manganese source solution, and then solid-liquid separation and drying treatment are carried out to obtain a bulk precursor loaded with a manganese source;
preferably, the solvent in the manganese source solution is water or a mixed solvent of water and an organic solvent; the organic solvent is at least one of C1-C4 alcohol and acetone;
preferably, the manganese source is a water-soluble manganese compound, preferably permanganate;
preferably, the mass ratio of the manganese element in the manganese source to the N element in the formula 1 is 1-10: 1.
6. The method for preparing manganese oxide @ nitrogen-doped bulk carbon aerogel material according to claim 1, wherein the calcination process is carried out under the protection of inert gas;
preferably, the protective atmosphere is at least one of nitrogen or an inert atmosphere;
preferably, the calcining temperature is 300-1200 ℃;
preferably, the calcination time is 1-24 h.
7. The manganese oxide @ nitrogen-doped bulk carbon aerogel material prepared by the preparation method of any one of claims 1 to 6;
preferably, the nitrogen-doped bulk gel carbon comprises a three-dimensional network structure and manganese oxide nanoparticles loaded on the surface of the nitrogen-doped bulk gel carbon;
preferably, the specific surface area of the manganese oxide @ nitrogen-doped bulk carbon aerogel material is 100-500 m2Per g, pore volume of 0.007cm3/g～0.3cm3The manganese content is 0.5 to 11 percent;
the particle size of the manganese oxide nano-particles is 50-300 nm.
8. The application of the manganese oxide @ nitrogen-doped bulk carbon aerogel material prepared by the preparation method according to any one of claims 1 to 6 is characterized in that the manganese oxide @ nitrogen-doped bulk carbon aerogel material is used as an antibiotic adsorption material.
9. The use according to claim 8 as an adsorbent for the combined physical-chemical adsorption of tetracycline antibiotics in a body of water;
preferably, the antibiotic is at least one of tetracycline, oxytetracycline and chlortetracycline;
preferably, in the adsorption process, the dosage of the adsorbent is 0.8-1.2 g/L.
10. The use of claim 9, wherein the adsorbent is regenerated cyclically.
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