CN114471443B - 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

Info

Publication number
CN114471443B
CN114471443B CN202111632108.9A CN202111632108A CN114471443B CN 114471443 B CN114471443 B CN 114471443B CN 202111632108 A CN202111632108 A CN 202111632108A CN 114471443 B CN114471443 B CN 114471443B
Authority
CN
China
Prior art keywords
manganese
use according
carbon aerogel
nitrogen
aerogel material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111632108.9A
Other languages
Chinese (zh)
Other versions
CN114471443A (en
Inventor
侯浩波
陈家骜
李嘉豪
曾天宇
曾庆媛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute Of Resources And Environmental Technology Wuhan University Zhaoqing
Wuhan University WHU
Original Assignee
Institute Of Resources And Environmental Technology Wuhan University Zhaoqing
Wuhan University WHU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute Of Resources And Environmental Technology Wuhan University Zhaoqing, Wuhan University WHU filed Critical Institute Of Resources And Environmental Technology Wuhan University Zhaoqing
Priority to CN202111632108.9A priority Critical patent/CN114471443B/en
Publication of CN114471443A publication Critical patent/CN114471443A/en
Application granted granted Critical
Publication of CN114471443B publication Critical patent/CN114471443B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0091—Preparation of aerogels, e.g. xerogels
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28042—Shaped bodies; Monolithic structures
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28047—Gels
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention belongs to the field of wastewater treatment, and in particular relates to a preparation method of a manganese oxide @ nitrogen doped block carbon aerogel material, which comprises the steps of preparing a phenolic resin,The gelation reaction is carried out in methanol to prepare a block precursor: and then loading a manganese source into the block precursor and calcining 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 phenolic resin and the compound of formula 1 are adopted to be gelled in methanol and are further matched with a manganese source for bakingThe burning treatment can improve the adsorption activity of 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 adsorption materials.
Background
In recent years, due to the wide applicability of carbon aerogel in various fields, such as solar cells, supercapacitors, electrochemistry and environmental science, attention of researchers has been paid. The aerogel has a pore structure with interconnected three-dimensional (3D) networks, can realize high water absorption, and provides a large specific adsorption surface area, so that the carbon aerogel is also receiving more and more attention in the adsorption of heavy metals and organic pollutants. However, the adsorption capacity of carbon aerogel for pollutants in wastewater is still limited, so that physical and chemical properties of carbon aerogel must be improved to further remove pollutants in wastewater, and in recent years, doping modification of carbon aerogel to obtain unique excellent performance has become a research hot spot.
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 it can replace carbon atoms in the carbon aerogel, the nitrogen atoms having an additional nuclear electron that provides an electron for pi electrons in the Sp2 mixed carbon framework. Research shows that nitrogen doped carbon materials have partial unpaired electrons and thus find wide application in the catalytic and adsorption fields. Some studies also suggest that nitrogen doping may reduce the surface area and pore volume of biochar, and thus modifying the carbon aerogel by nitrogen doping can greatly alter its adsorption properties. However, carbon aerogel incorporating nitrogen alone cannot provide more functional groups on its surface, and further modification methods are required to increase the functional groups of the carbon aerogel. Meanwhile, the existing carbon aerogel material generally has the technical problems of low synthesis efficiency, long preparation process, high cost, difficult recovery, unsatisfactory cyclical adsorption and 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 compatible, the first aim of the invention is to provide a preparation method of a manganese oxide@nitrogen doped block carbon aerogel material, and the aim is to prepare a material with excellent adsorption performance and adsorption stability.
The second aim of the invention is to provide the manganese oxide@nitrogen doped block 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 block carbon aerogel material prepared by the preparation method in the adsorption of antibiotics, in particular tetracycline antibiotics.
The existing antibiotic adsorption material is mainly a powder material, and the material has good specific surface area and better adsorption performance in theory, but the wettability of the material in aqueous solution is not ideal, the material is difficult to recycle and regenerate, and the regeneration adsorption stability is not ideal. However, making the adsorbent material into a block is theoretically advantageous for material recovery, but may affect the adsorption capacity of the material to some extent. Aiming at the technical problems that the adsorption activity and the regeneration adsorption stability of the material are difficult to be simultaneously considered, 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 under the condition that the phenolic resin and the compound are gelled in methanol, and the prepared material is favorable for recovery and has excellent cycle stability. The preparation method can prepare the material with good adsorption activity and cyclic adsorption stability.
In the invention, gelation of the phenolic resin, the compound of formula 1 and a methanol system and roasting treatment under the assistance of manganese are key to synergistically improve adsorption capacity and cyclic adsorption stability. According to the preparation method, the nano-scale manganese-nitrogen doped block carbon aerogel material which has the characteristics of large specific surface area, developed pore structure, more micropore structure, high adsorption capacity for organic pollutants, high adsorption efficiency, excellent cyclical adsorption stability and the like and contains a large number of functional groups can be prepared.
The parameters of the phenolic resin are not particularly required in the present invention, for example, the phenolic resin purity is BR.
In the invention, the mass ratio of the phenolic resin to the compound of the formula 1 is 2-8:1; preferably 2.5-6:1; further preferably 4 to 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 50mL/g.
In the present invention, the temperature of the gelation reaction is 50 to 80 ℃.
Preferably, the block precursor is prepared by aging and drying after the gelation reaction forms gel;
preferably, the temperature of aging 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 block precursor by adopting an impregnation method;
preferably, the block precursor is immersed in a manganese source solution, and then subjected to solid-liquid separation and drying treatment to obtain a manganese source-loaded block precursor;
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 alcohol with the carbon number of 1-4 and acetone;
preferably, the manganese source is a water-soluble manganese compound, preferably a permanganate.
Preferably, the stirring and soaking process time is 10-24 hours;
preferably, the temperature of the stirring impregnation 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 to 5:1; still 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. The drying is, for example, freeze drying, vacuum drying, supercritical drying, normal temperature and normal pressure drying, or the like.
In the invention, 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 calcination temperature is 300-1200 ℃; further preferably 500 to 900 ℃; still more preferably 700 to 800 ℃.
Preferably, the calcination time is 1 to 24 hours; more 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 block gel carbon comprises a three-dimensional network structure and manganese oxide nano particles loaded on the surface of the nitrogen-doped block gel carbon;
preferably, the specific surface area of the manganese oxide@nitrogen doped block carbon aerogel material is 100-500 m 2 Per gram, pore volume of 0.007cm 3 /g～0.3cm 3 Per gram, the manganese content is 0.5 to 11 percent;
the particle size of the manganese oxide nano particles is 50-300nm.
The invention also provides application of the manganese oxide@nitrogen doped block carbon aerogel material prepared by the preparation method in an adsorption material of antibiotics.
The application of the invention is used as an adsorbent for physical-chemical combination adsorption of tetracycline antibiotics in water.
The research of the invention discovers that the material constructed by the special preparation method can improve the adsorption effect of the tetracycline antibiotics based on the synergistic effect of physics and special chemistry.
Preferably, the antibiotic is at least one of tetracycline, oxytetracycline and aureomycin;
preferably, the dosage of the adsorbent is 0.8-1.2 g/L in the adsorption process;
the preferred application is to recycle the adsorbent.
The beneficial effects are that:
1. the phenolic resin and the compound of formula 1 are adopted to be further matched with manganese source roasting treatment under methanol, so that the adsorption activity of the prepared material can be improved, the recovery is facilitated, and the cycle stability is excellent. The preparation method can prepare the material with good adsorption activity and cyclic adsorption stability.
The preparation method is simple, no toxic pollutant is generated, the reaction condition is simple, and the preparation method is suitable for large-scale production.
2. The material prepared by the preparation process has excellent physical and chemical synergistic adsorption activity on antibiotics, particularly tetracycline antibiotics, is favorable for regeneration circulation and has excellent cyclic adsorption stability.
Drawings
FIG. 1 is a graph of the scanning electron microscope characterization of the Mn-N doped carbon aerogel material of example 1;
FIG. 2 is a graph of the scanning electron microscope characterization of the Mn-N doped carbon aerogel material of example 2;
FIG. 3 is a graph of the scanning electron microscope characterization of the Mn-N doped carbon aerogel material of example 3;
FIG. 4 is a scanning electron microscope characterization map of the nitrogen-doped carbon aerogel material of comparative example 1;
FIG. 5 is a macroscopic view of the precursor aerogel material of example 1;
fig. 6 is XRD patterns of examples 1 to 3 and comparative example 1.
Detailed Description
In order to better explain the technical scheme and advantages of the present invention, the present invention will be further described in detail with reference to the following examples. It is noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as will be apparent to those skilled in the art upon examination of the foregoing disclosure.
In the present invention, the parameters of the phenolic resin are not particularly limited, and in the following cases, the phenolic resin used is a resin supplied by Alatting corporation. The above resins are only examples of embodiments of the present invention and do not constitute a necessary limitation of the technical scheme of the present invention.
Example 1:
the preparation method of the manganese-nitrogen doped carbon aerogel material specifically comprises the following steps:
(1) Aerogel precursor preparation: 15g of phenolic resin and 3g of 1 are weighed and dissolved in 100ml of absolute methanol, and stirred and mixed until the dissolution is uniform. And sealing the phenolic resin type 1 mixed ethanol solution in a regular container, placing the container in a constant-temperature water bath (60 ℃) at the gel temperature for sol-gel reaction, enabling the solution just prepared to be light yellow (the color depth is deepened along with the increase of the concentration of reactants), aging for 7 days in the water bath reaction (60 ℃) until the color is deepened gradually, and finally taking out the wet gel. Drying for 1 day at normal temperature (25 ℃) and normal pressure, and then drying for 1 day (65 ℃) in an oven to obtain a phenolic resin-based organic aerogel precursor;
(2) Preparing a potassium permanganate solution: 0.57g of potassium permanganate powder is weighed, filled into a 500ml beaker, deionized water is added to reach 300ml of scale marks, 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, so that the mass ratio of manganese element to nitrogen element in the formula 1 is 1:1 respectively. Mechanical stirring is adopted, and continuous stirring is carried out for 24 hours, so that the gel precursor is completely soaked in the potassium permanganate solution. And (3) centrifuging, filtering, drying at normal pressure and 65 ℃ and then heating for 2 hours at 700 ℃ in a tube furnace under nitrogen atmosphere, cooling and taking out black solid 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 is prepared. The manganese nitrogen doped carbon gasThe specific surface area of the gel material is 368m 2 Per g, average pore diameter 2.82nm, pore volume 0.025cm 3 /g。
Taking the manganese-nitrogen doped carbon aerogel material in the embodiment 1 as an adsorbent, preparing tetracycline solutions with different concentration gradients (the concentration is 10-200 mg/L), adding the manganese-nitrogen doped carbon aerogel material with the addition amount of 1.2g/L, adsorbing for 48 hours at the temperature of 25 ℃ under the condition of 200r/min, and analyzing the adsorbed water sample by utilizing high performance liquid chromatography, wherein the saturated adsorption amount of the manganese-nitrogen doped carbon aerogel material synthesized in the embodiment 1 is as follows: 730.8mg/g.
Example 2:
the preparation method of the manganese-nitrogen doped carbon aerogel material specifically comprises the following steps:
(1) Aerogel precursor preparation: 15g of phenolic resin and 3g of 1 are weighed and dissolved in 100ml of absolute methanol, and stirred and mixed until the dissolution is uniform. And sealing the phenolic resin type 1 mixed ethanol solution in a regular container, placing the container in a constant-temperature water bath (60 ℃) at the gel temperature for sol gelation reaction, enabling the newly prepared solution to be light yellow (the color depth is deepened along with the increase of the concentration of reactants), aging (60 ℃) for 7 days during the water bath reaction, gradually deepening the color, and finally taking out the gel. Drying for 1 day at normal temperature (25 ℃) and normal pressure, and then drying for 1 day (65 ℃) in an oven to obtain a phenolic resin-based organic aerogel precursor;
(2) Preparing a potassium permanganate solution: 1.71g of potassium permanganate powder was weighed, charged into a 500ml beaker, and deionized water was added to reach 300ml of scale marks to obtain a potassium permanganate solution.
(3) Preparing manganese-nitrogen doped carbon aerogel: and adding the prepared aerogel precursor into the potassium permanganate solution, so that the mass ratio of manganese element to nitrogen element is 3:1 respectively. Mechanical stirring is adopted, and continuous stirring is carried out for 24 hours, so that the gel precursor is completely soaked in the potassium permanganate solution. And (3) centrifuging, filtering, drying at normal pressure and 65 ℃ and then heating for 2 hours at 700 ℃ in a tube furnace under nitrogen atmosphere, cooling and taking out black solid 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 is prepared.The specific surface area of the manganese-nitrogen doped carbon aerogel material is 292m 2 Per g, average pore diameter 3.43nm, pore volume 0.013cm 3 /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 10-200 mg/L), adding the manganese-nitrogen doped carbon aerogel material with the addition amount of 1.2g/L, adsorbing for 48 hours at the temperature of 25 ℃ under the condition of 200r/min, and analyzing the adsorbed water sample by utilizing 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: 828.3mg/g.
Example 3:
the preparation method of the manganese-nitrogen doped carbon aerogel material specifically comprises the following steps:
(1) Aerogel precursor preparation: 15g of phenolic resin and 3g of 1 are weighed and dissolved in 100ml of absolute methanol, and stirred and mixed until the dissolution is uniform. And sealing the phenolic resin type 1 mixed ethanol solution in a regular container, placing the container in a constant-temperature water bath (60 ℃) at the gel temperature for sol gelation reaction, enabling the newly prepared solution to be light yellow (the color depth is deepened along with the increase of the concentration of reactants), aging (60 ℃) for 7 days during the water bath reaction, gradually deepening the color, and finally taking out the gel. Drying for 1 day at normal temperature (25 ℃) and normal pressure, and then drying for 1 day (65 ℃) in an oven to obtain a phenolic resin-based organic aerogel precursor;
(2) Preparing a potassium permanganate solution: 2.86g of potassium permanganate powder was weighed, placed in a 500ml beaker, and deionized water was added to reach 300ml of scale marks to obtain a potassium permanganate solution.
(3) Preparing manganese-nitrogen doped carbon aerogel: adding the prepared aerogel precursor into the potassium permanganate solution, so that the mass ratio of manganese element to nitrogen element is 5:1 respectively; mechanical stirring is adopted, and continuous stirring is carried out for 24 hours, so that the gel precursor is completely soaked in the potassium permanganate solution. And (3) centrifuging, filtering, drying at normal pressure and 65 ℃ and then heating for 2 hours at 700 ℃ in a tube furnace under nitrogen atmosphere, cooling and taking out black solid to obtain manganese nitrogen doped carbon aerogel, and storing in a cool and dry place.
Manganese nitrogen doping prepared by the preparation methodCarbon aerogel materials. The specific surface area of the manganese nitrogen doped carbon aerogel material is 125m 2 Per g, average pore diameter 3.85nm, pore volume 0.008cm 3 /g。
Taking the manganese-nitrogen doped carbon aerogel material in the embodiment 3 as an adsorbent, preparing tetracycline solutions with different concentration gradients (the concentration is 10-200 mg/L), adding the manganese-nitrogen doped carbon aerogel material with the addition amount of 1.2g/L, adsorbing for 48 hours at 25 ℃ under the condition of 200r/min, and analyzing the adsorbed water sample by utilizing high performance liquid chromatography, wherein the saturated adsorption amount of the manganese-nitrogen doped carbon aerogel material synthesized in the embodiment 3 is as follows: 917.2mg/g.
Example 4:
compared with the embodiment 3, the main difference is that the proportion of the phenolic resin and the formula 1 is regulated, and the specific steps are as follows:
(1) Aerogel precursor preparation: 15g of phenolic resin and 6g of 1 are weighed and dissolved in 100ml of absolute methanol, and stirred and mixed until the dissolution is uniform. And sealing the phenolic resin type 1 mixed ethanol solution in a regular container, placing the container in a constant-temperature water bath (60 ℃) at the gel temperature for sol gelation reaction, enabling the newly prepared solution to be light yellow (the color depth is deepened along with the increase of the concentration of reactants), aging (60 ℃) for 7 days during the water bath reaction, gradually deepening the color, and finally taking out the gel. Drying for 1 day at normal temperature (25 ℃) and normal pressure, and then drying for 1 day (65 ℃) in an oven to obtain a phenolic resin-based organic aerogel precursor;
(2) Preparing a potassium permanganate solution: 2.86g of potassium permanganate powder was weighed, placed in a 500ml beaker, and deionized water was added to reach 300ml of scale marks to obtain a potassium permanganate solution.
(3) Preparing manganese-nitrogen doped carbon aerogel: and adding the prepared aerogel precursor into the potassium permanganate solution, so that the mass ratio of manganese element to nitrogen element is 5:1 respectively. Mechanical stirring is adopted, and continuous stirring is carried out for 24 hours, so that the gel precursor is completely soaked in the potassium permanganate solution. And (3) centrifuging, filtering, drying at normal pressure and 65 ℃ and then heating for 2 hours at 700 ℃ in a tube furnace under nitrogen atmosphere, cooling and taking out black solid to obtain manganese nitrogen doped carbon aerogel, and storing in a cool and dry place.
Is made from the aboveThe manganese-nitrogen doped carbon aerogel material prepared by the method. The specific surface area of the manganese nitrogen doped carbon aerogel material is 187m 2 Per g, average pore diameter 4.12nm, pore volume 0.012cm 3 /g。
Taking the manganese-nitrogen doped carbon aerogel material in the embodiment 4 as an adsorbent, preparing tetracycline solutions with different concentration gradients (the concentration is 10-200 mg/L), adding the manganese-nitrogen doped carbon aerogel material with the addition amount of 1.2g/L, adsorbing for 48 hours at 25 ℃ under the condition of 200r/min, and analyzing the adsorbed water sample by utilizing high performance liquid chromatography, wherein the saturated adsorption amount of the manganese-nitrogen doped carbon aerogel material synthesized in the embodiment 4 is as follows: 638.5mg/g.
Example 5:
the main difference compared to example 3 is that the calcination temperature is 500 ℃, the specific steps are:
(1) Aerogel precursor preparation: 15g of phenolic resin and 3g of 1 are weighed and dissolved in 100ml of absolute methanol, and stirred and mixed until the dissolution is uniform. And sealing the phenolic resin type 1 mixed ethanol solution in a regular container, placing the container in a constant-temperature water bath (60 ℃) at the gel temperature for sol gelation reaction, enabling the newly prepared solution to be light yellow (the color depth is deepened along with the increase of the concentration of reactants), aging (60 ℃) for 7 days during the water bath reaction, gradually deepening the color, and finally taking out the gel. Drying for 1 day at normal temperature (25 ℃) and normal pressure, and then drying for 1 day (65 ℃) in an oven to obtain a phenolic resin-based organic aerogel precursor;
(2) Preparing a potassium permanganate solution: 2.86g of potassium permanganate powder was weighed, placed in a 500ml beaker, and deionized water was added to reach 300ml of scale marks to obtain a potassium permanganate solution.
(3) Preparing manganese-nitrogen doped carbon aerogel: and adding the prepared aerogel precursor into the potassium permanganate solution, so that the mass ratio of manganese element to nitrogen element is 5:1 respectively. Mechanical stirring is adopted, and continuous stirring is carried out for 24 hours, so that the gel precursor is completely soaked in the potassium permanganate solution. And (3) centrifuging, filtering, drying at normal pressure and 65 ℃ and then heating for 2 hours at 500 ℃ in a tube furnace under nitrogen atmosphere, cooling and taking out black solid 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 is prepared. The specific surface area of the manganese nitrogen doped carbon aerogel material is 110m 2 Per gram, average pore diameter 3.21nm, pore volume 0.005cm 3 /g。
Taking the manganese-nitrogen doped carbon aerogel material in the embodiment 5 as an adsorbent, preparing tetracycline solutions with different concentration gradients (the concentration is 10-200 mg/L), adding the manganese-nitrogen doped carbon aerogel material with the addition amount of 1.2g/L, adsorbing for 48 hours at 25 ℃ under the condition of 200r/min, and analyzing the adsorbed water sample by utilizing high performance liquid chromatography, wherein the saturated adsorption amount of the manganese-nitrogen doped carbon aerogel material synthesized in the embodiment 5 is as follows: 562.7mg/g.
EXAMPLE 6 recycle
A method for cyclical adsorption stability of manganese nitrogen doped carbon aerogel material (prepared in example 3), specifically comprising the steps of:
(1) The adsorption method of the manganese-nitrogen doped carbon aerogel material comprises the following steps: the manganese-nitrogen doped carbon aerogel material in the example 3 is taken as an adsorbent, tetracycline solutions with different concentration gradients (the concentration is 10-200 mg/L) are prepared, the manganese-nitrogen doped carbon aerogel material is added in an adding amount of 1.2g/L, and the mixture is adsorbed for 48 hours at the temperature of 25 ℃ and the temperature of 200 r/min.
(2) The desorption method of the manganese-nitrogen doped carbon aerogel material comprises the following steps: a solvent elution method is used to desorb the adsorbed manganese nitrogen doped carbon aerogel. The desorbing agent is H 2 O, immersing the manganese nitrogen-doped carbon aerogel adsorbed with the tetracycline solution into a flask filled with distilled water. And then cleaning by ultrasonic vibration, wherein the step of cleaning the manganese-nitrogen doped carbon aerogel is repeated three times. The cleaned manganese nitrogen doped carbon aerogel is directly applied to the next adsorption cycle after being dried.
The adsorption and desorption experiments are repeated for 5 times, and the removal rate of the manganese-nitrogen doped carbon aerogel to the tetracycline solution reaches 75% in the fifth time.
Comparative example 1:
compared with the examples, the main difference is that Mn is not compounded on the surface, and the steps are as follows:
(1) Aerogel precursor preparation: 15g of phenolic resin and 3g of 1 are weighed and dissolved in 100ml of absolute methanol, and stirred and mixed until the dissolution is uniform. And sealing the phenolic resin type 1 mixed ethanol solution in a regular container, placing the container in a constant-temperature water bath (60 ℃) at the gel temperature for sol gelation reaction, enabling the newly prepared solution to be light yellow (the color depth is deepened along with the increase of the concentration of reactants), aging (60 ℃) for 7 days during the water bath reaction, gradually deepening the color, and finally taking out the gel. Drying for 1 day at normal temperature (25 ℃) and normal pressure, and then drying for 1 day (65 ℃) in an oven to obtain a phenolic resin-based organic aerogel precursor;
(3) Preparing nitrogen-doped carbon aerogel: and (3) centrifuging, filtering, drying at normal pressure and 65 ℃ the prepared aerogel precursor, heating for 2 hours at 700 ℃ in a tube furnace under nitrogen atmosphere, cooling, taking out black solid, and thus obtaining the nitrogen-doped carbon aerogel, and storing in a shade and dry place.
The nitrogen-doped carbon aerogel material prepared by the preparation method is prepared. The specific surface area of the nitrogen-doped carbon aerogel material is 429m 2 Per g, average pore diameter 2.19nm, pore volume 0.3cm 3 /g。
The nitrogen-doped carbon aerogel material in comparative example 1 is used as an adsorbent, tetracycline solutions with different concentration gradients (the concentration is 10-200 mg/L) are prepared, the nitrogen-doped carbon aerogel material is added in an adding amount of 1.2g/L, the mixture is adsorbed for 48 hours under the conditions of 25 ℃ and 200r/min, and a water sample after adsorption is analyzed by utilizing high performance liquid chromatography, wherein the saturated adsorption amount of the manganese-nitrogen-doped carbon aerogel material synthesized in comparative example 1 is as follows: 234.7mg/g.
Comparative example 2:
the only difference compared to example 3 is that the melamine of equal mass is used instead of formula 1. As a result of measurement of adsorption performance by the method of example 3, it was found that the saturated adsorption capacity was 356.9mg/g.
Comparative example 4:
the difference compared to example 3 is that the same volume of absolute ethanol is used instead of the absolute methanol, and other parameters and adsorption modes are the same as in example 3. The saturated adsorption capacity was 425.7mg/g. The performance is significantly worse than in example 3.

Claims (24)

1. The application of the manganese oxide@nitrogen doped block carbon aerogel material is characterized in that the manganese oxide@nitrogen doped block carbon aerogel material is used as an adsorption material of antibiotics;
the preparation method of the manganese oxide@nitrogen doped block carbon aerogel material comprises the following steps:
carrying out gelation reaction on phenolic resin and a compound of formula 1 in methanol to obtain a block precursor: then loading a manganese source in the block precursor and calcining to prepare the manganese oxide@nitrogen doped block carbon aerogel material;
formula 1.
2. The use according to claim 1, wherein the mass ratio of phenolic resin to compound of formula 1 is 2-8:1.
3. The use according to claim 2, wherein the mass ratio of phenolic resin to compound of formula 1 is 2.5-6:1.
4. Use according to claim 1, wherein the phenolic resin has a purity BR.
5. The use according to claim 1, wherein the temperature of the gelation reaction is 50-80 ℃.
6. The method according to claim 1, wherein the block precursor is obtained by aging and drying after the gelation reaction.
7. The use according to claim 6, wherein the ageing temperature is 40-60 ℃.
8. The use according to claim 6, wherein the ageing is carried out for a period of 7-9 d.
9. The use according to claim 6, wherein 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 ℃ for 12-24 hours; the temperature of the second stage drying process is 50-65 ℃ and the time is 1-2 days.
10. The use according to claim 1, wherein the manganese source is loaded in the bulk precursor by impregnation.
11. The use according to claim 10, wherein the bulk precursor is immersed in a manganese source solution, followed by solid-liquid separation and drying to obtain a manganese source-loaded bulk precursor.
12. The use according to claim 11, wherein the solvent in the manganese source solution is water or a water-organic solvent mixture; the organic solvent is at least one of alcohol with the carbon number of C1-C4 and acetone.
13. Use according to claim 12, wherein the manganese source is a water-soluble manganese compound.
14. The use according to claim 13, wherein the manganese source is a permanganate.
15. The use according to claim 1, wherein the mass ratio of manganese element in the manganese source to N element in formula 1 is 1-10:1.
16. The use according to claim 1, wherein the calcination process is carried out under protection of at least one of nitrogen or an inert gas.
17. The use according to claim 1, wherein the calcination temperature is 300-1200 ℃.
18. The use according to claim 1, wherein the calcination time is 1 to 24 hours.
19. The use according to claim 1, wherein the manganese oxide @ nitrogen-doped bulk carbon aerogel material comprises a three-dimensional network of nitrogen-doped bulk gel carbon and manganese oxide nanoparticles supported on the surface thereof.
20. The application of claim 19, wherein the manganese oxide @ nitrogen doped bulk carbon aerogel material has a specific surface area of 100-500 m 2 Per gram, pore volume of 0.007cm 3 /g~0.3cm 3 Per gram, the manganese content is 0.5% -11%;
the particle size of the manganese oxide nano particles is 50-300nm.
21. The use according to any one of claims 1 to 20, wherein the manganese oxide @ nitrogen doped bulk carbon aerogel material is used for the physical-chemical combination adsorption of tetracycline antibiotics in a body of water.
22. The use of claim 21, wherein the antibiotic is at least one of tetracycline, oxytetracycline, and aureomycin.
23. The use according to claim 21, wherein the adsorbent is used in an amount of 0.8 to 1.2g/L during the adsorption process.
24. Use according to claim 21, wherein the adsorbent is regenerated by recycling.
CN202111632108.9A 2021-12-28 2021-12-28 Manganese oxide@nitrogen doped block carbon aerogel material and preparation and application thereof Active CN114471443B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111632108.9A CN114471443B (en) 2021-12-28 2021-12-28 Manganese oxide@nitrogen doped block carbon aerogel material and preparation and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111632108.9A CN114471443B (en) 2021-12-28 2021-12-28 Manganese oxide@nitrogen doped block carbon aerogel material and preparation and application thereof

Publications (2)

Publication Number Publication Date
CN114471443A CN114471443A (en) 2022-05-13
CN114471443B true CN114471443B (en) 2023-09-29

Family

ID=81496399

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111632108.9A Active CN114471443B (en) 2021-12-28 2021-12-28 Manganese oxide@nitrogen doped block carbon aerogel material and preparation and application thereof

Country Status (1)

Country Link
CN (1) CN114471443B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106311142A (en) * 2016-09-09 2017-01-11 上海电力学院 Preparation method of carbon aerogel desulfurizer for high-temperature desulfuration
CN111876160A (en) * 2020-08-19 2020-11-03 武汉大学 Carbon aerogel material, preparation method thereof and application of carbon aerogel material as heavy metal contaminated soil remediation material
EP3780197A1 (en) * 2019-08-14 2021-02-17 Commissariat à l'Energie Atomique et aux Energies Alternatives Method for preparing a porous carbonaceous and nitrogenous material with metallic dopant, in particular useful as a catalyst for oxygen reduction reaction (orr)
CN112892483A (en) * 2021-01-29 2021-06-04 武汉大学 Nitrogen-doped carbon aerogel nano-microsphere as well as preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106311142A (en) * 2016-09-09 2017-01-11 上海电力学院 Preparation method of carbon aerogel desulfurizer for high-temperature desulfuration
EP3780197A1 (en) * 2019-08-14 2021-02-17 Commissariat à l'Energie Atomique et aux Energies Alternatives Method for preparing a porous carbonaceous and nitrogenous material with metallic dopant, in particular useful as a catalyst for oxygen reduction reaction (orr)
CN111876160A (en) * 2020-08-19 2020-11-03 武汉大学 Carbon aerogel material, preparation method thereof and application of carbon aerogel material as heavy metal contaminated soil remediation material
CN112892483A (en) * 2021-01-29 2021-06-04 武汉大学 Nitrogen-doped carbon aerogel nano-microsphere as well as preparation method and application thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
MnO2/N-3DG气凝胶催化剂的制备及臭氧催化反应器优化设计模拟;孟富臣;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》(第1期);正文第21页2.3.2节至第22页2.3.3节 *
Removal of tetracycline from an aqueous solution using manganese dioxide modified biochar derived from Chinese herbal medicine residues;Qibin Shen et al.;《Environmental Research》;第183卷;109195 *
Self-assembly of 3D MnO2/N-doped graphene hybrid aerogel for catalytic degradation of water pollutants : Structure-dependent activity;Qi Dong et al.;《Chemical Engineering Journal》》;第369卷;1049-1058 *
石墨烯气凝胶的制备方法及去除水中抗生素研究进展;巨龙等;《安徽农学通报》;第27卷(第12期);128-132 *

Also Published As

Publication number Publication date
CN114471443A (en) 2022-05-13

Similar Documents

Publication Publication Date Title
Pan et al. Cation exchanged MOF-derived nitrogen-doped porous carbons for CO 2 capture and supercapacitor electrode materials
Li et al. Mechanochemical synthesis of Cu-BTC@ GO with enhanced water stability and toluene adsorption capacity
KR101438854B1 (en) High surface area carbon and process for its production
Li et al. Effect of pyrolytic temperature on the adsorptive removal of p-benzoquinone, tetracycline, and polyvinyl alcohol by the biochars from sugarcane bagasse
KR101608850B1 (en) Hollow porous carbon particles and their synthetic method
CN104525119A (en) G-C3N4/ZnO/activated carbon functional charcoal adsorption material and preparation method thereof
CN105854801A (en) Nitrogen-doped porous carbon material and preparation method and application thereof
CN109833847B (en) Nickel oxide modified porous boron nitride adsorbent and preparation method thereof
JP3446771B2 (en) Method for producing high specific surface area carbon material
CN112044401A (en) Porous organic cage adsorbing material and preparation method thereof
KR102056435B1 (en) Activated carbon with improved butane adsorption capacity and method of producing the same
WO2016140266A1 (en) Carbon porous body, method for manufacturing same, ammonia adsorbent, and canister and method for manufacturing same
JP4893918B2 (en) Nitrogen-containing carbon-based electrode catalyst
CN110841595A (en) Preparation method and application of nitrogen-doped graphitized carbon material
WO2021223901A1 (en) Adsorbent material on the basis of a metal-organic framework, method for the production and use of the same
JP6042922B2 (en) Porous carbon, production method thereof, and ammonia adsorbent
CN114471443B (en) Manganese oxide@nitrogen doped block carbon aerogel material and preparation and application thereof
CN116850956A (en) Modified ZIF-8-based nitrogen-doped carbon CO 2 Method for preparing adsorbent
CN115403042A (en) Hierarchical porous carbon material for efficiently capturing iodine and preparation method and application thereof
Yang et al. Preparation and properties of BiOI with high sorption capacity
CN112915966A (en) Preparation method and application of polyaniline-based activated carbon
Fan et al. Oil-Tea Shell Derived N-Doped Porous Carbon for Selective Separation of CO2, CH4, and N2
CN101439282A (en) Method for preparing modified expanded graphite and use in benzene gas processing
JP5256120B2 (en) Method for producing CO adsorption / desorption agent
Zhu et al. Fabrication of carbonized derivatives from a novel azo polymer as a precursor for the layered adsorption of iodine and bromine

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant