CN114558603A - Nitrogen-doped hollow hierarchical pore carbon microsphere with high oxygen content and preparation method and application thereof - Google Patents

Nitrogen-doped hollow hierarchical pore carbon microsphere with high oxygen content and preparation method and application thereof Download PDF

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CN114558603A
CN114558603A CN202210229951.0A CN202210229951A CN114558603A CN 114558603 A CN114558603 A CN 114558603A CN 202210229951 A CN202210229951 A CN 202210229951A CN 114558603 A CN114558603 A CN 114558603A
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oxygen content
nitrogen
high oxygen
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microspheres
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CN114558603B (en
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吴铎
蒋管赟
吴张雄
高兴敏
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Suzhou University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B01J35/50—
    • B01J35/51—
    • B01J35/617—
    • B01J35/618—
    • B01J35/633—
    • B01J35/635—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention provides a preparation method of nitrogen-doped hollow hierarchical porous carbon microspheres with high oxygen content, which comprises the following steps: dissolving histidine and a salt template agent in a hydrochloric acid aqueous solution, and then stirring and mixing at room temperature to obtain a precursor solution; carrying out spray drying on the precursor solution to obtain hollow microspheres with unique forms, wherein the temperature of the top of the tower in the spray drying process is 150-200 ℃; calcining the hollow microspheres in an inert atmosphere at the temperature of 600-1000 ℃; and removing the salt template agent by washing to obtain the nitrogen-doped hollow hierarchical porous carbon microsphere with high oxygen content. The hollow carbon microspheres prepared by combining a salt template method and a spray drying technology have good catalytic performance on an ozone oxidation reaction.

Description

Nitrogen-doped hollow hierarchical pore carbon microsphere with high oxygen content and preparation method and application thereof
Technical Field
The invention belongs to the technical field of microsphere preparation and ozone oxidation catalysis, and particularly relates to a nitrogen-doped hollow hierarchical pore carbon microsphere with high oxygen content, and a preparation method and application thereof.
Background
The hierarchical porous carbon material has great potential in the aspects of energy storage and conversion, heterogeneous catalysis, adsorption, separation and life science application. In recent years, remarkable progress is made in the design and synthesis of such materials, and salt templates have been widely used in the synthesis of hierarchical porous carbon materials due to their advantages of low price, abundant varieties, easy removal, and the like.
At present, in the research on the preparation of the multi-level porous carbon material by using the salt template method, except that a few of the researches directly mix and grind a carbon precursor and selected salt and then calcine the mixture, most researches dissolve the carbon precursor and inorganic salt in ultrapure water, so that the subsequent drying is necessary. The solvent is generally evaporated by means of water bath drying or freeze drying, but both methods have their own disadvantages. For water bath drying, thermal stress is inevitably generated in the drying process, so that the finally obtained dried material has cracks of different degrees, and the structure of the material is damaged; for freeze drying, although thermal stress can be avoided and the sublimation of ice crystals in the drying process can also create a macroporous structure, the drying time is too long (1-3 days), and the electric power cost is too high.
In addition, the high-temperature carbonization process inevitably leads to reduction of a large number of oxygen-containing functional groups, so that sufficient active sites are lacked in the carbon material, which greatly limits the practical application of the porous carbon in the field of water treatment. For this reason, researchers have conducted intensive studies on the functional modification of porous carbon materials, and the most effective method is wet oxidation, in which the carbon material is immersed in a strongly oxidizing solution such as nitric acid, sulfuric acid, hydrogen peroxide, etc. and refluxed for a certain period of time. Although a large number of oxygen-containing functional groups can be introduced, the method can observe that the pore structure of the porous carbon is obviously damaged and toxic and harmful gases are emitted during the reflux treatment.
Disclosure of Invention
In view of the above, the present invention aims to provide a nitrogen-doped hollow multi-level porous carbon microsphere with high oxygen content, a preparation method and an application thereof, so as to overcome the defects of the prior art.
The invention provides a preparation method of nitrogen-doped hollow hierarchical porous carbon microspheres with high oxygen content, which comprises the following steps:
(1) uniformly mixing histidine, a salt template agent and a hydrochloric acid aqueous solution to obtain a precursor solution;
(2) carrying out spray drying on the precursor solution to obtain hollow microspheres;
(3) calcining the hollow microspheres to obtain a calcined product;
(4) and washing the calcined product with water to remove the template agent to obtain the nitrogen-doped hollow hierarchical porous carbon microsphere with high oxygen content.
Preferably, the tower top temperature in the spray drying process is 150-200 ℃.
Preferably, the pressure in the spray drying process is 0.1-0.5 kg/cm2(ii) a The vibration frequency is 5-15 kHz; the amplitude is 10-20 Vpp.
Preferably, the calcining temperature is 600-1000 ℃.
Preferably, the total mass concentration of histidine and the salt template in the precursor solution is 6-12 wt%.
Preferably, the salt templating agent is selected from potassium chloride and/or sodium chloride.
Preferably, the mass ratio of the histidine to the salt template is 1: (1-10).
Preferably, the diameter of the hollow microsphere is 85-95 μm.
The invention provides a nitrogen-doped hollow hierarchical pore carbon microsphere with high oxygen content, which is prepared by the method in the technical scheme and has the specific surface area of 695-1224 m2Per g, pore volume of 0.33-0.70 cm3Per g, oxygen content 11.15～25.88wt％。
In yet another aspect, the present invention provides an ozone oxidation catalyst comprising:
the nitrogen-doped hollow hierarchical porous carbon microsphere with high oxygen content is prepared by the method in the technical scheme.
By means of the technical scheme, the invention at least has the following advantages:
inorganic salts with high thermal stability (such as sodium chloride or potassium chloride, etc.) used in the present invention are a good coating agent, template agent and porogen; in the whole calcining process, the carbon source can be always limited in the gaps of the salt crystal grains stacked layer by layer, and the thermal decomposition of the original oxygen-containing functional group can be inhibited to a certain extent; when the calcination temperature is below the melting temperature of the inorganic salt, the inorganic salt can exist as a structural template; when the calcination temperature exceeds its melting temperature, the energetic ions from the molten salt can etch the carbon skeleton to create pores, thereby forming a hierarchical pore structure.
The invention utilizes the spray drying technology, the conversion from the atomized small liquid drops to the dried microspheres is only within 2s, and the limited domain assembly of histidine and a salt template agent can be realized in the micro liquid drops in the drying process, so that histidine crystal particles cover salt crystal particles and are limited among the salt crystal particles stacked layer by layer, which plays an important role in maintaining the hollow spherical morphology, improving the specific surface area and oxygen content and forming a multi-level pore structure.
Drawings
FIG. 1 is an SEM image of a spray dried sample prepared according to example 1 of the present invention;
FIG. 2 is an SEM image of a carbon material prepared in example 1 of the present invention;
FIG. 3 is an SEM image of a carbon material prepared in comparative example 1 of the present invention;
FIG. 4 shows N in carbon materials prepared in examples 1 to 3 of the present invention and comparative example 12Adsorption and desorption isotherms and pore size distribution maps;
FIG. 5 shows the results of analyzing the elemental contents of the carbon materials prepared in examples 1 to 3 of the present invention and comparative example 1 (the analytical data was obtained by quantitative analysis using a Thermo Fisher Scientific flash CHNS/O elemental analyzer);
FIG. 6 shows the results of the test of the carbon material prepared in examples 1-3 of the present invention and comparative example 1 for catalyzing the ozone oxidation of sodium oxalate;
FIG. 7 shows the physicochemical properties of the carbon materials prepared in examples 2 and 5 of the present invention and the results of the tests on the catalytic ozonation of sodium oxalate.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of nitrogen-doped hollow hierarchical porous carbon microspheres with high oxygen content, which comprises the following steps:
(1) uniformly mixing histidine, a salt template agent and a hydrochloric acid aqueous solution to obtain a precursor solution;
(2) carrying out spray drying on the precursor solution to obtain hollow microspheres;
(3) calcining the hollow microspheres to obtain a calcined product;
(4) and washing the calcined product with water to remove the template agent to obtain the nitrogen-doped hollow hierarchical porous carbon microsphere with high oxygen content.
In the present invention, the salt templating agent is preferably selected from potassium chloride and/or sodium chloride.
In the present invention, the mass concentration of the aqueous hydrochloric acid solution is preferably 0 to 0.3 wt% (excluding 0), and more preferably 0.1 to 0.2 wt%.
In the present invention, the mass ratio of histidine to the salt template is preferably 1: (1-10), more preferably 1: (2-8), more preferably 1: (4-8), most preferably 1: (5-6).
In the invention, the total mass concentration of histidine and the salt template in the precursor solution is preferably 6-12 wt%, more preferably 7-9 wt%, and most preferably 8 wt%.
In the present invention, the method of mixing preferably comprises: dissolving histidine and salt template agent in hydrochloric acid water solution, and mixing.
In the present invention, the mixing is preferably performed under stirring; the mixing temperature is preferably room temperature, more preferably 20-30 ℃, and most preferably 25 ℃.
In the present invention, the spray drying is preferably carried out by breaking up into uniform small droplets through a microfluidic aerosol nozzle.
In the invention, the tower top temperature in the spray drying process is preferably 150-200 ℃, more preferably 160-190 ℃, and most preferably 170-180 ℃; the pressure in the spray drying process is preferably 0.1-0.5 kg/cm2More preferably 0.2 to 0.4kg/cm2Most preferably 0.3kg/cm2(ii) a The working vibration frequency of the atomizer is preferably 5-15 kHz, more preferably 8-12 kHz, and most preferably 10 kHz; the amplitude is preferably 10-20 Vpp, more preferably 13-17 Vpp, and most preferably 15 Vpp; the flow rate of the hot air is preferably 250 to 350L/min, more preferably 280 to 320L/min, and most preferably 300L/min.
In the invention, the diameter of the hollow microsphere is preferably 85-95 μm, more preferably 88-92 μm, and most preferably 90 μm. In the invention, the particle size of the obtained hollow microspheres can be regulated and controlled by controlling the size and the air speed of a nozzle in the spray drying process.
In the present invention, as long as the spray drying conditions remain constant, the properties of the resulting dried microspheres remain unchanged; the spray drying device is very easy to operate, can feed continuously, has high drying speed and high yield, and is suitable for industrial large-scale production.
In the present invention, the calcination is preferably carried out by charging the spray-dried powder into a corundum ark and placing the corundum ark into a tube furnace.
In the present invention, the calcination is preferably carried out in an inert atmosphere, preferably argon and/or nitrogen; the calcination temperature is preferably 600-1000 ℃, more preferably 700-950 ℃, more preferably 800-950 ℃, and most preferably 900-950 ℃; the calcination time is preferably 2-4 h, and more preferably 3 h.
In the invention, the temperature is preferably raised from room temperature to the calcination temperature (600-1000 ℃) in the calcination process; the heating speed is preferably 2-5 ℃/min, and more preferably 3-4 ℃/min.
In the present invention, the washing is preferably carried out in a shaking table to remove the salt template by shaking; after the washing is finished, preferably drying the obtained washing liquid to recover the salt template agent, so as to realize the recycling of the salt template agent; the drying method is preferably drying.
In the present invention, the method of water washing preferably includes: and soaking the calcined product in water for constant-temperature oscillation.
In the present invention, the water is preferably ultrapure water; the soaking is preferably performed in a glass container containing ultrapure water; the isothermal oscillation is preferably carried out in an isothermal oscillator; the constant-temperature oscillation time is preferably 2-4 h, and more preferably 3 h.
In the present invention, it is preferable that the washing further comprises: and filtering, washing and drying the product after water washing to obtain the nitrogen-doped hollow hierarchical pore carbon microsphere with high oxygen content.
In the present invention, the method of filtration is preferably vacuum filtration; the washing method preferably adopts ultrapure water washing to completely remove salt components in the carbon material; the drying temperature is preferably 50-70 ℃, more preferably 55-65 ℃, and most preferably 60 ℃; the drying method is preferably vacuum drying; more preferably overnight vacuum drying.
The invention provides a nitrogen-doped hollow hierarchical pore carbon microsphere with high oxygen content, which is prepared by the method in the technical scheme; the specific surface area is preferably 695-1224 m2The pore volume is preferably 0.33-0.70 cm/g3The preferred oxygen content is 11.15-25.88 wt./g.
The present invention provides an ozone oxidation catalyst comprising:
the nitrogen-doped hollow hierarchical porous carbon microsphere with high oxygen content is prepared by the method in the technical scheme.
In the present invention, the ozone oxidation catalyst can be used to catalyze ozone oxidation reactions, such as the oxidation of sodium oxalate by ozone.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings. The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
Weighing 4g of histidine and 16g of potassium chloride, adding the histidine and the potassium chloride into 0.2 wt% of HCl aqueous solution, and stirring at room temperature for 3 hours, wherein the total mass concentration of the histidine and the potassium chloride in the precursor solution is 8 wt%;
pouring the precursor liquid into a polytetrafluoroethylene material tank, and compressing air to break the precursor liquid in the material tank into uniform small droplets through a microfluidic aerosol nozzle; spray drying the precursor solution under the conditions that the temperature at the top of the tower is 170 ℃ and the flow rate of hot air is 300L/min;
putting the collected dry powder into a corundum ark, putting the corundum ark into a tubular furnace for calcining, heating the corundum ark to the corresponding temperature of 950 ℃ at the heating rate of 2 ℃/min under the argon atmosphere, and keeping the temperature for 3 hours; and soaking the calcined sample in a glass container containing ultrapure water, placing the glass container into a constant-temperature oscillator for oscillation for 3 hours, carrying out vacuum filtration, washing the glass container with a certain amount of ultrapure water to completely remove salt components in the carbon material, and finally carrying out vacuum drying on the carbon material at 60 ℃ overnight to obtain the nitrogen-doped hollow hierarchical porous carbon microsphere with high oxygen content.
Fig. 1 is a SEM test result of a sample after spray drying in example 1 of the present invention, and it can be seen that the surfaces of the obtained dried microsphere particles appear rhombic wrinkles, which is caused by some crystal angular protrusions of potassium chloride, the particle size of the microspheres is mainly distributed between 85 to 95 μm, and the interior of the particles presents a hollow structure.
Fig. 2 is a SEM test result of the nitrogen-doped hollow multi-level pore carbon microsphere with high oxygen content obtained after the calcination, water washing and drying processes of example 1 of the present invention, and it can be seen that the particles calcined at 950 ℃ still maintain the original hollow spherical shape well, and diamond-shaped macropores are distributed on the surface and inside of the particles.
Example 2
Nitrogen-doped hollow multi-stage porous carbon microspheres having a high oxygen content were prepared according to the method of example 1, except that the mass of histidine was 4g and the mass of potassium chloride was 24g, from example 1.
Example 3
Nitrogen-doped hollow multi-porous carbon microspheres having a high oxygen content were prepared according to the method of example 1, except that the mass of histidine was 4g and the mass of potassium chloride was 32g, from example 1.
Comparative example 1
A carbon material was prepared according to the method of example 1, except that potassium chloride was not added to the carbon material of example 1.
Fig. 3 is a SEM test result of the carbon material obtained in comparative example 1 after the processes of calcination, water washing, and drying, and it can be seen that the spherical shape of the microsphere particles obtained by spray-drying pure histidine could not be maintained after calcination at 950 ℃, and a dense sheet structure was exhibited.
Performance detection
N treatment of carbon materials prepared in examples 1 to 3 of the present invention and comparative example 12And (3) detecting the adsorption and desorption isotherm and the pore size distribution, wherein the detection method comprises the following steps: obtained by testing at-196 ℃ using a Micromeritics ASAP2020 instrument.
The results are shown in FIG. 4 and the following table, in which S isBETRefers to the specific surface area, V, of the material calculated according to the BET modeltotalIs the pore volume of the material:
SBET(m2/g) Vtotal(cm3/g)
example 1 1080 0.57
Example 2 1224 0.70
Example 3 958 0.50
Comparative example 1 470 0.22
As can be seen from fig. 4 and the above table, the use of potassium chloride as a salt template has a great promoting effect on the increase of the specific surface area of the carbon material and the generation of the hierarchical pore structure.
When the carbon materials prepared in examples 1 to 3 and comparative example 1 were analyzed for element content, and fig. 5 is the results of the analysis of element content for the carbon materials prepared in examples 1 to 3 and comparative example 1, it can be seen that the introduction of potassium chloride suppresses the decomposition of oxygen-containing functional groups of the material, thereby increasing the oxygen content of the carbon material, as compared with the oxygen content of the carbon material obtained without adding potassium chloride.
Example 4 catalytic ozonation of sodium oxalate
The carbon materials prepared in examples 1-3 and comparative example 1 are used as catalysts for catalyzing ozone oxidation of sodium oxalate, and the ozone oxidation and the catalytic ozone oxidation are carried out in a two-neck flask in a semi-batch mode, and the specific method is as follows:
mixing 100mL of 50ppm grassAdding sodium salt solution and 20mg of catalyst into a reactor, and stirring by using a magnetic stirrer at the same time; ozone is prepared by dry high-purity oxygen (18mL/min) through an ozone generator, the concentration of gas-phase ozone is 50ppm, and the gas-phase ozone is continuously introduced into a sodium oxalate solution; taking water sample in a certain period, immediately passing through the membrane, and then adding quenching agent Na2S2O3And (4) stopping the oxidation-reduction reaction in the water sample (quenching the residual ozone in the water sample).
Determination of sodium oxalate content in Water samples by ion chromatography (ICS-600, Sammer Feishell science Co., Ltd.) with Na2CO3/NaHCO3The mobile phase velocity was 0.8 mL/min.
Comparative example 2
The catalytic ozonation of sodium oxalate was carried out according to the method of example 4, differing from example 4 in that no catalyst was added.
Fig. 6 is a graph of degradation of sodium oxalate catalyzed by ozone oxidation by different carbon materials prepared in examples and comparative examples, compared with the case of sodium oxalate oxidized by ozone alone (comparative example 2), the degradation of sodium oxalate is obviously accelerated after the catalyst is added, and the removal rate of sodium oxalate oxidized by ozone alone is increased from less than 10% to 74.7%, which shows that the nitrogen-doped hollow multi-stage porous carbon microsphere with high oxygen content prepared by the invention has good catalytic activity in catalyzing the degradation of sodium oxalate oxidized by ozone as the catalyst.
Example 5
Weighing 4g of histidine and 24g of potassium chloride, adding the histidine and the potassium chloride into 0.2 wt% HCl solution, and stirring at room temperature for 3 hours, wherein the total mass concentration of the histidine and the potassium chloride in the precursor solution is 8 wt%;
subsequently, the solvent was removed using a rotary evaporator under a vacuum of 50mbar, the rotary flask was rotated at 60rpm and immersed in a water bath at 60 ℃ and the resulting product was dried in an oven under vacuum at 60 ℃ overnight to remove residual solvent;
and (3) carrying out subsequent calcination, cleaning and drying on the dried product, wherein the specific method is consistent with that of the example 1.
Fig. 7 is a graph showing the specific surface area and pore volume, element content, XRD diffraction, and sodium oxalate degradation (experimental procedure and detection method as in example 4) of the nitrogen-doped carbon microspheres prepared in examples 2 and 5, and it can be seen that changing the drying manner does not affect the specific surface area and pore volume of the prepared carbon microspheres, but does not mean that the pore structures of the two are the same, because the ASAP2020 instrument is not sensitive to detecting macropores. The carbon microspheres prepared by the rotary evaporation drying technique have higher graphitization degree (as shown in XRD diffraction pattern) but lower oxygen content compared with the carbon microspheres prepared by the spray drying technique, and the carbon microspheres with lower oxygen content have poorer catalytic performance under the condition of almost the same specific surface area and pore volume, which not only shows that the high oxygen content can promote the catalytic degradation of the carbon material, but also shows the importance of the spray drying technique.
According to the invention, by using a spray drying technology, the conversion from atomized small liquid droplets to dried microspheres only needs 0-2 s, and the limited domain assembly of histidine and a salt template agent can be realized in the micro-droplets in the drying process, so that salt crystal particles are coated by histidine crystal particles and are limited between the stacked salt crystal particles layer by layer, which plays an important role in maintaining the hollow spherical morphology, improving the specific surface area and oxygen content and forming a multi-level pore structure.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
While the invention has been described and illustrated with reference to specific embodiments thereof, these descriptions and illustrations do not limit the invention. It will be clearly understood by those skilled in the art that various changes in form and details may be made therein without departing from the true spirit and scope of the invention as defined by the appended claims, to adapt a particular situation, material, composition of matter, substance, method or process to the objective, spirit and scope of this application. All such modifications are intended to be within the scope of the claims appended hereto. Although the methods disclosed herein have been described with reference to particular operations performed in a particular order, it should be understood that these operations may be combined, sub-divided, or reordered to form equivalent methods without departing from the teachings of the present disclosure. Accordingly, unless specifically indicated herein, the order and grouping of the operations is not a limitation of the present application.

Claims (10)

1. A preparation method of nitrogen-doped hollow hierarchical porous carbon microspheres with high oxygen content comprises the following steps:
(1) uniformly mixing histidine, a salt template agent and a hydrochloric acid aqueous solution to obtain a precursor solution;
(2) carrying out spray drying on the precursor solution to obtain hollow microspheres;
(3) calcining the hollow microspheres to obtain a calcined product;
(4) and washing the calcined product with water to remove the template agent to obtain the nitrogen-doped hollow hierarchical porous carbon microsphere with high oxygen content.
2. The method according to claim 1, wherein the temperature at the top of the spray drying tower is 150-200 ℃.
3. The method according to claim 1, wherein the pressure during the spray drying is 0.1 to 0.5kg/cm2(ii) a The vibration frequency is 5-15 kHz; the amplitude is 10-20 Vpp.
4. The method according to claim 1, wherein the temperature of the calcination is 600 to 1000 ℃.
5. The method according to claim 1, wherein the total mass concentration of histidine and the salt template in the precursor solution is 6-12 wt%.
6. The method of claim 1, wherein the salt templating agent is selected from potassium chloride and/or sodium chloride.
7. The method of claim 1, wherein the mass ratio of histidine to salt template is 1: (1-10).
8. The method of claim 1, wherein the hollow microspheres have a diameter of 85 to 95 μm.
9. The nitrogen-doped hollow hierarchical porous carbon microsphere with high oxygen content prepared by the method of claim 1, and the specific surface area of the carbon microsphere is 695-1224 m2Per g, pore volume of 0.33-0.70 cm3The oxygen content is 11.15-25.88 wt%.
10. An ozone oxidation catalyst comprising: the nitrogen-doped hollow hierarchical porous carbon microsphere with high oxygen content prepared by the method of claim 1.
CN202210229951.0A 2022-03-10 2022-03-10 Nitrogen-doped hollow hierarchical pore carbon microsphere with high oxygen content and preparation method and application thereof Active CN114558603B (en)

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CN202210229951.0A CN114558603B (en) 2022-03-10 2022-03-10 Nitrogen-doped hollow hierarchical pore carbon microsphere with high oxygen content and preparation method and application thereof
PCT/CN2022/087828 WO2023168800A1 (en) 2022-03-10 2022-04-20 Nitrogen-doped hollow hierarchically-porous carbon microsphere with high oxygen content, and preparation method therefor and use thereof

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