CN112201799A - Ultrathin disk-shaped mesoporous carbon material and preparation method and application thereof - Google Patents
Ultrathin disk-shaped mesoporous carbon material and preparation method and application thereof Download PDFInfo
- Publication number
- CN112201799A CN112201799A CN202010571448.4A CN202010571448A CN112201799A CN 112201799 A CN112201799 A CN 112201799A CN 202010571448 A CN202010571448 A CN 202010571448A CN 112201799 A CN112201799 A CN 112201799A
- Authority
- CN
- China
- Prior art keywords
- carbon material
- mesoporous carbon
- temperature
- waste tire
- pyrolysis oil
- 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.)
- Granted
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electrochemistry (AREA)
- Composite Materials (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Silicon Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides an ultrathin disk-shaped mesoporous carbon material and a preparation method and application thereof, wherein the ultrathin disk-shaped mesoporous carbon material is obtained by firstly calcining a mixture of spherical silicon dioxide and waste tire pyrolysis oil at high temperature under inert atmosphere, and then washing, filtering and drying a product obtained by high-temperature calcination at room temperature. The method takes the waste tire pyrolysis oil as a carbon source and the spherical silicon dioxide as a template agent, and adopts the template method to directionally construct and prepare the ultrathin disk-shaped mesoporous carbon material; when the carbon material is used as an electrocatalyst of a fuel cell, the carbon material shows good electrocatalysis characteristics, solves the problems of high cost, insufficient durability and the like of an oxygen reduction catalyst of the fuel cell, and has wide application prospects in the field of electrochemical energy storage. The preparation method of the ultrathin disk-shaped mesoporous carbon material provided by the invention is simple to operate, strong in repeatability, controllable in synthesis process, low in cost of used raw materials, easy to obtain and capable of effectively utilizing waste tire pyrolysis oil.
Description
Technical Field
The invention relates to an ultrathin disk-shaped mesoporous carbon material and a preparation method and application thereof, belonging to the technical field of electrocatalysis of fuel cells.
Background
The energy problem is one of three major problems in the development of the current society, and has become more serious. The traditional energy utilization mode is limited by the Carnot cycle of the heat engine efficiency, the energy utilization efficiency is lower, and the fuel cell is taken as a novel clean, efficient and high-energy-density energy source. Over the years of effort by countless researchers, research in fuel cells has made breakthrough progress. Since the cathode oxygen reduction reaction rate of many fuel cells is slow, the cathode oxygen reduction reaction catalyst becomes a key factor affecting the electrocatalytic reaction rate thereof.
At present, the fuel cell usually adopts a Pt-based catalyst as a catalyst for cathode oxygen reduction reaction, but the adoption of the Pt-based catalyst has high cost, low durability and resource shortage, which seriously restricts the large-scale development and application of the fuel cell. Therefore, the development of a non-noble metal catalyst with low price and durability is urgently needed.
The carbon material is widely applied to fuel cell catalyst carriers due to simple preparation, easy mass production and good chemical property and mechanical stability. Many researchers have studied to prepare porous carbon materials from asphalt, which have the advantages of large specific surface area, strong chemical stability and thermal stability, etc., and few people use waste tire pyrolysis oil as a carbon source. The waste tyre cracking oil mainly comes from colloid self-cracking products in rubber, organic additives in rubber and cracking products thereof, and operation oil (naphthalene oil or anthracene oil) in rubber production formula, and is a complex mixture with wide boiling point (Journal of Analytical and Applied Pyrolysis,2004,71: 914-. The cracked oils were studied in detail by the research team of professor Roy, university of Laval, canada (Journal of Analytical and Applied Pyrolysis,1999,51:201-221.) and by the research team of university of thunberg, china, academy of china, and the physicochemical properties, elemental composition, and fraction composition, as well as the chemical composition of some of the hydrocarbons and non-hydrocarbon compounds in the cracked oils, etc. They believe that Pyrolysis oils are heavy oils of high density, high heating value, low flash point, low viscosity, which are highly aromatic and have a high amount of olefins present (Journal of Analytical and Applied Pyrolysis,2001,57: 91-107.). At present, the waste tire pyrolysis oil is mainly used as boiler fuel, and the economic value is not high, so that the production of the carbon material with high added value by using the waste tire pyrolysis oil is a new way for efficiently converting the waste tire pyrolysis oil and improving the resource utilization rate of the waste tire pyrolysis oil.
Disclosure of Invention
In order to solve the above disadvantages and shortcomings, it is an object of the present invention to provide an ultra-thin disk-shaped mesoporous carbon material.
The invention also aims to provide a preparation method of the ultrathin round sheet-shaped mesoporous carbon material.
Still another object of the present invention is to provide the use of the ultrathin, disk-shaped, mesoporous carbon material as described above as an electrocatalyst for a fuel cell.
In order to achieve the above objects, in one aspect, the present invention provides an ultra-thin disk-shaped mesoporous carbon material, wherein the ultra-thin disk-shaped mesoporous carbon material is obtained by firstly calcining a mixture of spherical silica and waste tire pyrolysis oil at a high temperature under an inert atmosphere, then washing a product obtained by the high-temperature calcination at a room temperature to remove a spherical silica template, filtering, and drying.
Preferably, the size of the ultrathin round sheet-shaped mesoporous carbon material is 150nm, the thickness is 5-10nm, and the specific surface area is 300-500m2The pore diameter is 2-50 nm.
In the ultrathin disk-shaped mesoporous carbon material, the mass ratio of the spherical silica to the waste tire pyrolysis oil is preferably 2:1-4: 1;
more preferably, the spherical silica has a particle size of 50 to 200 nm.
In the above ultra-thin disk-shaped mesoporous carbon material, preferably, the waste tire pyrolysis oil is a heavy fraction of the waste tire pyrolysis oil;
more preferably, the heavy fraction of the waste tire pyrolysis oil is distillate oil with the temperature of more than 350 ℃.
In the ultrathin disk-shaped mesoporous carbon material, the inert atmosphere preferably includes one or a combination of nitrogen, helium and argon.
In the ultrathin disk-shaped mesoporous carbon material, the high-temperature calcination is preferably carried out at the temperature of 700-900 ℃ for 1-3 h;
more preferably, the temperature increase rate of the high-temperature calcination is 5 to 10 ℃/min.
In the ultrathin disk-shaped mesoporous carbon material, preferably, the washing is performed by using hydrofluoric acid to remove the spherical silica template;
more preferably, the mass concentration of the hydrofluoric acid is 30-50%;
still more preferably, the washing time is 20-24 h.
In the ultrathin disk-like mesoporous carbon material, the drying temperature is preferably 90 to 100 ℃.
In the above ultra-thin disk-shaped mesoporous carbon material, preferably, the spherical silica is prepared by a preparation method including the following steps:
1) stirring and mixing absolute ethyl alcohol, deionized water and ammonia water uniformly;
2) adding Tetraethoxysilane (TEOS) into the mixed solution obtained in the step 1), and reacting for a period of time at a constant temperature;
more preferably, the reaction is carried out for 2-4h at the constant temperature and at the temperature of 55-70 ℃;
3) repeatedly centrifuging, washing and drying the product obtained in the step 2) to obtain spherical silicon dioxide;
still more preferably, the centrifugal washing is washing with anhydrous ethanol 3 to 4 times;
still more preferably, the temperature of the drying is 90-100 ℃.
In another aspect, the present invention further provides a preparation method of the ultrathin disk-shaped mesoporous carbon material, wherein the preparation method comprises the following steps:
calcining the mixture of the spherical silica and the pyrolysis oil of the waste tire at high temperature in an inert atmosphere;
and washing, filtering and drying the product obtained by high-temperature calcination at room temperature.
In another aspect, the invention also provides an application of the ultrathin disk-shaped mesoporous carbon material as an electrocatalyst of a fuel cell.
The invention takes waste tire pyrolysis oil as a carbon source and spherical silicon dioxide as a template agent, adopts the template method to directionally construct and prepare the ultrathin disk-shaped mesoporous carbon material, and comprises the following specific processes: the method comprises the following steps of mixing waste tire pyrolysis oil with spherical silicon dioxide, and after the obtained mixture is subjected to high-temperature pyrolysis carbonization, coating a thin carbon layer on the surface of the spherical silicon dioxide (in the carbonization process, the spherical silicon dioxide can also catalyze the waste tire pyrolysis oil to be quickly cracked to form a carbon layer on the surface, so that the spherical silicon dioxide used in the method has double functions of interface catalysis and carbon layer bearing), removing a spherical silicon dioxide template through hydrofluoric acid, forming a cavity inside the spherical silicon dioxide template, contracting the thin carbon layer on the outer surface of the spherical silicon dioxide template, and gradually contracting the thin carbon layer from a sphere into a disc shape in the contraction process to finally form the ultrathin disc-shaped mesoporous carbon material; when the ultrathin disk-shaped mesoporous carbon material is used as an electrocatalyst of a fuel cell, the ultrathin disk-shaped mesoporous carbon material shows high-efficiency oxygen reduction electrochemical performance (shows good electrocatalysis characteristic), solves the problems of high cost, insufficient durability and the like of the oxygen reduction catalyst of the fuel cell, and has wide application prospect in the field of electrochemical energy storage.
The preparation method of the ultrathin disk-shaped mesoporous carbon material provided by the invention is simple to operate, strong in repeatability, controllable in synthesis process, low in cost of used raw materials, easy to obtain and capable of effectively utilizing waste tire pyrolysis oil.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a scanning electron microscope image of the ultrathin disk-shaped mesoporous carbon material prepared in example 1 of the present invention.
Fig. 2 is an adsorption/desorption graph of the ultrathin disk-shaped mesoporous carbon material prepared in example 1 of the present invention.
Fig. 3 is a pore size distribution diagram of the ultrathin disk-shaped mesoporous carbon material prepared in example 1 of the present invention.
FIG. 4 shows that the ultra-thin disk-shaped mesoporous carbon material prepared in example 1 of the present invention is saturated with O when used as an oxygen reduction catalyst of a fuel cell2In the electrolyte solution (0.1M KOH), the linear scanning curves at different rotation speeds.
FIG. 5 is a scanning electron microscope image of the ultrathin disk-shaped mesoporous carbon material prepared in example 2 of the present invention.
FIG. 6 is a scanning electron microscope image of the ultrathin disk-shaped mesoporous carbon material prepared in example 3 of the present invention.
FIG. 7 is a scanning electron micrograph of the mesoporous carbon material prepared in comparative example 1 according to the present invention.
Detailed Description
In order to clearly understand the technical features, objects and advantages of the present invention, the following detailed description of the technical solutions of the present invention will be made with reference to the following specific examples, which should not be construed as limiting the implementable scope of the present invention.
Example 1
The embodiment provides a preparation method of an ultrathin disk-shaped mesoporous carbon material, wherein the preparation method comprises the following steps:
(1) adding 60mL of absolute ethyl alcohol, 30mL of deionized water and 10mL of ammonia water into a 100mL beaker, stirring for 10min, adding 10mL of TEOS, keeping the temperature to 60 ℃, and continuing to react for 3 h.
And repeatedly centrifuging and washing the product for 3 times by using absolute ethyl alcohol, and drying at 100 ℃ to obtain the spherical silicon dioxide.
Fully mixing spherical silicon dioxide and waste tire pyrolysis oil according to the mass ratio of 3: 1; in this embodiment, the waste tire pyrolysis oil is a heavy fraction of the waste tire pyrolysis oil, and the heavy fraction of the waste tire pyrolysis oil is a distillate oil with a temperature greater than 350 ℃.
(2) Placing the mixture into a corundum porcelain boat, placing the corundum porcelain boat into a horizontal furnace, introducing argon, raising the temperature in the horizontal furnace to 800 ℃ at the speed of 10 ℃/min, maintaining for 1h, taking out a reaction product after the temperature in the horizontal furnace is naturally cooled to room temperature, stirring and washing the reaction product for 20h at normal temperature by using an HF solution (hydrofluoric acid, wherein the mass concentration of the used hydrofluoric acid is 30-50%), placing the reaction product into a 100 ℃ drying oven, and drying to obtain the ultrathin disk-shaped mesoporous carbon material.
FIG. 1 is a scanning electron microscope image of the ultrathin disk-shaped mesoporous carbon material prepared in this example, and it can be seen from FIG. 1 that the carbon material prepared in this example is ultrathin disk-shaped, and has a hollow structure, a size of 100-150nm, and a thickness of 5-10 nm.
Fig. 2 is an adsorption/desorption curve diagram of the ultrathin disk-shaped mesoporous carbon material prepared in the embodiment, and it can be seen from fig. 2 that an obvious hysteresis exists in the curve, and the hysteresis reflects the existence of a mesoporous structure in the material.
FIG. 3 is a pore size distribution diagram of the ultrathin disk-shaped mesoporous carbon material prepared in this example, and it can be seen from FIG. 3 that the carbon material has a wide pore size distribution, a pore size of 2-50nm, and a specific surface area of 372.6m2/g。
FIG. 4 is a linear scanning curve diagram of the carbon material prepared in this example for oxygen reduction at different rotation speeds in an oxygen saturation state. The catalytic activity of the catalyst in the oxygen reduction reaction is tested by adopting a Rotating Disk Electrode (RDE) technology, a reference electrode is a saturated calomel electrode, and the electrolyte is 0.1M KOH solution. The rotation speeds from top to bottom in FIG. 4 are 400rmp, 625rmp, 900rmp, 1225rmp, 1600rmp, respectively, and the scanning speed is 10 mv/s.
As can be seen from FIG. 4, there was no significant change in the oxygen reduction current density with increasing rotational speed over the voltage range of-0.27 to 0V, indicating that the oxygen reduction current is primarily kinetically controlled over this voltage range; and in the voltage range of-1.0 to-0.27V, the oxygen reduction current density is continuously increased along with the increase of the rotating speed, which shows that in the voltage range, the oxygen reduction current is mainly controlled by diffusion.
It can also be seen from FIG. 4 that the limiting current density gradually increases with increasing rotational speed, and at a rotational speed of 1600rmp, the initial potential and the half-wave potential are 0.865V and 0.555V (vs RHE), respectively, and the limiting current density is 3.58mA cm-2Compared with commercial platinum catalysts and other oxygen reduction catalysts, the ultrathin disk-shaped mesoporous carbon material provided by the embodiment of the invention has better oxygen reduction catalytic activity when used as an electrocatalyst of a fuel cell.
Example 2
The embodiment provides a preparation method of an ultrathin disk-shaped mesoporous carbon material, wherein the preparation method comprises the following steps:
(1) adding 60mL of absolute ethyl alcohol, 30mL of deionized water and 10mL of ammonia water into a 100mL beaker, stirring for 10min, adding 10mL of TEOS, keeping the temperature to 60 ℃, and continuing to react for 3 h.
And repeatedly centrifuging and washing the product for 3 times by using absolute ethyl alcohol, and drying at 100 ℃ to obtain the spherical silicon dioxide.
Fully mixing spherical silicon dioxide and waste tire pyrolysis oil according to the mass ratio of 2: 1; in this embodiment, the waste tire pyrolysis oil is a heavy fraction of the waste tire pyrolysis oil, and the heavy fraction of the waste tire pyrolysis oil is a distillate oil with a temperature greater than 350 ℃.
(2) Placing the mixture into a corundum porcelain boat, placing the corundum porcelain boat into a horizontal furnace, introducing argon, raising the temperature in the horizontal furnace to 850 ℃ at the speed of 10 ℃/min, maintaining for 1h, taking out a reaction product after the temperature in the horizontal furnace is naturally cooled to room temperature, stirring and washing the reaction product for 22h at normal temperature by using an HF solution (hydrofluoric acid, wherein the mass concentration of the used hydrofluoric acid is 30-50%), placing the reaction product into a 100 ℃ oven for drying, and obtaining the ultrathin disk-shaped mesoporous carbon material after drying.
FIG. 5 is a scanning electron microscope image of the ultrathin disk-shaped mesoporous carbon material prepared in example 2 of the present invention, and it can be seen from FIG. 5 that the carbon material prepared in this example is ultrathin disk-shaped, and has a hollow structure, a size of 100 and 150nm, and a thickness of 5-10 nm.
Example 3
The embodiment provides a preparation method of an ultrathin disk-shaped mesoporous carbon material, wherein the preparation method comprises the following steps:
(1) adding 60mL of absolute ethyl alcohol, 30mL of deionized water and 10mL of ammonia water into a 100mL beaker, stirring for 10min, adding 10mL of TEOS, keeping the temperature to 60 ℃, and continuing to react for 3 h.
And repeatedly centrifuging and washing the product for 3 times by using absolute ethyl alcohol, and drying at 100 ℃ to obtain the spherical silicon dioxide.
Fully mixing spherical silicon dioxide and waste tire pyrolysis oil according to a mass ratio of 4: 1; in this embodiment, the waste tire pyrolysis oil is a heavy fraction of the waste tire pyrolysis oil, and the heavy fraction of the waste tire pyrolysis oil is a distillate oil with a temperature greater than 350 ℃.
(2) Placing the mixture into a corundum porcelain boat, placing the corundum porcelain boat into a horizontal furnace, introducing argon, raising the temperature in the horizontal furnace to 900 ℃ at the speed of 10 ℃/min, maintaining for 1h, naturally cooling the temperature in the horizontal furnace to room temperature, taking out a reaction product, stirring and washing the reaction product for 24h at normal temperature by using an HF solution (hydrofluoric acid, wherein the mass concentration of the used hydrofluoric acid is 30-50%), placing the reaction product into a 100 ℃ oven for drying, and obtaining the ultrathin disk-shaped mesoporous carbon material after drying.
FIG. 6 is a scanning electron microscope image of the ultrathin disk-shaped mesoporous carbon material prepared in this example, and it can be seen from FIG. 6 that the carbon material prepared in this example is ultrathin disk-shaped, and has a hollow structure, a size of 100-150nm, and a thickness of 5-10 nm.
Example 4
The embodiment provides a preparation method of an ultrathin disk-shaped mesoporous carbon material, wherein the preparation method comprises the following steps:
(1) adding 60mL of absolute ethyl alcohol, 30mL of deionized water and 10mL of ammonia water into a 100mL beaker, stirring for 10min, adding 10mL of TEOS, keeping the temperature to 60 ℃, and continuing to react for 3 h.
And repeatedly centrifuging and washing the product for 3 times by using absolute ethyl alcohol, and drying at 100 ℃ to obtain the spherical silicon dioxide.
Fully mixing spherical silicon dioxide and waste tire pyrolysis oil according to a mass ratio of 4: 1; in this embodiment, the waste tire pyrolysis oil is a heavy fraction of the waste tire pyrolysis oil, and the heavy fraction of the waste tire pyrolysis oil is a distillate oil with a temperature greater than 350 ℃.
(2) Placing the mixture in a corundum porcelain boat, placing the corundum porcelain boat in a horizontal furnace, introducing argon, raising the temperature in the horizontal furnace to 900 ℃ at the speed of 10 ℃/min, maintaining for 2 hours, naturally cooling the temperature in the horizontal furnace to room temperature, taking out a reaction product, stirring and washing the reaction product for 24 hours at normal temperature by using an HF solution (hydrofluoric acid, wherein the mass concentration of the used hydrofluoric acid is 30-50%), placing the reaction product in a 100 ℃ oven for drying, and obtaining the ultrathin disk-shaped mesoporous carbon material after drying.
Example 5
The embodiment provides a preparation method of an ultrathin disk-shaped mesoporous carbon material, wherein the preparation method comprises the following steps:
(1) adding 60mL of absolute ethyl alcohol, 30mL of deionized water and 10mL of ammonia water into a 100mL beaker, stirring for 10min, adding 10mL of TEOS, keeping the temperature to 60 ℃, and continuing to react for 3 h.
And repeatedly centrifuging and washing the product for 3 times by using absolute ethyl alcohol, and drying at 100 ℃ to obtain the spherical silicon dioxide.
Fully mixing spherical silicon dioxide and waste tire pyrolysis oil according to a mass ratio of 4: 1; in this embodiment, the waste tire pyrolysis oil is a heavy fraction of the waste tire pyrolysis oil, and the heavy fraction of the waste tire pyrolysis oil is a distillate oil with a temperature greater than 350 ℃.
(2) Placing the mixture in a corundum porcelain boat, then placing the corundum porcelain boat in a horizontal furnace, introducing argon, raising the temperature in the horizontal furnace to 800 ℃ at the speed of 10 ℃/min, maintaining for 2 hours, naturally cooling the temperature in the horizontal furnace to room temperature, taking out a reaction product, stirring and washing the reaction product for 24 hours at normal temperature by using an HF solution (hydrofluoric acid, wherein the mass concentration of the used hydrofluoric acid is 30-50%), then placing the reaction product in a 100 ℃ oven for drying, and obtaining the ultrathin disk-shaped mesoporous carbon material after drying.
Comparative example 1
(1) Adding 60mL of absolute ethyl alcohol, 30mL of deionized water and 10mL of ammonia water into a 100mL beaker, stirring for 10min, adding 10mL of TEOS, keeping the temperature to 60 ℃, and continuing to react for 3 h.
And repeatedly centrifuging and washing the product for 3 times by using absolute ethyl alcohol, and drying at 100 ℃ to obtain the spherical silicon dioxide.
Fully mixing spherical silicon dioxide and waste tire pyrolysis oil according to the mass ratio of 1: 2; in the comparative example, the waste tire pyrolysis oil is heavy fraction of the waste tire pyrolysis oil, and the heavy fraction of the waste tire pyrolysis oil is distillate oil with the temperature of more than 350 ℃.
(2) Placing the mixture in a corundum porcelain boat, placing the corundum porcelain boat in a horizontal furnace, introducing argon, raising the temperature in the horizontal furnace to 850 ℃ at the speed of 10 ℃/min, maintaining for 1h, naturally cooling the temperature in the horizontal furnace to room temperature, taking out a reaction product, stirring and washing with an HF solution (hydrofluoric acid, wherein the mass concentration of the hydrofluoric acid is 30-50%) at normal temperature for 22h, placing the reaction product in a 100 ℃ oven for drying, and obtaining the mesoporous carbon material after drying.
FIG. 7 is a scanning electron microscope image of a mesoporous carbon material prepared in comparative example 1 of the present invention, and it can be seen from FIG. 7 that the mesoporous carbon material prepared in comparative example 1 does not exhibit an ultra-thin disk shape since the spherical silica and the waste tire pyrolysis oil used in the preparation process are in a mass ratio of 1:2, which is not within the range of the spherical silica and the waste tire pyrolysis oil required in the present invention.
The above description is only exemplary of the invention and should not be taken as limiting the scope of the invention, so that the invention is intended to cover all modifications and equivalents of the embodiments described herein. In addition, the technical features and the technical inventions of the present invention, the technical features and the technical inventions, and the technical inventions can be freely combined and used.
Claims (10)
1. The ultrathin disk-shaped mesoporous carbon material is characterized in that a mixture of spherical silica and waste tire pyrolysis oil is calcined at high temperature in an inert atmosphere, and a product obtained by high-temperature calcination is washed at room temperature to remove a spherical silica template, filtered and dried to obtain the ultrathin disk-shaped mesoporous carbon material.
2. The ultra-thin disk-shaped mesoporous carbon material as claimed in claim 1, wherein the mass ratio of the spherical silica to the waste tire pyrolysis oil is 2:1 to 4: 1;
preferably, the size of the ultrathin round sheet-shaped mesoporous carbon material is 150nm, the thickness is 5-10nm, and the specific surface area is 300-500m2Per g, the aperture is 2-50 nm;
also preferably, the spherical silica has a particle size of 50 to 200 nm.
3. The ultra-thin disc-like mesoporous carbon material according to claim 1 or 2, wherein the waste tire pyrolysis oil is a heavy fraction of the waste tire pyrolysis oil;
preferably, the heavy fraction of the waste tire pyrolysis oil is distillate oil with the temperature of more than 350 ℃.
4. The ultra-thin disk-like mesoporous carbon material as claimed in claim 1, wherein the inert atmosphere comprises one or a combination of nitrogen, helium and argon.
5. The ultra-thin disk-shaped mesoporous carbon material as claimed in claim 1, wherein the high temperature calcination is carried out at a temperature of 700-900 ℃ for 1-3 h;
preferably, the temperature rise rate of the high-temperature calcination is 5-10 ℃/min.
6. The ultra-thin disk-like mesoporous carbon material according to claim 1, wherein the washing is performed with hydrofluoric acid;
preferably, the mass concentration of the hydrofluoric acid is 30-50%;
also preferably, the washing time is 20-24 h.
7. The ultra-thin disk-like mesoporous carbon material as claimed in claim 1, wherein the drying temperature is 90 to 100 ℃.
8. The ultra-thin disk-like mesoporous carbon material as claimed in claim 1, wherein the spherical silica is prepared by a preparation method comprising:
1) stirring and mixing absolute ethyl alcohol, deionized water and ammonia water uniformly;
2) adding tetraethoxysilane into the mixed solution obtained in the step 1), and reacting for a period of time at a constant temperature;
preferably, the reaction is carried out for 2-4h at the constant temperature and at the temperature of 55-70 ℃;
3) repeatedly centrifuging, washing and drying the product obtained in the step 2) to obtain spherical silicon dioxide;
also preferably, the centrifugal washing is washing 3-4 times by using absolute ethyl alcohol;
also preferably, the temperature of the drying is 90-100 ℃.
9. The method for producing an ultrathin, discoid, mesoporous carbon material according to any one of claims 1 to 8, comprising the steps of:
calcining the mixture of the spherical silica and the pyrolysis oil of the waste tire at high temperature in an inert atmosphere;
and washing, filtering and drying the product obtained by high-temperature calcination at room temperature.
10. Use of the ultrathin, discoid, mesoporous carbon material according to any one of claims 1 to 8 as an electrocatalyst for a fuel cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010571448.4A CN112201799B (en) | 2020-06-22 | 2020-06-22 | Ultrathin disk-shaped mesoporous carbon material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010571448.4A CN112201799B (en) | 2020-06-22 | 2020-06-22 | Ultrathin disk-shaped mesoporous carbon material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112201799A true CN112201799A (en) | 2021-01-08 |
| CN112201799B CN112201799B (en) | 2021-09-10 |
Family
ID=74006095
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010571448.4A Active CN112201799B (en) | 2020-06-22 | 2020-06-22 | Ultrathin disk-shaped mesoporous carbon material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112201799B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103168002A (en) * | 2010-10-25 | 2013-06-19 | 赫罗伊斯石英玻璃股份有限两合公司 | Porous carbon product, method for the production thereof, and use of the same |
| CN103288070A (en) * | 2013-04-02 | 2013-09-11 | 大连理工大学 | Method for preparing nitrogen-doped porous carbon from heavy organic component in coal liquefaction residue |
| CN105110317A (en) * | 2015-08-27 | 2015-12-02 | 中南大学 | Preparation method and application of ultrathin-sheet porous carbon |
| US20170008769A1 (en) * | 2014-01-24 | 2017-01-12 | Heraeus Quarzglas Gmbh & Co. Kg | Porous carbon particles having a core/shell structure, and method for producing same |
| CN106430144A (en) * | 2016-08-29 | 2017-02-22 | 宝泰隆新材料股份有限公司 | Method for preparing asphalt-based hierarchical porous carbon sheet based on sheet-shaped magnesium oxide template and application thereof |
| US20170342014A1 (en) * | 2016-05-24 | 2017-11-30 | Ut-Battelle, Llc | Surface treated carbon catalysts produced from waste tires for fatty acids to biofuel conversion |
| CN107674694A (en) * | 2017-09-20 | 2018-02-09 | 山东朋百环保装备有限公司 | The method and device that a kind of junked tire cracking recycles |
-
2020
- 2020-06-22 CN CN202010571448.4A patent/CN112201799B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103168002A (en) * | 2010-10-25 | 2013-06-19 | 赫罗伊斯石英玻璃股份有限两合公司 | Porous carbon product, method for the production thereof, and use of the same |
| CN103288070A (en) * | 2013-04-02 | 2013-09-11 | 大连理工大学 | Method for preparing nitrogen-doped porous carbon from heavy organic component in coal liquefaction residue |
| US20170008769A1 (en) * | 2014-01-24 | 2017-01-12 | Heraeus Quarzglas Gmbh & Co. Kg | Porous carbon particles having a core/shell structure, and method for producing same |
| CN105110317A (en) * | 2015-08-27 | 2015-12-02 | 中南大学 | Preparation method and application of ultrathin-sheet porous carbon |
| US20170342014A1 (en) * | 2016-05-24 | 2017-11-30 | Ut-Battelle, Llc | Surface treated carbon catalysts produced from waste tires for fatty acids to biofuel conversion |
| CN106430144A (en) * | 2016-08-29 | 2017-02-22 | 宝泰隆新材料股份有限公司 | Method for preparing asphalt-based hierarchical porous carbon sheet based on sheet-shaped magnesium oxide template and application thereof |
| CN107674694A (en) * | 2017-09-20 | 2018-02-09 | 山东朋百环保装备有限公司 | The method and device that a kind of junked tire cracking recycles |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112201799B (en) | 2021-09-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110752380A (en) | ZIF-8 derived hollow Fe/Cu-N-C type oxygen reduction catalyst and preparation method and application thereof | |
| CN110350211B (en) | Preparation method of ZIF-8 derived N, S-codoped non-metallic carbon-based nano oxygen reduction electrocatalyst | |
| CN109012722B (en) | Cerium dioxide/titanium nitride nanotube taking Ce-MOF as precursor and preparation method and application thereof | |
| CN107658474A (en) | A kind of nitrogen sulphur codope porous carbon microsphere and preparation method, purposes and oxygen reduction electrode | |
| CN109174157B (en) | Preparation method of cobalt-nitrogen co-doped biomass carbon oxidation reduction catalyst | |
| CN104258892B (en) | N-doped meso-macro hierarchical porous carbon oxygen reduction catalyst material and preparation method thereof | |
| CN108786805B (en) | Composite catalyst and preparation method and application thereof | |
| CN109665525B (en) | Preparation method of dumbbell-shaped iron-nitrogen double-doped porous carbon | |
| CN109449448B (en) | Fuel cell cathode catalyst and preparation method and application thereof | |
| CN112820886B (en) | Three-dimensional hierarchical porous nonmetal carbon-based material, and preparation method and application thereof | |
| CN113659155B (en) | Metal-nitrogen-carbon coated carbon nanocage electrocatalyst and preparation method and application thereof | |
| CN110975912A (en) | Preparation and application of cobalt-nitrogen doped catalyst derived from bimetallic MOFs (metal-organic frameworks) | |
| CN114628697B (en) | FeCo alloy@nitrogen doped graphene hierarchical pore aerogel serving as oxygen reduction reaction catalyst and preparation method and application thereof | |
| CN113813975A (en) | ZIF-8 derived hierarchical pore M-N-C catalyst and preparation method thereof | |
| CN114784297A (en) | Preparation method of monatomic cobalt ORR catalyst | |
| CN114284515B (en) | Ternary heterostructure FePc/Ti 3 C 2 /g-C 3 N 4 Preparation method and application of composite material | |
| CN113430554B (en) | Monoatomic nickel-nitrogen coordination co-doped porous carbon/nano zirconia composite electrode and preparation method and application thereof | |
| CN112201799B (en) | Ultrathin disk-shaped mesoporous carbon material and preparation method and application thereof | |
| CN110492114B (en) | Nitrogen-doped porous carbon-oxygen reduction catalyst and preparation method and application thereof | |
| CN110773212A (en) | Iron carbide-porous carbon composite material and preparation method and application thereof | |
| CN106602080A (en) | Three-dimensional porous Fe-N-C catalyst based on cetyl trimethyl ammonium bromide as carbon material pore-forming agent and preparation method | |
| CN110085881A (en) | A kind of preparation method and applications of iron compound filling nitrogen-phosphor codoping carbon nano tube compound material | |
| CN112264067B (en) | Non-noble metal transition metal-based carbon dioxide electroreduction catalyst and preparation method thereof | |
| CN113948718A (en) | Rare earth polyphenol supermolecule coated covalent organic polymer cerium-based carbon nanosphere | |
| CN111874886B (en) | Nitrogen-doped porous carbon material and preparation method and application thereof |
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 |