CN111689484A - Nitrogen and phosphorus co-doped porous carbon derived from aerogel and preparation method and application thereof - Google Patents
Nitrogen and phosphorus co-doped porous carbon derived from aerogel and preparation method and application thereof Download PDFInfo
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- CN111689484A CN111689484A CN201910192756.3A CN201910192756A CN111689484A CN 111689484 A CN111689484 A CN 111689484A CN 201910192756 A CN201910192756 A CN 201910192756A CN 111689484 A CN111689484 A CN 111689484A
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 96
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 48
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 48
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000004964 aerogel Substances 0.000 title claims abstract description 39
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 39
- 239000011574 phosphorus Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims abstract description 37
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000017 hydrogel Substances 0.000 claims abstract description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 11
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000004108 freeze drying Methods 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 8
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 238000006722 reduction reaction Methods 0.000 claims description 16
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 12
- 229920001400 block copolymer Polymers 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 6
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 6
- 229940068041 phytic acid Drugs 0.000 claims description 6
- 235000002949 phytic acid Nutrition 0.000 claims description 6
- 239000000467 phytic acid Substances 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 4
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 4
- 229910052786 argon Inorganic materials 0.000 claims 2
- 239000002243 precursor Substances 0.000 abstract description 6
- 125000005842 heteroatom Chemical group 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 239000003575 carbonaceous material Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000004502 linear sweep voltammetry Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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Abstract
The invention discloses nitrogen and phosphorus codoped porous carbon derived from aerogel and a preparation method and application thereof, wherein the preparation method comprises the steps of preparing nitrogen and phosphorus codoped hydrogel by a one-step hydrothermal method, then freeze-drying the hydrogel to prepare the nitrogen and phosphorus codoped aerogel, and finally carbonizing the aerogel at high temperature or activating the aerogel by carbon dioxide to obtain the nitrogen and phosphorus codoped porous carbon; the specific surface area of the prepared nitrogen-phosphorus co-doped porous carbon is 1700-2900m2Per g, average pore diameter of 0.5-1.5nm, pore volume of 0.8-2.3cm3(ii) in terms of/g. The method for preparing the precursor nitrogen-phosphorus co-doped aerogel provided by the invention is unique and ingenious, and the prepared precursor has the advantages of a porous structure and uniform nitrogen-phosphorus co-doping; the prepared nitrogen-phosphorus co-doped porous carbon has high specific surface area, obvious porous structure and doped heteroatoms; the preparation method of the nitrogen-phosphorus co-doped porous carbon has the advantages of mild conditions, simple process, easily available and cheap raw materials, suitability for mass production and wide application prospect.
Description
Technical Field
The invention relates to the technical field of porous carbon materials, and particularly relates to nitrogen and phosphorus co-doped porous carbon derived from aerogel and a preparation method and application thereof.
Background
With the increasing demand for sustainable and green energy, fuel cells are receiving much attention. The oxygen reduction reaction has attracted extensive research interest as a key reaction in fuel cells. Currently, platinum-based catalysts are the most commonly used electrocatalysts in oxygen reduction reactions. However, many of the disadvantages of platinum-based catalysts, such as resource shortage, high cost, and low durability, limit their commercial applications. Therefore, it is an urgent problem to find an advanced catalyst that can replace the conventional platinum-based catalyst, such as developing a new metal-free catalyst or reducing the platinum content in the platinum-based catalyst.
Carbon materials with heteroatom doping, such as nitrogen, phosphorus, fluorine or boron doped carbon materials, are considered to be potential metal-free catalysts in oxygen reduction reactions. Nitrogen doping in the porous carbon, particularly the presence of graphite type nitrogen and pyridine type nitrogen, can greatly promote the catalytic activity of the oxygen reduction reaction. Meanwhile, in consideration of different atom sizes and electronegativity of different heteroatoms, nitrogen and phosphorus double doping in the carbon material can further introduce charged defects and change the surface polarity in the carbon skeleton. Therefore, due to the existence of the synergistic effect, nitrogen and phosphorus double doping in the carbon material can further enhance the catalytic activity of the oxygen reduction reaction. Besides impurity atom doping, rich porous structure and high specific surface area play an important role in improving oxygen reduction reaction activity. The porous structure allows the electrolyte to rapidly enter the interior of the material and contact the reaction sites. At present, carbon dioxide activation has been widely applied to the preparation of porous carbon materials. In addition, the aerogel can be used as a relatively ideal precursor for carbon dioxide activation to prepare heteroatom-doped carbon materials with high porosity. Therefore, it is necessary to develop nitrogen and phosphorus co-doped porous carbon derived from nitrogen and phosphorus co-doped aerogel and use the nitrogen and phosphorus co-doped porous carbon as an oxygen reduction electrocatalyst.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides nitrogen and phosphorus co-doped porous carbon derived from aerogel and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the nitrogen-phosphorus-codoped porous carbon derived from the aerogel comprises the steps of preparing nitrogen-phosphorus-codoped hydrogel by a one-step hydrothermal method, then carrying out freeze drying on the hydrogel to prepare the nitrogen-phosphorus-codoped aerogel, and finally carrying out high-temperature carbonization or carbon dioxide activation on the aerogel to obtain the nitrogen-phosphorus-codoped porous carbon.
Specifically, the nitrogen-phosphorus co-doped aerogel has the characteristics of a porous structure and nitrogen-phosphorus co-doping, and provides a suitable precursor for the preparation of subsequent nitrogen-phosphorus co-doped porous carbon.
In the above technical solution, the preparation method comprises the following steps:
s1, adding the block copolymer P123, phytic acid and pyrrole into water, uniformly mixing, placing in a hydrothermal kettle, carrying out hydrothermal reaction to obtain nitrogen and phosphorus co-doped hydrogel, and carrying out freeze drying on the hydrogel to obtain nitrogen and phosphorus co-doped aerogel;
s2, carbonizing the nitrogen and phosphorus co-doped aerogel at 850-950 ℃ or activating the nitrogen and phosphorus co-doped aerogel with carbon dioxide to prepare the nitrogen and phosphorus co-doped porous carbon.
In the above technical scheme, in step S1, the reaction temperature and the reaction time of the hydrothermal reaction are 160-.
Further, in the above technical solution, in step S1, the molar ratio of the block copolymer P123, the phytic acid and the pyrrole is (0.01-0.03): (0.8-1.2): (0.8-1.2).
Further, in the above technical solution, in step S1, the freezing temperature and the freezing time of the freeze-drying are-45 to-55 ℃ and 60-85h, respectively.
In the above technical scheme, in the step S2, the high-temperature carbonization is specifically performed by heating to 850-.
In the above technical scheme, in the step S2, the carbon dioxide activation is specifically performed by heating to 850-.
The invention also provides nitrogen and phosphorus co-doped porous carbon derived from the aerogel prepared by the preparation method.
Specifically, the specific surface area of the nitrogen-phosphorus co-doped porous carbon is 1700-2900m2Per g, average pore diameter of 0.5-1.5nm, pore volume of 0.8-2.3cm3/g。
In detail, the nitrogen-phosphorus co-doped porous carbon has the characteristics of high specific surface area, obvious porous structure, heteroatom doping and the like, and has good application in electrocatalytic oxygen reduction reaction.
The invention also provides a preparation method or application of the nitrogen and phosphorus co-doped porous carbon, and particularly the nitrogen and phosphorus co-doped porous carbon is applied to electro-catalysis of oxygen reduction reaction of a fuel cell, a super capacitor or gas adsorption.
The invention has the advantages that:
(1) the method for preparing the precursor nitrogen-phosphorus co-doped aerogel provided by the invention is unique and ingenious, and the prepared precursor nitrogen-phosphorus co-doped aerogel has the advantages of a porous structure and uniform nitrogen-phosphorus co-doping, so that a foundation is laid for the subsequent preparation of the nitrogen-phosphorus co-doped porous carbon material with a high specific surface area;
(2) the nitrogen-phosphorus co-doped porous carbon prepared by the preparation method provided by the invention has the characteristics of high specific surface area, obvious porous structure, heteroatom doping and the like, has good application in electrocatalytic oxygen reduction reaction, and has potential application prospect in the fields of supercapacitors and gas adsorption;
(3) the preparation method of the nitrogen-phosphorus co-doped porous carbon derived from the aerogel, provided by the invention, has the advantages of mild conditions, simple process, stable chemical structure and performance of the product, easily available and cheap raw materials, simple equipment, strong controllability, high production efficiency, suitability for large-scale industrial production, excellent product adsorption performance, wide application prospect and great theoretical and practical significance.
Drawings
Fig. 1 is a photograph of nitrogen and phosphorus co-doped hydrogel prepared in example 1 of the present invention;
FIG. 2 is a photograph of nitrogen and phosphorus co-doped aerogel prepared in example 2 of the present invention;
fig. 3 is a scanning electron microscope photograph of the nitrogen and phosphorus co-doped porous carbon prepared in example 2 of the present invention;
fig. 4 is a transmission electron microscope photograph of the nitrogen and phosphorus co-doped porous carbon prepared in example 2 of the present invention;
fig. 5 is a nitrogen adsorption and desorption graph of the nitrogen-phosphorus co-doped porous carbon prepared in example 2 of the present invention;
fig. 6 is a Cyclic Voltammetry (CV) graph of the nitrogen and phosphorus co-doped porous carbon prepared in example 2 of the present invention in the catalysis process of the oxygen reduction reaction;
fig. 7 is a Linear Sweep Voltammetry (LSV) graph of the nitrogen and phosphorus co-doped porous carbon prepared in example 2 of the present invention in the catalysis process of the oxygen reduction reaction.
Detailed Description
The following detailed description of embodiments of the invention is provided in connection with the accompanying drawings and the examples.
The following examples are intended to illustrate the present invention, but not to limit the scope of the invention, which is defined by the claims.
Unless otherwise specified, experimental reagents and materials used in the examples of the present invention are commercially available, and unless otherwise specified, technical means used in the examples of the present invention are conventional means well known to those skilled in the art.
In the following examples, scanning electron micrographs were obtained using a cold field emission scanning electron microscope (Hitachi S4800); the transmission electron microscope photograph is obtained by using a field emission transmission electron microscope (Tecnai G2F 20U-TWIN); the nitrogen adsorption-desorption curve is obtained by a 3-Flex specific surface and pore size analyzer of Mac instruments USA, and the Cyclic Voltammetry (CV) curve and the Linear Sweep Voltammetry (LSV) curve in the catalytic process of the oxygen reduction reaction are measured by an electrochemical workstation (CHI 760E).
Example 1
The embodiment of the invention provides a preparation method of nitrogen and phosphorus co-doped porous carbon derived from aerogel, which comprises the following specific steps:
s1, adding 2.0g of block copolymer P123 into 60.0mL of 0.25mol/L phytic acid aqueous solution, stirring for 5 hours at 35 ℃ until the block copolymer P123 is dissolved, then adding 1.0mL of pyrrole, stirring and mixing for 2 minutes to obtain a milky uniform dispersion liquid, transferring the milky uniform dispersion liquid into a high-pressure reaction kettle, carrying out hydrothermal reaction for 12 hours at 180 ℃ to obtain nitrogen-phosphorus co-doped hydrogel, washing the prepared nitrogen-phosphorus co-doped hydrogel with ultrapure water for several times, and freeze-drying for 72 hours at-55 ℃ to obtain nitrogen-phosphorus co-doped aerogel;
s2, placing the prepared nitrogen-phosphorus co-doped aerogel into a quartz boat, heating at a speed of 5 ℃/min in a tubular furnace in a nitrogen atmosphere, heating to 950 ℃, then preserving the heat for 100min, and cooling to room temperature after the reaction is finished to obtain a black solid, namely the nitrogen-phosphorus co-doped porous carbon.
Fig. 1 is a photograph showing nitrogen and phosphorus co-doped hydrogel prepared in example 1 of the present invention; as can be seen from FIG. 1, a hydrogel was prepared after one hydrothermal step.
Example 2
The embodiment of the invention provides a preparation method of nitrogen and phosphorus co-doped porous carbon derived from aerogel, which comprises the following specific steps:
s1, adding 2.0g of block copolymer P123 into 60.0mL of 0.25mol/L phytic acid aqueous solution, stirring for 5 hours at 35 ℃ until the block copolymer P123 is dissolved, then adding 1.0mL of pyrrole, stirring and mixing for 2 minutes to obtain a milky uniform dispersion liquid, transferring the milky uniform dispersion liquid into a high-pressure reaction kettle, carrying out hydrothermal reaction for 12 hours at 180 ℃ to obtain nitrogen-phosphorus co-doped hydrogel, washing the prepared nitrogen-phosphorus co-doped hydrogel with ultrapure water for several times, and freeze-drying for 72 hours at-55 ℃ to obtain nitrogen-phosphorus co-doped aerogel;
s2, placing the prepared nitrogen-phosphorus co-doped aerogel into a quartz boat, heating at a speed of 5 ℃/min in a nitrogen atmosphere by using a tube furnace, switching the atmosphere into carbon dioxide when the temperature rises to 950 ℃, preserving heat and activating for 100min at 950 ℃, switching into a nitrogen atmosphere after the activation reaction is finished, and cooling the sample to room temperature to obtain black solid, namely the nitrogen-phosphorus co-doped porous carbon.
FIG. 2 is a photograph showing nitrogen and phosphorus co-doped aerogel prepared in example 2 of the present invention; as can be seen from fig. 2, the aerogel obtained after freeze-drying maintains a good shape.
Fig. 3 and 4 are a scanning electron microscope photograph and a transmission electron microscope photograph of the nitrogen-phosphorus co-doped porous carbon prepared in example 2 of the present invention, respectively; as can be seen from fig. 3, the morphology of the nitrogen-phosphorus co-doped porous carbon consists of spheres with different particle sizes (< 2 μm in diameter); as can be seen from fig. 4, the nitrogen-phosphorus co-doped porous carbon has a highly porous structure. .
Fig. 5 is a nitrogen adsorption and desorption graph of the nitrogen-phosphorus co-doped porous carbon prepared in embodiment 2 of the present invention, and analysis and calculation show that the BET specific surface area of the nitrogen-phosphorus co-doped porous carbon prepared in embodiment 2 of the present invention is 2850m2Per g, pore volume of 2.21cm3/g。
The nitrogen-phosphorus co-doped porous carbon prepared in the embodiment 2 of the invention is used as a working electrode, a platinum wire is used as a counter electrode, Ag/AgCl is used as a reference electrode, the electrochemical performance of the nitrogen-phosphorus co-doped porous carbon is tested in a three-electrode system, and the electrolyte is 0.1mol/L KOH aqueous solution.
The sweep rate of the Cyclic Voltammetry (CV) curve was 5mV/s, and the results are shown in FIG. 6.
As can be seen from fig. 6, the sample does not have any peak in the KOH aqueous solution saturated with nitrogen, however, in the KOH aqueous solution saturated with oxygen at the same scan rate, a characteristic peak of the cathode can be observed, which indicates that the nitrogen-phosphorus co-doped porous carbon material prepared has catalytic activity for the oxygen reduction reaction.
Linear Sweep Voltammetry (LSV) curves were obtained at sweep rates of 5mV/s at different rotational speeds (100rpm, 400rpm, 900rpm, and 1600rpm), with the results shown in FIG. 7.
From the results in the figure, the initial potential of the obtained material was 0.90V vs. RHE, the half-wave potential was 0.81Vvs. RHE, and the limiting current density at 400rpm was-2.46 mA/cm2The results show that the obtained nitrogen-phosphorus co-doped porous carbon has higher electrocatalytic activity of oxygen reduction reaction.
The above embodiments are merely illustrative of the present invention, and not restrictive, and many modifications and changes may be made by those skilled in the art without departing from the spirit of the invention, and it is intended that all such modifications and changes as fall within the true spirit of the invention and the scope of the claims be determined by those skilled in the art.
Claims (10)
1. The preparation method of the nitrogen-phosphorus-codoped porous carbon derived from the aerogel is characterized by comprising the steps of preparing nitrogen-phosphorus-codoped hydrogel by a one-step hydrothermal method, then carrying out freeze drying on the hydrogel to prepare the nitrogen-phosphorus-codoped aerogel, and finally carrying out high-temperature carbonization or carbon dioxide activation on the aerogel to obtain the nitrogen-phosphorus-codoped porous carbon.
2. The method of claim 1, comprising the steps of:
s1, adding the block copolymer P123, phytic acid and pyrrole into water, uniformly mixing, placing in a hydrothermal kettle, carrying out hydrothermal reaction to obtain nitrogen and phosphorus co-doped hydrogel, and carrying out freeze drying on the hydrogel to obtain nitrogen and phosphorus co-doped aerogel;
s2, carbonizing the nitrogen and phosphorus co-doped aerogel at 850-950 ℃ or activating the nitrogen and phosphorus co-doped aerogel with carbon dioxide to prepare the nitrogen and phosphorus co-doped porous carbon.
3. The preparation method as claimed in claim 2, wherein in step S1, the reaction temperature and reaction time of the hydrothermal reaction are respectively 160-200 ℃ and 10-15 h.
4. The production method according to claim 2 or 3, wherein in step S1, the molar ratio of the block copolymer P123, the phytic acid and the pyrrole is (0.01 to 0.03): (0.8-1.2): (0.8-1.2).
5. The method according to claim 2 or 3, wherein the freezing temperature and freezing time of the freeze-drying in step S1 are-45 to-55 ℃ and 60-85 hours, respectively.
6. The method as claimed in claim 2, wherein in step S2, the carbonization step is carried out by heating to 850-.
7. The method as claimed in claim 2, wherein in step S2, the carbon dioxide activation is performed by heating to 850-950 ℃ at a rate of 1-8 ℃/min under the protection of nitrogen or argon, then activating under the protection of carbon dioxide for 60-100min, and finally cooling under the protection of nitrogen or argon.
8. The aerogel-derived nitrogen-phosphorus co-doped porous carbon prepared by the preparation method according to any one of claims 1 to 7.
9. The aerogel-derived nitrogen-phosphorus-codoped porous carbon according to claim 8, wherein the specific surface area of the nitrogen-phosphorus-codoped porous carbon is 1700-2900m2Per g, average pore diameter of 0.5-1.5nm, pore volume of 0.8-2.3cm3/g。
10. The use of the nitrogen and phosphorus co-doped porous carbon according to any one of claims 1 to 7 or 8 to 9, wherein the nitrogen and phosphorus co-doped porous carbon is used in fuel cell oxygen reduction reaction electrocatalysis, supercapacitors or gas adsorption.
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