CN113620271B - Three-dimensional porous carbon sponge and preparation method and application thereof - Google Patents
Three-dimensional porous carbon sponge and preparation method and application thereof Download PDFInfo
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- CN113620271B CN113620271B CN202110780915.9A CN202110780915A CN113620271B CN 113620271 B CN113620271 B CN 113620271B CN 202110780915 A CN202110780915 A CN 202110780915A CN 113620271 B CN113620271 B CN 113620271B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 229920000642 polymer Polymers 0.000 claims abstract description 121
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 238000010000 carbonizing Methods 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 45
- 239000000463 material Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000446 fuel Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 238000001179 sorption measurement Methods 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- PKWIYNIDEDLDCJ-UHFFFAOYSA-N guanazole Chemical compound NC1=NNC(N)=N1 PKWIYNIDEDLDCJ-UHFFFAOYSA-N 0.000 claims description 8
- 229920005603 alternating copolymer Polymers 0.000 claims description 7
- 238000003763 carbonization Methods 0.000 claims description 7
- 238000001338 self-assembly Methods 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 9
- 230000007613 environmental effect Effects 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 8
- 239000010411 electrocatalyst Substances 0.000 description 5
- 238000000429 assembly Methods 0.000 description 4
- 230000000712 assembly Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000000502 dialysis Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- -1 and the like Substances 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
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- 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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28042—Shaped bodies; Monolithic structures
- B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
-
- 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
- H01M4/8605—Porous electrodes
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- 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
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- 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
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- Chemical & Material Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a three-dimensional porous carbon sponge and a preparation method and application thereof. The method is characterized in that: the three-dimensional porous carbon sponge is obtained by carbonizing a spongy polymer assembly, a through three-dimensional network is formed inside the three-dimensional porous carbon sponge, and the specific surface area reaches 363m 2 g ‑1 The pore diameter is distributed at 1-20nm, and the porous structure of micropores, small mesopores and large mesopores is provided. The three-dimensional porous carbon sponge is obtained by carbonizing a spongy polymer assembly, a through three-dimensional network is formed inside the three-dimensional porous carbon sponge, and the three-dimensional porous carbon sponge has a porous structure of micropores, small mesopores and large mesopores, so that the transmission efficiency of electrons and substances is remarkably improved. And a preparation method of the three-dimensional porous carbon sponge, which has the advantages of simple steps, high nitrogen doping amount, environmental friendliness and capability of mass preparation.
Description
Technical Field
The invention relates to a three-dimensional porous carbon sponge and a preparation method and application thereof.
Background
The energy source is one of the main source power for promoting the industrialized progress and the social development. What changes is our living environment, invariably is the need for energy. Although the material economy of the present invention reaches an unprecedented level, the mode of taking energy from the nature is mainly fossil energy, and the ecological and living environment of the present invention is seriously damaged due to the excessive consumption of fossil energy. The over exploitation and use of fossil energy sources brings a series of problems, such as geological destruction of the earth surface, energy shortage, environmental pollution and the like, and the development of new energy source technology has strong necessity and urgency. Therefore, various countries in the world advocate energy conservation and emission reduction, put into a great deal of manpower and material resources to develop new energy (such as nuclear energy, solar energy, wind energy and the like) which can replace traditional fossil fuel and advanced energy storage and conversion technologies (such as fuel cells, lithium ion batteries, super capacitors and the like), hope to relieve global energy crisis by means of technological innovation, improve ecological balance and guarantee sustainable development of society and economy.
The electric energy is sustainable and environment-friendly secondary energy, and the efficient energy storage and conversion system is a key for relieving the current energy situation. Electrochemical energy storage devices include fuel cells, lithium ion batteries, electrochemical capacitors, and the like, and fuel cells can replace traditional fossil energy fuels, and are one of the most promising clean energy technologies. The oxygen reduction reaction (Oxygen Reduction Reaction, ORR) acts as a cathode reaction for the fuel cell, limiting the development of the fuel cell. It is therefore urgent to develop an ORR electrocatalyst that is efficient. The current large-scale commercialized ORR electrocatalyst is mainly noble metal-based catalyst (such as Pt-based catalyst), and the Pt-based material is the ORR electrocatalyst with highest current efficiency due to high initial potential and high diffusion current density in the electrocatalytic oxygen reduction process. However, the scarcity of platinum metal in earth content and its high cost limit the wide, large-scale application of Pt-based electrocatalytic materials. Accordingly, research has been focused on finding efficient, durable, inexpensive Pt-based ORR electrocatalyst alternatives.
Carbon-based materials have recently attracted attention from researchers due to their low cost, easy regulation of structure, high electrical conductivity, thermal conductivity, specific surface area, unique electronic structure and properties, and are considered to be one of the ORR electrocatalysts with broad application prospects. The preparation of three-dimensional porous carbon sponge still faces serious challenges, and particularly, the control of pore size is difficult to obtain a porous structure with micropores, small mesopores and large mesopores.
Disclosure of Invention
One of the purposes of the invention is to provide a three-dimensional porous carbon sponge, wherein a through three-dimensional network is formed inside the sponge, and the sponge has a porous structure of micropores, small mesopores and large mesopores, so that the transmission efficiency of electrons and substances is remarkably improved;
the second purpose of the invention is to provide a preparation method of the three-dimensional porous carbon sponge, which has simple steps, high nitrogen doping amount, environmental friendliness and capability of realizing mass preparation;
it is a further object of the present invention to provide a use of the three-dimensional porous carbon sponge.
A three-dimensional porous carbon sponge, which is characterized in that: the three-dimensional porous carbon sponge is obtained by carbonizing a spongy polymer assembly, a through three-dimensional network is formed inside the three-dimensional porous carbon sponge, and the specific surface area reaches 363m 2 g -1 The pore diameter is distributed at 1-20nm, and the porous structure of micropores, small mesopores and large mesopores is provided.
A preparation method of a three-dimensional porous carbon sponge is characterized by comprising the following steps: firstly, polymer self-assembly is carried out through a solvent exchange method to obtain a spongy polymer assembly, and the spongy polymer assembly is used as a precursor to be carbonized in an inert atmosphere to obtain the three-dimensional porous carbon sponge.
The spongy polymer assembly is specifically prepared by self-assembling a polymer through a solvent exchange method, wherein the polymer is an alternating copolymer of 1,2,4, 5-pyromellitic dianhydride and 3, 5-diamino-1, 2, 4-triazole.
Wherein the spongy polymer assembly is formed by connecting and stacking polymer skeletons.
Wherein the preparation method of the spongy polymer assembly comprises the following steps: firstly, dissolving the polymer in dimethylformamide at the concentration of 10.0-100.0 mg/mL, then dripping water to induce the polymer solution to self-assemble, then self-assemble by a solvent exchange method to obtain spongy polymer assembly dispersion liquid, dialyzing to remove dimethylformamide, freezing the spongy polymer assembly dispersion liquid, and drying in vacuum to obtain spongy polymer assembly powder.
Wherein the inert gas is one or more of nitrogen, hydrogen and ammonia; the carbonization temperature is 600-1200 ℃.
The application of three-dimensional porous carbon sponge as an adsorption material.
Use of a three-dimensional porous carbon sponge as electrocatalytic material for a fuel cell.
In order to solve the problems in the prior art, the invention provides a three-dimensional porous carbon sponge, a preparation method and application thereof, wherein the three-dimensional porous carbon sponge is obtained by carbonizing a spongy polymer assembly, a through three-dimensional network is formed inside the three-dimensional porous carbon sponge, and the three-dimensional porous carbon sponge has a porous structure of micropores, small mesopores and large mesopores, so that the transmission efficiency of electrons and substances is remarkably improved. And a preparation method of the three-dimensional porous carbon sponge, which has the advantages of simple steps, high nitrogen doping amount, environmental friendliness and capability of mass preparation.
By adopting the scheme, the invention has the beneficial effects that:
the three-dimensional porous carbon sponge provided by the invention is a three-dimensional network which is internally penetrated, has a porous structure of micropores, small mesopores and large mesopores, is beneficial to effective transmission of electrons and substances, and can obviously improve the electrocatalytic performance.
Secondly, the preparation method of the three-dimensional porous carbon sponge is simple and convenient in steps, high in nitrogen doping amount and capable of being prepared in a large amount. And water is dripped into the polymer solution for self-assembly, a spongy polymer assembly is obtained after freeze drying, and the three-dimensional porous carbon sponge is obtained after carbonization in inert atmosphere, so that the preparation steps are simple, the nitrogen doping amount is high, the period is short, and the preparation can be performed in a large amount.
Thirdly, the polymer is an alternating copolymer of 1,2,4, 5-pyromellitic dianhydride and 3, 5-diamino-1, 2, 4-triazole, and the three-dimensional porous carbon sponge obtained after carbonization has high in-situ nitrogen doping amount and very good electrocatalytic oxygen reduction capacity due to high nitrogen content of the polymer. In addition, the porous structure of micropores, small mesopores and large mesopores of the multi-three-dimensional porous carbon sponge is beneficial to effective transmission of electrons and substances, and can be used as an active electrocatalytic material of a fuel cell.
Fourth, the three-dimensional porous carbon sponge provided by the invention is obtained by directly carbonizing a spongy polymer assembly and has three pore structures of micropores, mesopores and macropores. The porous structure enables the three-dimensional carbon sponge to have excellent adsorption performance, so that the three-dimensional carbon sponge can be used as a high-efficiency adsorption material.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a spongy polymer assembly according to example 1 of the present invention;
FIG. 2 is a Transmission Electron Microscope (TEM) image of a three-dimensional porous carbon sponge according to example 1 of the present invention;
FIG. 3 is N of a three-dimensional porous carbon sponge according to example 1 of the present invention 2 Suction and desorption drawing;
FIG. 4 is a pore size distribution diagram of a three-dimensional porous carbon sponge in example 1 of the present invention;
FIG. 5 is a graph showing the electrocatalytic performance of a three-dimensional porous carbon sponge according to example 1 of the present invention.
Detailed Description
The invention provides a three-dimensional porous carbon sponge, a preparation method and application thereof. The preparation method comprises the following steps: taking 1,2,4, 5-pyromellitic dianhydride and 3, 5-diamino-1, 2, 4-triazole as monomers, and obtaining a polymer through condensation polymerization; the polymer is self-assembled by a solvent exchange method to obtain a spongy polymer assembly, and the assembly is taken as a precursor to be carbonized in an inert atmosphere to obtain a three-dimensional porous carbon sponge; the three-dimensional porous carbon sponge obtained after carbonization completely inherits the three-dimensional porous structure characteristics of the spongy polymer assembly. The preparation process is convenient and environment-friendly, and a template is not needed; the nitrogen atoms contained in the polymer can be utilized to realize intrinsic nitrogen doping of the three-dimensional porous carbon sponge and improve the contents of pyridine nitrogen and graphitized nitrogen. Because the unique internal penetrating network structure and porous structure of the three-dimensional porous carbon sponge are beneficial to charge and substance transmission, the three-dimensional porous carbon sponge has excellent adsorption and electrocatalytic performance, and can be used as an adsorption material and an electrocatalytic material of a fuel cell.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the three-dimensional porous carbon sponge is characterized in that the three-dimensional porous carbon sponge is obtained by carbonizing a spongy polymer assembly, inherits the porous structure characteristics of the spongy polymer assembly, forms a through three-dimensional network inside, and has a porous structure of micropores, small mesopores and large mesopores.
A method of preparing a three-dimensional porous carbon sponge comprising the steps of: carbonizing the spongy polymer assembly serving as a precursor in an inert atmosphere to obtain a three-dimensional porous carbon sponge; the spongy polymer assembly is obtained by self-assembling a polymer through a solvent exchange method, wherein the polymer is an alternating copolymer of 1,2,4, 5-pyromellitic dianhydride and 3, 5-diamino-1, 2, 4-triazole, and the main chain of the polymer contains a large number of benzene rings and five-membered heterocyclic rings.
The preparation method of the spongy polymer assembly comprises the following steps: dissolving polymer in dimethylformamide at the concentration of 10.0-100.0 mg/mL, dripping water-based polymer for self-assembly, self-assembly by a solvent exchange method to obtain spongy polymer assembly dispersion, freezing, and vacuum drying to obtain spongy polymer assembly powder.
In the above method for producing a spongy polymer assembly, the water dropping rate is 0.1 to 5 mL/min.
In the preparation method of the three-dimensional porous carbon sponge, the inert gas can be one or more of nitrogen, hydrogen and ammonia; the calcination temperature can be 600-1200 ℃; the spongy polymer assembly is formed by connecting and stacking polymer frameworks.
The three-dimensional porous carbon sponge can be applied as an adsorption material or an electrocatalytic material of a fuel cell.
The invention provides a three-dimensional porous carbon sponge, a preparation method thereof and application of the three-dimensional porous carbon sponge.
< three-dimensional porous carbon sponge >
The three-dimensional porous carbon sponge provided by the invention is obtained by carbonizing a spongy polymer assembly, inherits the porous structure characteristics of the spongy polymer assembly, forms a through three-dimensional network inside, and has a porous structure of micropores, small mesopores and large mesopores.
< method for preparing three-dimensional porous carbon sponge >
The preparation method of the three-dimensional porous carbon sponge comprises the following steps: and carbonizing the spongy polymer assembly serving as a precursor in an inert atmosphere to obtain the three-dimensional porous carbon sponge.
Wherein, the spongy polymer assembly is formed by self-assembling polymers through a solvent exchange method. The polymer is an alternating copolymer of 1,2,4, 5-pyromellitic dianhydride and 3, 5-diamino-1, 2, 4-triazole, and contains a large amount of benzene rings and five-membered heterocyclic rings.
The preparation method of the spongy polymer assembly comprises the following steps: dissolving a polymer in Dimethylformamide (DMF) at a concentration of 10.0-100.0 mg/mL, directly dripping water into the polymer solution under stirring for self-assembly, obtaining a spongy polymer assembly dispersion liquid through self-assembly by a solvent exchange method, dialyzing the spongy polymer assembly dispersion liquid, freezing and vacuum drying to obtain the spongy polymer assembly.
In the above method for producing a spongy polymer assembly, the water dropping rate is 0.1 to 5 mL/min, preferably 2 mL/min.
In the above method for preparing a three-dimensional porous carbon sponge, the inert gas may be one or more of nitrogen, hydrogen and ammonia. The carbonization and calcination temperature is 600-1200 ℃.
< application of three-dimensional porous carbon sponge >
1. The three-dimensional porous carbon sponge of the present invention can be used as an adsorbent material.
The three-dimensional porous carbon sponge is obtained by carbonizing a spongy polymer assembly serving as a precursor in an inert atmosphere. The spongy polymer assembly is formed by self-assembling alternating copolymers of 1,2,4, 5-pyromellitic dianhydride and 3, 5-diamino-1, 2, 4-triazole. The spongy polymer assembly is formed by connecting and stacking polymer frameworks, so that the three-dimensional porous carbon sponge formed after calcination has a porous structure and can be used as an adsorption material.
2. The three-dimensional porous carbon sponge can be used as an electrocatalytic material for oxygen reduction reaction of a fuel cell.
The three-dimensional porous carbon sponge is obtained by carbonizing a spongy polymer assembly serving as a precursor in an inert atmosphere. The three-dimensional porous carbon sponge inherits the porous structure characteristics of a spongy polymer assembly, forms a through three-dimensional network inside, has a porous structure with micropores, small mesopores and large mesopores, can promote the transmission rate of electrons and ions in the electrocatalytic process, can be used as an electrocatalytic material for the oxygen reduction reaction of a fuel cell, and can obviously improve the cycle stability and methanol toxicity resistance of the electrocatalytic oxygen reduction reaction.
The invention is further described below with reference to the drawings and examples.
Example 1:
the embodiment provides a three-dimensional porous carbon sponge and a preparation method thereof, wherein the three-dimensional porous carbon sponge is obtained by carbonizing a spongy polymer assembly, inherits the porous structure characteristics of the spongy polymer assembly, internally forms a through three-dimensional network, and has a porous structure of micropores, small mesopores and large mesopores. The preparation method comprises the following steps:
(1) Preparation of spongy polymer assemblies:
the chemical formula of the polymer is [ C 12 HO 6 N 5 ] n 780mg of the polymer was dissolved in dimethylformamide at a concentration of 30mg/mL, and 50mL of water was added dropwise to the polymer solution at a dropping rate of 0.1 mL/min to obtain a solution containing a spongy polymer assembly. The solution was transferred to 3500 dialysis bag, dialyzed against water in a beaker, frozen in liquid nitrogen, and dried in a freeze vacuum drier at-50℃for 36 hours to obtain a spongy polymer assembly (in powder form).
(2) The preparation method of the three-dimensional porous carbon sponge comprises the following steps:
carbonizing the spongy polymer assembly (in powder form) obtained in the step (1) at 800 ℃ under the protection of nitrogen, preserving heat at 800 ℃ for 1 hour, and naturally cooling to room temperature to obtain the three-dimensional porous carbon sponge with the porous structure.
As shown in FIG. 1, the resulting sponge-like polymer assembly has a three-dimensional block structure, the surface of which can be clearly seenA coarse structure. Fig. 2 shows that the three-dimensional porous carbon sponge is internally formed with a three-dimensional penetrating skeleton structure, and a plurality of gaps are formed between the polymer skeletons to form a porous structure. N-treatment of the three-dimensional porous carbon sponge obtained 2 The specific surface area of the three-dimensional porous carbon sponge is 363m through adsorption and desorption analysis 2 g -1 The pore size distribution is mainly concentrated at small mesopores of 2.2nm as shown in FIG. 3. The electrocatalytic test as shown in fig. 4 shows that the three-dimensional porous carbon sponge shows higher half-wave potential and has excellent cycle stability when used as an electrocatalytic material for oxygen reduction reaction of a fuel cell, and is an ideal electrocatalytic material.
Example 2:
the embodiment provides a three-dimensional porous carbon sponge and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) Preparation of spongy polymer assemblies:
the chemical formula of the polymer is [ C 12 HO 6 N 5 ] n 780mg of the polymer was dissolved in Dimethylformamide (DMF) at a concentration of 10mg/mL, and 156mL of water was added dropwise to the polymer solution for assembly, the water dropping rate being 0.5 mL/min, to obtain a solution containing a spongy polymer assembly. The solution was transferred to 3500 dialysis bag, dialyzed against water in a beaker, frozen in liquid nitrogen, and dried in a freeze vacuum drier at-50℃for 36 hours to obtain a spongy polymer assembly (in powder form).
(2) The preparation method of the three-dimensional porous carbon sponge comprises the following steps:
carbonizing the spongy polymer assembly (in powder form) obtained in the step (1) at 600 ℃ under the protection of nitrogen, preserving heat at 600 ℃ for 1 hour, and naturally cooling to room temperature to obtain the three-dimensional porous carbon sponge with the porous structure.
Example 3:
the embodiment provides a three-dimensional porous carbon sponge and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) Preparation of spongy polymer assemblies:
polymer chemistryIs [ C ] 12 HO 6 N 5 ] n 780mg of the polymer was dissolved in Dimethylformamide (DMF) at a concentration of 60mg/mL, and 26mL of water was added dropwise to the polymer solution at a dropping rate of 2 mL/min to obtain a solution containing a spongy polymer assembly. The solution was transferred to 3500 dialysis bag, dialyzed against water in a beaker, frozen in liquid nitrogen, and dried in a freeze vacuum drier at-50℃for 36 hours to obtain a spongy polymer assembly (in powder form).
(2) The preparation method of the three-dimensional porous carbon sponge comprises the following steps:
carbonizing the spongy polymer assembly (in powder form) obtained in the step (1) at 1000 ℃ under the protection of hydrogen, preserving heat at 1000 ℃ for 1 hour, and naturally cooling to room temperature to obtain the three-dimensional porous carbon sponge with the porous structure.
Example 4:
the embodiment provides a three-dimensional porous carbon sponge and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) Preparation of spongy polymer assemblies:
the chemical formula of the polymer is [ C 12 HO 6 N 5 ] n 780mg of the polymer was dissolved in Dimethylformamide (DMF) at a concentration of 100mg/mL, and 15.6mL of water was added dropwise to the polymer solution at a dropping rate of 5 mL/min to obtain a solution containing a spongy polymer assembly. The solution was transferred to 3500 dialysis bag, dialyzed against water in a beaker, frozen in liquid nitrogen, and dried in a freeze vacuum drier at-50℃for 36 hours to obtain a spongy polymer assembly (in powder form).
(2) The preparation method of the three-dimensional porous carbon sponge comprises the following steps:
carbonizing the spongy polymer assembly (in powder form) obtained in the step (1) at 1200 ℃ under the protection of ammonia gas, preserving heat for 1 hour at 1200 ℃, and naturally cooling to room temperature to obtain the three-dimensional porous carbon sponge with the porous structure.
In summary, the preparation method of the three-dimensional porous carbon sponge of the invention uses a spongy polymer assembly as a precursor, specifically, uses polymers with different solubilities in DMF and water, and obtains a spongy polymer assembly dispersion liquid by dripping water and self-assembling by a solvent exchange method. The solution was dialyzed, frozen, and dried in a freeze-vacuum dryer for 36 hours to obtain a spongy polymer assembly (in powder form). The spongy polymer assembly is used as a precursor, and carbonized in inert atmosphere to prepare the three-dimensional porous carbon sponge. In this production method, since the spongy polymer assembly is formed by connecting and stacking polymer backbones, the structure of the spongy polymer assembly is retained after carbonization, and the resulting three-dimensional porous carbon sponge has a porous structure (fig. 2). The preparation method has the advantages of simple steps, high nitrogen doping amount, simple operation and low raw material cost, and can be used for preparing a large amount of three-dimensional porous carbon sponge. The obtained three-dimensional porous carbon sponge has a porous structure, can efficiently adsorb different types of metal ions, and is an ideal adsorption material. In addition, the porous structure of the three-dimensional porous carbon sponge can effectively promote the transmission of electrons and ions in the electrocatalytic oxygen reduction process, so that the three-dimensional porous carbon sponge has better electrocatalytic capacity and is an ideal electrocatalytic material.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (7)
1. A three-dimensional porous carbon sponge, characterized in that: the three-dimensional porous carbon sponge is obtained by carbonizing a spongy polymer assembly, a through three-dimensional network is formed inside the three-dimensional porous carbon sponge, and the specific surface area reaches 363m 2 g ‒1 The pore diameter is distributed in 1-20nm, and the porous structure of micropores, small mesopores and large mesopores is provided;
the spongy polymer assembly is specifically prepared by self-assembling a polymer through a solvent exchange method, wherein the polymer is an alternating copolymer of 1,2,4, 5-pyromellitic dianhydride and 3, 5-diamino-1, 2, 4-triazole.
2. The method for preparing the three-dimensional porous carbon sponge according to claim 1, wherein: firstly, polymer self-assembly is carried out through a solvent exchange method to obtain a spongy polymer assembly, and the spongy polymer assembly is used as a precursor to be carbonized in an inert atmosphere to obtain a three-dimensional porous carbon sponge;
the spongy polymer assembly is specifically prepared by self-assembling a polymer through a solvent exchange method, wherein the polymer is an alternating copolymer of 1,2,4, 5-pyromellitic dianhydride and 3, 5-diamino-1, 2, 4-triazole.
3. The method for preparing the three-dimensional porous carbon sponge according to claim 2, wherein: wherein the spongy polymer assembly is formed by connecting and stacking polymer skeletons.
4. The method for preparing the three-dimensional porous carbon sponge according to claim 2, wherein: wherein the preparation method of the spongy polymer assembly comprises the following steps: firstly, dissolving the polymer in dimethylformamide at the concentration of 10.0-100.0 mg/mL, then dripping water to induce the polymer solution to self-assemble, then self-assemble by a solvent exchange method to obtain spongy polymer assembly dispersion liquid, dialyzing to remove dimethylformamide, freezing the spongy polymer assembly dispersion liquid, and drying in vacuum to obtain spongy polymer assembly powder.
5. The method for preparing the three-dimensional porous carbon sponge according to claim 2, wherein: wherein the inert gas is one or more of nitrogen, hydrogen and ammonia; the carbonization temperature is 600-1200 ℃.
6. Use of a three-dimensional porous carbon sponge according to claim 1 as an adsorption material.
7. Use of a three-dimensional porous carbon sponge according to claim 1 as electrocatalytic material for a fuel cell.
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