CN113611878A - Nitrogen-rich bio-oil-based porous carbon and preparation method and application thereof - Google Patents
Nitrogen-rich bio-oil-based porous carbon and preparation method and application thereof Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 248
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 124
- 239000012075 bio-oil Substances 0.000 title claims abstract description 82
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000197 pyrolysis Methods 0.000 claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 238000006722 reduction reaction Methods 0.000 claims abstract description 19
- 239000002028 Biomass Substances 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 230000007935 neutral effect Effects 0.000 claims abstract description 3
- -1 nitrogen-containing compound Chemical class 0.000 claims abstract description 3
- 238000010000 carbonizing Methods 0.000 claims abstract 2
- 239000000047 product Substances 0.000 claims description 25
- 230000003197 catalytic effect Effects 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000011257 shell material Substances 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 5
- 239000011654 magnesium acetate Substances 0.000 claims description 5
- 235000011285 magnesium acetate Nutrition 0.000 claims description 5
- 229940069446 magnesium acetate Drugs 0.000 claims description 5
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims description 4
- 241000018646 Pinus brutia Species 0.000 claims description 4
- 235000011613 Pinus brutia Nutrition 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- 235000012254 magnesium hydroxide Nutrition 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 3
- 244000105624 Arachis hypogaea Species 0.000 claims description 3
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 3
- 235000018262 Arachis monticola Nutrition 0.000 claims description 3
- 240000007049 Juglans regia Species 0.000 claims description 3
- 235000009496 Juglans regia Nutrition 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 3
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 235000020232 peanut Nutrition 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- 239000010902 straw Substances 0.000 claims description 3
- 235000020234 walnut Nutrition 0.000 claims description 3
- 241000609240 Ambelania acida Species 0.000 claims description 2
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- 239000004677 Nylon Substances 0.000 claims description 2
- 239000010905 bagasse Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000002699 waste material Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 25
- 238000000967 suction filtration Methods 0.000 abstract description 7
- 239000007787 solid Substances 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 description 16
- 238000005303 weighing Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- 125000004355 nitrogen functional group Chemical group 0.000 description 7
- 229910003481 amorphous carbon Inorganic materials 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000005087 graphitization Methods 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000001237 Raman spectrum Methods 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- PNNCWTXUWKENPE-UHFFFAOYSA-N [N].NC(N)=O Chemical compound [N].NC(N)=O PNNCWTXUWKENPE-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000002186 photoelectron spectrum Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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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
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
- H01M4/861—Porous electrodes with a gradient in the porosity
-
- 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
- H01M4/88—Processes of manufacture
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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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- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a nitrogen-enriched bio-oil-based porous carbon and a preparation method and application thereof; the preparation method comprises the following steps: preparing nitrogen-rich bio-oil by co-pyrolysis by taking biomass and a nitrogen-containing compound as raw materials; preparing a uniform mixture of a precursor and a template agent by taking nitrogen-rich bio-oil as a carbon and nitrogen precursor and metal salt as the template agent; carbonizing the mixture at high temperature to obtain a carbonized product; acid washing is carried out on the carbonized product, deionized water is used for washing until the carbonized product is neutral, and nitrogen-rich bio-oil-based porous carbon is obtained after suction filtration and drying; the invention takes the nitrogen-rich bio-oil as a precursor, has the advantages of low ash content and high nitrogen content, does not need to add a nitrogen source in the pyrolysis process, is more suitable for a template method than solid biomass, and the obtained porous carbon has the characteristics of regular pore structure, concentrated pore diameter and rich nitrogen and oxygen functional groups on the surface, and shows good oxygen reduction reaction electrocatalysis performance.
Description
Technical Field
The invention belongs to the field of electrochemical and new energy material preparation, and relates to nitrogen-rich bio-oil-based porous carbon and a preparation method and application thereof.
Background
The Oxygen Reduction Reaction (ORR) is the main reaction of the cathode in green energy conversion devices such as fuel cells, metal-air cells and the like, and the slow kinetic process thereof causes low overall efficiency, so that a cathode catalyst must be used to improve the problem. At present, a platinum-carbon (Pt/C) catalyst commonly used in commerce has optimal catalytic activity, but a noble metal catalyst has the problems of high cost, scarce resources, poor stability, poor methanol toxicity resistance and the like, and the large-scale popularization and use of the catalyst still faces dilemma. Nitrogen-doped porous carbon, which exhibits excellent ORR catalytic activity and stability and resistance to methanol toxicity higher than those of Pt/C catalysts, is considered to be one of the most promising non-metallic catalysts.
Biomass is the only renewable carbon source in nature, has wide source, low cost and environmental protection, and is often used as a raw material of a carbon material. Nitrogen doping and pore-forming are common modification methods for preparing carbon by high-temperature pyrolysis, and usually a nitrogen source is required to be added, so that the process is complex. The pore diameter distribution of the obtained nitrogen-doped porous carbon is not concentrated and the structure is irregular, so that the final electrochemical catalytic performance is influenced. The bio-oil is a main product in the thermochemical conversion process of biomass, has high carbon and oxygen contents and low ash content, is rich in aromatic products, and is extremely easy to condense and carbonize. In addition, the liquid nature of bio-oil makes it more suitable for the templating method than solid feedstocks, resulting in porous carbons with more regular pore structure.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the technical problems of non-centralized pore size distribution, irregular structure, poor electrochemical catalytic performance and the like of nitrogen-doped porous carbon in the prior art, the nitrogen-rich bio-oil-based porous carbon and the preparation method thereof are provided. The porous carbon has regular pore structure, concentrated pore diameter and high graphitization degree, and the surface of the porous carbon is rich in nitrogen and oxygen functional groups. Can be widely applied to the aspect of electrochemical catalytic oxygen reduction reaction.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: the nitrogen-rich bio-oil-based porous carbon is characterized in that nitrogen-rich bio-oil obtained by co-pyrolysis of biomass and nitrogen-containing compounds is used as a precursor, metal salt is used as a template agent, and the porous carbon is prepared by one-step carbonization.
Further, a preparation method of the nitrogen-enriched bio-oil-based porous carbon comprises the following steps:
(1) preparing nitrogen-enriched bio-oil: uniformly mixing biomass and a nitrogen-containing raw material, and co-pyrolyzing the mixture in an inert gas atmosphere to obtain nitrogen-rich bio-oil;
(2) mixing the nitrogen-rich biological oil with a template agent: adding a template agent and absolute ethyl alcohol into the nitrogen-rich bio-oil obtained in the step (1), uniformly stirring under a heating condition, and cooling to room temperature to obtain a mixture of the nitrogen-rich bio-oil and the template agent;
(3) preparing nitrogen-enriched bio-oil-based porous carbon: pyrolyzing the mixture in the step (2) in an inert gas atmosphere, keeping the temperature constant after heating, and naturally cooling to room temperature after the reaction is finished to obtain a carbonized product;
(4) and (4) carrying out acid washing treatment on the carbonized product in the step (3), washing the carbonized product to be neutral by using deionized water, and filtering and drying the product to obtain the final product.
Further, the biomass in the step (1) is at least one of pine, rice hull, coconut shell, walnut shell, peanut shell, straw and bagasse, and the nitrogen-containing raw material is at least one of waste nylon (polyamide), urea and melamine.
Further, the mass ratio of the biomass to the nitrogen-containing raw material in the step (1) is 0.5:1-2: 1.
Further, the pyrolysis conditions in the step (1) are as follows: the heating rate is 1-50 ℃/min, the pyrolysis temperature is 500-.
Further, in the step (2), the template agent is at least one of zinc chloride, magnesium acetate, magnesium hydroxide, potassium chloride, sodium chloride and potassium carbonate.
Further, the mass ratio of the nitrogen-rich biological oil to the template agent in the step (2) is 1:2-1: 5.
Further, the carbonization conditions in the step (3) are as follows: the heating rate is 1-20 ℃/min, the temperature is raised to 500-1000 ℃ and kept constant, the heat preservation time is 1-3h, and the gas flow rate is 10-500 mL/min.
Further, the acid washing conditions of the step (4) are as follows: using 0.1-3mol/L dilute hydrochloric acid solution, washing for 1-12h, and pickling at 25-60 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1. the biomass and the nitrogen-containing raw material have synergistic effect in the co-pyrolysis process, the nitrogen-containing compound can promote the carbonyl product to be converted into the nitrogen-containing heterocyclic product, compared with the single biomass pyrolysis, the nitrogen content in the co-pyrolysis liquid product is increased from 0.8-2.1% to 8.5-12.7%, and the nitrogen-rich bio-oil with low ash content, high carbon content and rich aromatic compounds can be obtained and can be directly used as a carbon and nitrogen precursor in the carbon making process without adding a nitrogen source.
2. The nitrogen-rich bio-oil is in a liquid state and is easy to be uniformly mixed with a metal salt template agent, so that the porous carbon with regular and ordered pore structures is obtained, and the method is more suitable for a template method than a solid biomass.
3. The zinc chloride, magnesium acetate, magnesium hydroxide, potassium chloride, sodium chloride, potassium carbonate and the like used in the method are all cheap metal salt template agents, and after pyrolysis and acid washing removal, a multi-level pore structure which is centralized in pore diameter, uniform in distribution and mainly mesoporous can be generated in a carbonized product.
4. The specific surface area of the nitrogen-rich bio-oil-based porous carbon prepared by the method can reach 343.26-1039.84m2The pore volume reaches 0.16-1.24cm3A nitrogen content of 2.50-4.82 wt.%, wherein the total relative content of pyridine-type nitrogen and graphite-type nitrogen is 30-56%, which facilitates the generation of catalytically active sites. As an electrocatalyst for oxygen reduction reaction, the nitrogen-enriched bio-oil-based porous carbon shows good catalytic activity, high stability and methanol toxicity resistance.
Drawings
FIG. 1 is a nitrogen desorption curve and a pore size distribution diagram of the catalyst prepared in example 1.
FIG. 2 is an X photoelectron spectrum of the catalyst prepared in example 1.
FIG. 3 is a Raman spectrum of the catalyst prepared in example 1.
FIG. 4 is a linear voltammogram of the catalyst prepared in example 1 in a 0.1mol/L KOH solution saturated with oxygen.
Detailed Description
In order to more clearly explain the technical solution of the present invention, the present invention will be described in further detail with reference to the following examples and drawings, but the embodiments of the present invention are not limited thereto. The parameter processing which is not indicated can be carried out according to the conventional technology.
Example 1
A preparation method of nitrogen-enriched bio-oil-based porous carbon comprises the following steps:
1) preparing nitrogen-enriched bio-oil: weighing 150g of dry pine molding particles and 150g of polyamide, uniformly mixing, and then pyrolyzing in a nitrogen atmosphere at a heating rate of 10 ℃/min and a pyrolysis temperature of 600 ℃, keeping the temperature for 1h and a nitrogen flow rate of 500mL/min to obtain nitrogen-rich bio-oil, which is recorded as A1.
2) Preparing a mixture of the nitrogen-enriched bio-oil and a template agent: weighing 10g A1 and 10g zinc chloride, adding ethanol, stirring at 85 ℃, cooling to room temperature to obtain a mixture of nitrogen-enriched bio-oil and template agent, and recording as B1.
3) Preparing nitrogen-enriched bio-oil-based porous carbon: weighing 8g B1, and pyrolyzing in argon atmosphere at a heating rate of 10 ℃/min and a pyrolysis temperature of 800 ℃, and keeping the temperature for 2h at a nitrogen flow rate of 100 mL/min. After the reaction is finished, cooling to room temperature, and taking out the carbonized product. The product was ground to a powder in a mortar, acid-washed with 2mol/L hydrochloric acid solution at normal temperature for 12 hours, followed by suction filtration of the acid-washed solution, and washed with deionized water to neutrality. Finally, drying in an oven at 105 ℃ for 12h gave a nitrogen-enriched bio-oil-based porous carbon for catalytic oxygen reduction reaction, noted NC 1.
Electrochemical test conditions were as follows: in 0.1mol/L KOH solution, a three-electrode system is adopted for electrochemical test, wherein a working electrode is a glassy carbon electrode (the diameter is 3mm) or a rotating ring disk electrode (the diameter is 3mm)5.61mm), the counter electrode is a platinum wire electrode, and the reference electrode is an Ag/AgCl electrode. Mixing the catalyst with water, absolute ethyl alcohol and
the solutions were mixed to make a homogeneous suspension. And dripping a certain amount of suspension liquid on the surface of the glassy carbon electrode or the rotating disk electrode, and standing and drying to obtain the working electrode to be tested. The catalytic performance of the catalysts described in the examples was investigated for oxygen reduction reactions using Cyclic Voltammetry (CV) and linear voltammetry (LSV).
As shown in FIG. 4, the test results of CV and LSV demonstrated that NC1 has catalytic performance for oxygen reduction reaction, and the initial potential and half-wave potential of NC1 were 0.044V and-0.158V, respectively, in LSV test in 0.1mol/L KOH solution, which are comparable to commercial Pt/C catalyst (initial potential and half-wave potential of 0.048V and-0.148V, respectively). The result of analysis by a nitrogen adsorption and desorption test is shown in fig. 1, developed pores exist in NC1, the NC1 mainly comprises micropores and small-sized mesopores, and the specific surface area is measured to be 920.58m2Per g, pore volume of 0.58cm3The results of elemental analysis and X-ray photoelectron spectroscopy are shown in FIG. 2, which shows that NC1 contains 3.68 wt% of nitrogen, the total content of graphite-type and pyridine-type nitrogen in the nitrogen functional groups is 56%, and the NC1 surface contains abundant oxygen functional groups. As a result of raman spectroscopy analysis, it can be seen from fig. 3 that NC1 is composed of amorphous carbon and a graphite structure, and the degree of graphitization is high. As an ORR catalyst, abundant micropores in an NC1 structure are beneficial to exposing more active sites, and mesopores are beneficial to the transmission and diffusion of reaction substances. The graphite type nitrogen and pyridine type nitrogen functional groups on the surface of the catalyst are beneficial to generating ORR catalytic active sites on the surface of the porous carbon, and the oxygen functional groups enhance the hydrophilicity of the surface of the catalyst, so that the electrolyte can more fully infiltrate the surface of the catalyst. In addition, the graphitized structure of the material enhances the conductivity of the material.
Example 2
A preparation method of nitrogen-enriched bio-oil-based porous carbon comprises the following steps:
1) preparing nitrogen-enriched bio-oil: weighing 150g of dried pine wood particles and 150g of urea, uniformly mixing, and then pyrolyzing in a nitrogen atmosphere at a heating rate of 1 ℃/min and a pyrolysis temperature of 500 ℃ for 3h at a nitrogen flow rate of 10mL/min to obtain nitrogen-rich bio-oil, which is recorded as A2.
2) Preparing a mixture of the nitrogen-enriched bio-oil and a template agent: 10g A2 and 20g of magnesium hydroxide were weighed, ethanol was added to the mixture, the mixture was stirred at 85 ℃ and cooled to room temperature to obtain a mixture of nitrogen-enriched bio-oil and template agent, denoted as B2.
3) Preparing nitrogen-enriched bio-oil-based porous carbon: weighing 8g B2, and pyrolyzing in argon atmosphere at a heating rate of 1 ℃/min and a pyrolysis temperature of 500 ℃ for 3h at a nitrogen flow rate of 10 mL/min. After the reaction is finished, cooling to room temperature, and taking out the carbonized product. The product was ground to a powder in a mortar, acid-washed with 3mol/L hydrochloric acid solution at 60 ℃ for 6h, followed by suction filtration of the acid-washed solution, and washed to neutrality with deionized water. Finally, drying in an oven at 105 ℃ for 12h gave a nitrogen-enriched bio-oil-based porous carbon for catalytic oxygen reduction reaction, noted NC 2.
Test results of CV and LSV prove that NC2 has catalytic performance for oxygen reduction reaction, and the initial potential and half-wave potential of NC2 are 0.035V and-0.160V, respectively, in LSV test in 0.1mol/LKOH solution. NC3 has developed pores, mainly mesopores and a small amount of micropores, and the specific surface area is measured to be 573.99m2Per g, pore volume of 0.39cm3(ii) in terms of/g. The nitrogen content in NC2 was 4.82 wt%, and the total content of graphite-type and pyridine-type nitrogen in the nitrogen functional group was 30%. It is known from raman spectroscopic analysis that NC2 is composed mainly of amorphous carbon and a small amount of graphitized structures.
Example 3
A preparation method of nitrogen-enriched bio-oil-based porous carbon comprises the following steps:
1) preparing nitrogen-enriched bio-oil: weighing 300g of dried peanut shells and 150g of melamine, uniformly mixing, and then pyrolyzing in a nitrogen atmosphere at a heating rate of 50 ℃/min and a pyrolysis temperature of 800 ℃ for 2h, wherein the nitrogen flow rate is 200mL/min, so as to obtain nitrogen-rich bio-oil, which is recorded as A3.
2) Preparing a mixture of the nitrogen-enriched bio-oil and a template agent: 10g A3 and 5g of magnesium acetate were weighed, ethanol was added to the mixture, the mixture was stirred at 85 ℃ and cooled to room temperature to obtain a mixture of nitrogen-enriched bio-oil and template agent, denoted as B3.
3) Preparing nitrogen-enriched bio-oil-based porous carbon: weighing 8g B3, and pyrolyzing in argon atmosphere at a heating rate of 20 ℃/min and a pyrolysis temperature of 1000 ℃, keeping the temperature for 1h and a nitrogen flow rate of 200 mL/min. After the reaction is finished, cooling to room temperature, and taking out the carbonized product. The product was ground to a powder in a mortar, acid-washed with 0.1mol/L hydrochloric acid solution at 60 ℃ for 12h, followed by suction filtration of the acid-washed solution, and washed to neutrality with deionized water. Finally, drying in an oven at 105 ℃ for 12h gave a nitrogen-enriched bio-oil-based porous carbon for catalytic oxygen reduction reaction, noted NC 3.
Test results of CV and LSV prove that NC3 has catalytic performance for oxygen reduction reaction, and the initial potential and half-wave potential of NC3 are 0.021V and-0.166V respectively in LSV test in 0.1mol/LKOH solution. NC3 has developed pores, mainly mesopores and a small amount of micropores, and the specific surface area is measured to be 1066.81m2Per g, pore volume of 0.72cm3(ii) in terms of/g. The nitrogen content in NC3 was 3.11 wt%, the total content of graphitic and pyridinium nitrogen in the nitrogen functional groups was 52%. The Raman spectrum analysis shows that NC3 mainly consists of amorphous carbon and a graphitized structure, and the graphitization degree is high.
Example 4
A preparation method of nitrogen-enriched bio-oil-based porous carbon comprises the following steps:
1) preparing nitrogen-enriched bio-oil: weighing 150g of dry straw and 300g of urea, uniformly mixing, and then pyrolyzing in a nitrogen atmosphere at a heating rate of 50 ℃/min and a pyrolysis temperature of 800 ℃ for 2h at a nitrogen flow rate of 200mL/min to obtain nitrogen-rich bio-oil, which is recorded as A4.
2) Preparing a mixture of the nitrogen-enriched bio-oil and a template agent: 10g A4 and 10g of magnesium acetate were weighed, ethanol was added to the mixture, the mixture was stirred at 85 ℃ and cooled to room temperature to obtain a mixture of nitrogen-enriched bio-oil and template agent, denoted as B4.
3) Preparing nitrogen-enriched bio-oil-based porous carbon: weighing 8g B4, and pyrolyzing in argon atmosphere at a heating rate of 10 ℃/min and a pyrolysis temperature of 800 ℃, and keeping the temperature for 2h at a nitrogen flow rate of 100 mL/min. After the reaction is finished, cooling to room temperature, and taking out the carbonized product. The product was ground to a powder in a mortar, acid-washed with 2mol/L hydrochloric acid solution at 60 ℃ for 12h, followed by suction filtration of the acid-washed solution, and washed to neutrality with deionized water. Finally, drying in an oven at 105 ℃ for 12h gave a nitrogen-enriched bio-oil-based porous carbon for catalytic oxygen reduction reaction, noted NC 4.
Test results of CV and LSV demonstrated that NC4 has catalytic performance for oxygen reduction reaction, with the initial potential and half-wave potential of NC4 being 0.018V and-0.160V, respectively, in LSV testing in 0.1mol/LKOH solution. NC4 has developed pores, mainly mesopores and a small amount of micropores, and the specific surface area is measured to be 1039.84m2G, pore volume of 1.24cm3(ii) in terms of/g. The nitrogen content in NC4 was 2.5 wt%, and the total content of graphite-type and pyridine-type nitrogen in the nitrogen functional group was 48%. The Raman spectrum analysis shows that NC4 mainly consists of amorphous carbon and a graphitized structure, and the graphitization degree is high.
Example 5
A preparation method of nitrogen-enriched bio-oil-based porous carbon comprises the following steps:
1) preparing nitrogen-enriched bio-oil: weighing 150g of dry walnut shells and 150g of urea, uniformly mixing, and then pyrolyzing in a nitrogen atmosphere at a heating rate of 50 ℃/min and a pyrolysis temperature of 800 ℃ for 2h at a nitrogen flow rate of 200mL/min to obtain nitrogen-rich bio-oil, which is recorded as A5.
2) Preparing a mixture of the nitrogen-enriched bio-oil and a template agent: weighing 10g A5 and 15g magnesium carbonate, adding ethanol, stirring at 85 ℃, cooling to room temperature to obtain a mixture of nitrogen-enriched bio-oil and a template agent, and recording as B5.
3) Preparing nitrogen-enriched bio-oil-based porous carbon: weighing 8g B5, and pyrolyzing in argon atmosphere at a heating rate of 10 ℃/min and a pyrolysis temperature of 900 ℃, and keeping the temperature for 2h at a nitrogen flow rate of 500 mL/min. After the reaction is finished, cooling to room temperature, and taking out the carbonized product. The product was ground to a powder in a mortar, acid-washed with 2mol/L hydrochloric acid solution at 60 ℃ for 12h, followed by suction filtration of the acid-washed solution, and washed to neutrality with deionized water. Finally, drying in an oven at 105 ℃ for 12h gave a nitrogen-enriched bio-oil-based porous carbon for catalytic oxygen reduction reaction, noted NC 5.
Test results of CV and LSV prove that NC5 has catalytic performance for oxygen reduction reaction, and the initial potential and half-wave potential of NC5 are-0.011V and-0.172V respectively in LSV test in 0.1mol/LKOH solution. NC5 has developed pores, mainly mesopores and a small amount of micropores, and the specific surface area is measured to be 562.36m2Per g, pore volume of 0.31cm3(ii) in terms of/g. The nitrogen content of NC5 was 3.39 wt%, and the total content of graphite-type and pyridine-type nitrogen in the nitrogen functional group was 42%. The Raman spectrum analysis shows that NC5 mainly consists of amorphous carbon and a graphitized structure, and the graphitization degree is high.
Example 6
A preparation method of nitrogen-enriched bio-oil-based porous carbon comprises the following steps:
1) preparing nitrogen-enriched bio-oil: weighing 150g of dry rice hull and 150g of polyamide, uniformly mixing, and then pyrolyzing in a nitrogen atmosphere at a heating rate of 10 ℃/min and a pyrolysis temperature of 600 ℃, keeping the temperature for 2h and a nitrogen flow rate of 200mL/min to obtain nitrogen-rich bio-oil, which is recorded as A6.
2) Preparing a mixture of the nitrogen-enriched bio-oil and a template agent: 10g A6 and 40g of potassium chloride are weighed, ethanol is added into the mixture, the mixture is stirred evenly at 85 ℃, and the mixture is cooled to room temperature to obtain a mixture of the nitrogen-enriched bio-oil and the template agent, which is marked as B6.
3) Preparing nitrogen-enriched bio-oil-based porous carbon: weighing 8g B6, and pyrolyzing in argon atmosphere at a heating rate of 10 ℃/min and a pyrolysis temperature of 800 ℃, and keeping the temperature for 2h at a nitrogen flow rate of 100 mL/min. After the reaction is finished, cooling to room temperature, and taking out the carbonized product. The product was ground to a powder in a mortar, acid-washed with 2mol/L hydrochloric acid solution at 60 ℃ for 12h, followed by suction filtration of the acid-washed solution, and washed to neutrality with deionized water. Finally, drying in an oven at 105 ℃ for 12h gave a nitrogen-enriched bio-oil-based porous carbon for catalytic oxygen reduction reaction, noted NC 6.
Test results of CV and LSV prove that NC6 has catalytic performance for oxygen reduction reaction, and the initial potential and half-wave potential of NC6 in LSV test in 0.1mol/LKOH solutionrespectively-0.058V and-0.181V. NC6 has developed pores, mainly micropores and a small part of mesopores, and the specific surface area is measured to be 343.26m2Per g, pore volume of 0.22cm3(ii) in terms of/g. The nitrogen content in NC6 was 3.07 wt%, and the total content of graphite-type and pyridine-type nitrogen in the nitrogen functional group was 42%. The Raman spectrum analysis shows that NC5 mainly consists of amorphous carbon and a graphitized structure, and the graphitization degree is high.
Example 7 comparison of a method for preparing nitrogen-enriched bio-oil-based porous carbon with the prior art
Compared with the invention, patents 1 and 2 in the comparison table adopt similar carbon precursor tar, but do not mention the preparation mode of the tar, do not dope nitrogen, and have different application directions; patent 3 adopts general solid carbon source and urea nitrogen source (similar to the invention), but the pore-forming mode is traditional CO2Activation, low specific surface area and different pore structures; patents 4 and 5 are both nitrogen-doped porous carbon preparation and oxygen reduction catalytic application which are the same as the nitrogen-doped porous carbon preparation, and the physical and chemical properties and catalytic performance of the carbon are similar to those of the nitrogen-doped porous carbon preparation, however, the preparation methods are different from each other in two points, firstly, the carbon source adopts nitrogen-containing biomass, and secondly, the carbon source is activated by alkali, so that the raw material adaptability of the method is stronger, and the adopted template agent can be recycled, so that the method is more environment-friendly.
The foregoing description of the embodiments is provided to facilitate the understanding and use of the invention by those skilled in the art. It will be apparent to those skilled in the art that various modifications to these embodiments are possible, and that the generic principles defined herein may be applied to other experiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and improvements and modifications made without departing from the spirit and scope of the invention should be within the scope of the invention.
Claims (10)
1. The nitrogen-rich bio-oil-based porous carbon is characterized in that nitrogen-rich bio-oil obtained by co-pyrolysis of biomass and a nitrogen-containing compound is used as a precursor, metal salt is used as a template agent, and the porous carbon is prepared by one-step carbonization.
2. The method for preparing the nitrogen-enriched bio-oil-based porous carbon according to claim 1, comprising the following steps:
(1) preparing nitrogen-enriched bio-oil: uniformly mixing biomass and a nitrogen-containing raw material, and co-pyrolyzing the mixture in an inert gas atmosphere to obtain nitrogen-rich bio-oil;
(2) mixing the nitrogen-rich biological oil with a template agent: adding a template agent and absolute ethyl alcohol into the nitrogen-rich bio-oil obtained in the step (1), uniformly stirring under a heating condition, and cooling to room temperature to obtain a mixture of the nitrogen-rich bio-oil and the template agent;
(3) preparing nitrogen-enriched bio-oil-based porous carbon: carbonizing the mixture in the step (2) in an inert gas atmosphere, keeping the temperature constant after heating, and naturally cooling to room temperature after the reaction is finished to obtain a carbonized product;
(4) and (4) carrying out acid washing treatment on the carbonized product in the step (3), washing the carbonized product to be neutral by using deionized water, and filtering and drying the product to obtain the final product.
3. The method for preparing the nitrogen-enriched bio-oil-based porous carbon according to claim 2, wherein the method comprises the following steps: the biomass in the step (1) is at least one of pine, rice hull, coconut shell, walnut shell, peanut shell, straw and bagasse, and the nitrogenous raw material is at least one of waste nylon (polyamide), urea and melamine.
4. The method for preparing the nitrogen-enriched bio-oil-based porous carbon according to claim 2, wherein the method comprises the following steps: the mass ratio of the biomass to the nitrogen-containing raw material in the step (1) is 0.5:1-2: 1.
5. The method for preparing the nitrogen-enriched bio-oil-based porous carbon according to claim 2, wherein the method comprises the following steps: the pyrolysis conditions in the step (1) are as follows: the heating rate is 1-50 ℃/min, the pyrolysis temperature is 500-.
6. The method for preparing the nitrogen-enriched bio-oil-based porous carbon according to claim 2, wherein the method comprises the following steps: in the step (2), the template agent is at least one of zinc chloride, magnesium acetate, magnesium hydroxide, magnesium carbonate, potassium chloride and potassium carbonate.
7. The method for preparing the nitrogen-enriched bio-oil-based porous carbon according to claim 2, wherein the method comprises the following steps: the mass ratio of the nitrogen-rich biological oil to the template agent in the step (2) is 1:2-1: 5.
8. The method for preparing the nitrogen-enriched bio-oil-based porous carbon according to claim 2, wherein the method comprises the following steps: the carbonization conditions in the step (3) are as follows: the heating rate is 1-20 ℃/min, the temperature is raised to 500-1000 ℃ and kept constant, the heat preservation time is 1-3h, and the gas flow rate is 10-500 mL/min.
9. The method for preparing the nitrogen-enriched bio-oil-based porous carbon according to claim 2, wherein the method comprises the following steps: the acid washing conditions of the step (4) are as follows: using 0.1-3mol/L dilute hydrochloric acid solution, washing for 1-12h, and pickling at 25-60 deg.CoC。
10. Use of a nitrogen-enriched bio-oil-based porous carbon according to claims 1-9 in electrochemical catalytic oxygen reduction reactions.
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