CN114156494A - Catalyst taking waste paper as carbon base and preparation method thereof - Google Patents
Catalyst taking waste paper as carbon base and preparation method thereof Download PDFInfo
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- CN114156494A CN114156494A CN202111497790.5A CN202111497790A CN114156494A CN 114156494 A CN114156494 A CN 114156494A CN 202111497790 A CN202111497790 A CN 202111497790A CN 114156494 A CN114156494 A CN 114156494A
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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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- 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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- 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
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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
Abstract
The invention discloses a catalyst taking waste paper as carbon base and a preparation method thereof, the method takes waste paper as raw material to form transition metal-nitrogen-carbon and other active sites based on metal organic framework material, wherein the waste paper is doped with nitrogen source and metal salt and is etched and formed with holes at high temperature by ammonia gas to obtain a nano-pore structure. The catalyst has high-efficiency and stable catalytic activity of oxygen reduction reaction, is low in cost, and can be applied to fuel cells.
Description
Technical Field
The invention belongs to the technical field of fuel cell electro-catalysts, and particularly relates to a catalyst taking waste paper as a carbon base and a preparation method thereof.
Background
Proton exchange membrane fuel cells have received much attention from researchers due to their high conversion rates and zero emissions. Among these, the high efficiency electrocatalyst for the cathode ORR is a key material for fuel cell applications. In recent years, precious metal Pt nanomaterials have become widely used catalysts due to their superior performance for ORR. However, the expensive and extreme scarcity of Pt severely restricts the development of fuel cells. Therefore, it is urgently needed to find non-noble metal nano materials which can replace Pt and have excellent performance. At present, the non-noble metal doped M-N-C system composite material is considered as the most promising ORR catalytic material, and the catalytic material has good catalytic activity, low cost and easy industrial production.
Disclosure of Invention
The invention aims to provide a catalyst taking waste paper as carbon base and a preparation method thereof, wherein the catalyst has high-efficiency and stable ORR catalytic activity and low cost and can be applied to fuel cells.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a catalyst taking waste paper as a carbon base is characterized in that waste paper is used as a raw material, a nitrogen source and metal salt are added to form active sites such as transition metal-nitrogen-carbon (M-N-C) based on an MOF material, wherein the waste paper is doped with the nitrogen source and the metal salt, and is subjected to ammonia etching pore-forming treatment at high temperature to obtain a nano-pore structure, and the preparation method comprises the following specific steps:
(1) heating the waste paper and the solvent in a closed container, cooling, taking out, and drying to obtain a product A;
(2) weighing a proper amount of nitrogen source and metal salt to prepare a doping solution for later use;
(3) soaking the product A in the step (1) into the doping solution in the step (2), carrying out primary calcination in an Ar gas atmosphere, and introducing ammonia gas to obtain a product B;
(4) ball-milling the product B, then pickling with strong acid, and drying to obtain a product C;
(5) washing the product C with water to be neutral, and drying to obtain a product D;
(6) and (5) carrying out secondary calcination on the product D in Ar gas atmosphere, and cooling to obtain the catalyst with the nano pore structure.
In the step (1), the waste paper is domestic waste paper; the solvent is a mixed solution of ethanol and deionized water with the volume ratio of 1.0-1.5: 1.5-2.0; the heating is carried out at 130-150 ℃ for 0.1-0.5 hour.
In the step (2), the nitrogen source is one or more of nitrogen-containing salts, nitrogen-containing high molecular polymers and nitrogen-containing gas; the metal salt is one or more of manganese group salt, iron group salt, cobalt group salt and nickel group salt.
Further, the nitrogen source is one or more of polyaniline, hydroxylamine chloride, amino acid, melamine, ammonia gas and urea; the metal salt is one or more of manganese chloride, nickel nitrate, ferric acetylacetonate, ferric nitrate, cobalt chloride, cobalt nitrate and ferric chloride.
In the step (3), the primary calcination refers to calcining for 0.1-12 hours in a tubular furnace at the temperature of 700-1800 ℃, wherein ammonia gas is introduced for 20-50 minutes when the temperature reaches 300-700 ℃.
And (4) performing ball milling on the product B for 0.5-1.5 h, adding 3% dilute nitric acid for pickling, then placing the product B into a drying oven at the temperature of 60-80 ℃ for 6-12 h, drying, and cooling to room temperature to obtain a product C.
And (5) washing the product C with deionized water for 5-6 times until the pH value is neutral, and then drying.
In the step (6), the secondary calcination refers to calcination in a tube furnace at 700-1800 ℃ for 0.1-12 hours.
The invention has the beneficial effects that:
1. the invention provides a method for preparing a catalyst by taking domestic waste paper as a raw material, which has the advantages of simplicity, short reaction time, convenience and high efficiency in operation, low cost, high catalytic activity, good stability and the like.
2. The raw materials used in the invention have wide sources and low price, and the metal salt used is very environment-friendly.
3. The MOF structure formed by the M-N-C active sites has higher ORR catalytic activity. The synergistic effect of the doped nitrogen source and the metal source and the pore-forming effect of ammonia gas are beneficial to the formation of catalytic active sites.
Detailed Description
Example 1
A preparation method of a catalyst taking waste paper as carbon base comprises the following steps:
(1) placing a mixed solution of ethanol and deionized water in a volume ratio of 1:1.5 and 30g of waste paper in a closed container, heating in an oven at 130 ℃ for 0.5 hour, cooling to room temperature, and then placing in the oven for drying to obtain a product A;
(2) weighing 6.1g of ferric nitrate, 3.9g of cobalt chloride, 1.6g of poly (m-phenylenediamine) and 3.6g of melamine to prepare a uniform doping solution;
(3) weighing the product A in the step (1) and the doping solution in the step (2), placing the product A and the doping solution in the step (2) into a porcelain boat, placing the porcelain boat into a tube furnace, heating the tube furnace to 1600 ℃ within 30 minutes under the atmosphere of inert gas Ar, calcining the porcelain boat for 1 hour, introducing ammonia gas for 20 minutes when the temperature is raised to 500 ℃, and then cooling the porcelain boat to room temperature to obtain a product B;
(4) taking the product B out of the tube furnace, carrying out ball milling for 40 minutes, adding 3% dilute nitric acid for pickling, putting the product B into a 60 ℃ oven for baking for 8 hours, and then cooling to room temperature to obtain a product C;
(5) centrifugally cleaning the product C for 3 times by using deionized water until the product C is neutral, and then drying the product C in an oven at 80 ℃ to obtain a product D;
(6) and taking out the product D, putting the product D into a porcelain boat again, calcining the product D for 3 hours at 1500 ℃ in a tubular furnace under the inert atmosphere condition, and cooling the product D to room temperature to obtain the catalyst.
Example 2
A preparation method of a catalyst taking waste paper as carbon base comprises the following steps:
(1) placing a mixed solution of ethanol and deionized water with the volume ratio of 1:1.7 and 30g of waste paper in a closed container, heating in an oven at 130 ℃ for 0.5 hour, cooling to room temperature, and then placing in the oven for drying to obtain a product A;
(2) weighing 6.1g of ferric nitrate, 3.9g of cobalt chloride, 1.6g of poly (m-phenylenediamine) and 3.6g of melamine to prepare a uniform doping solution;
(3) weighing the dried product A in the step (1) and the doping solution in the step (2), placing the product A and the doping solution in the step (2) into a porcelain boat, placing the porcelain boat into a tube furnace, heating the porcelain boat to 1800 ℃ in the tube furnace in the atmosphere of inert gas Ar, calcining the porcelain boat for 1 hour, introducing ammonia gas for 20 minutes at 600 ℃, and then cooling the porcelain boat to room temperature to obtain a product B;
(4) taking the product B out of the tube furnace, adding 3% dilute nitric acid for pickling after ball milling for 40 minutes, and finally putting the product B into a 60 ℃ oven for drying for 8 hours to obtain a product C;
(5) centrifugally cleaning the product C for 3 times by using deionized water until the product C is neutral, and then drying the product C in an oven at 80 ℃ to obtain a product D;
(6) and taking out the product D, putting the product D into a porcelain boat again, calcining the product D for 3 hours at 1100 ℃ in a tubular furnace under the inert atmosphere condition, and cooling the product D to room temperature to obtain the catalyst.
Claims (10)
1. A preparation method of a catalyst taking waste paper as carbon base is characterized in that: the method comprises the following steps of taking waste paper as a raw material, adding a nitrogen source and metal salt to form an M-N-C active site based on an MOF material, doping the waste paper with the nitrogen source and the metal salt, and carrying out ammonia etching and pore-forming treatment at a high temperature to obtain the catalyst with a nano-pore structure.
2. The method for preparing a catalyst based on waste paper as claimed in claim 1, wherein the method comprises the following steps: the method comprises the following steps:
(1) heating the waste paper and the solvent in a closed container, cooling, taking out, and drying to obtain a product A;
(2) weighing nitrogen source and metal salt to prepare doping solution;
(3) immersing the product A into the doping solution, carrying out primary calcination in an inert atmosphere, and introducing ammonia gas to obtain a product B;
(4) ball-milling the product B, then pickling with strong acid, and drying to obtain a product C;
(5) washing the product C with water to be neutral, and drying to obtain a product D;
(6) and (4) carrying out secondary calcination on the product D in an inert atmosphere, and cooling to obtain the catalyst with the nano-pore structure.
3. The method for preparing a catalyst based on waste paper as claimed in claim 2, wherein the method comprises the following steps: in the step (1), the solvent is a mixed solution of ethanol and deionized water with the volume ratio of 1.0-1.5: 1.5-2.0; the heating is carried out at 130-150 ℃ for 0.1-0.5 hour.
4. The method for preparing a catalyst based on waste paper as claimed in claim 2, wherein the method comprises the following steps: in the step (2), the nitrogen source is one or more of nitrogen-containing salts, nitrogen-containing high molecular polymers and nitrogen-containing gas; the metal salt is one or more of manganese group salt, iron group salt, cobalt group salt and nickel group salt.
5. The method for preparing a catalyst based on waste paper as claimed in claim 4, wherein the method comprises the following steps: the nitrogen source is one or more of polyaniline, hydroxylamine chloride, amino acid, melamine, ammonia gas and urea; the metal salt is one or more of manganese chloride, nickel nitrate, ferric acetylacetonate, ferric nitrate, cobalt chloride, cobalt nitrate and ferric chloride.
6. The method for preparing a catalyst based on waste paper as claimed in claim 2, wherein the method comprises the following steps: in the step (3), the primary calcination refers to calcining for 0.1-12 hours in a tubular furnace at the temperature of 700-1800 ℃, wherein ammonia gas is introduced for 20-50 minutes when the temperature reaches 300-700 ℃.
7. The method for preparing a catalyst based on waste paper as claimed in claim 2, wherein the method comprises the following steps: in the step (4), the specific process is to ball mill the product B for 0.5-1.5 h, add 3% dilute nitric acid for pickling, then put into a baking oven at 60-80 ℃ for 6-12 h, dry and cool to room temperature to obtain the product C.
8. The method for preparing a catalyst based on waste paper as claimed in claim 2, wherein the method comprises the following steps: in the step (5), the specific process is that the product C is washed by deionized water for 5-6 times until the pH value is neutral, and then dried.
9. The method for preparing a catalyst based on waste paper as claimed in claim 2, wherein the method comprises the following steps: in the step (6), the secondary calcination refers to calcination in a tube furnace at 700-1800 ℃ for 0.1-12 hours.
10. The catalyst obtained by the production method according to any one of claims 1 to 9.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111497790.5A CN114156494A (en) | 2021-12-09 | 2021-12-09 | Catalyst taking waste paper as carbon base and preparation method thereof |
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| CN202111497790.5A CN114156494A (en) | 2021-12-09 | 2021-12-09 | Catalyst taking waste paper as carbon base and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140045098A1 (en) * | 2010-09-21 | 2014-02-13 | Los Alamos National Security, Llc | Non-precious metal catalysts |
| CN106824245A (en) * | 2017-02-20 | 2017-06-13 | 天津理工大学 | A kind of method for preparing oxygen reduction catalyst as raw material with insect wing |
| WO2018120067A1 (en) * | 2016-12-30 | 2018-07-05 | The University Of Hong Kong | Waste biomass-derived metal-free catalysts for oxygen reduction reaction |
| CN109473686A (en) * | 2018-12-26 | 2019-03-15 | 宁波石墨烯创新中心有限公司 | It is a kind of with biomass cotton be carbon-based catalyst and its preparation method and application |
-
2021
- 2021-12-09 CN CN202111497790.5A patent/CN114156494A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140045098A1 (en) * | 2010-09-21 | 2014-02-13 | Los Alamos National Security, Llc | Non-precious metal catalysts |
| WO2018120067A1 (en) * | 2016-12-30 | 2018-07-05 | The University Of Hong Kong | Waste biomass-derived metal-free catalysts for oxygen reduction reaction |
| CN106824245A (en) * | 2017-02-20 | 2017-06-13 | 天津理工大学 | A kind of method for preparing oxygen reduction catalyst as raw material with insect wing |
| CN109473686A (en) * | 2018-12-26 | 2019-03-15 | 宁波石墨烯创新中心有限公司 | It is a kind of with biomass cotton be carbon-based catalyst and its preparation method and application |
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