CN107346825B - Nitrogen and phosphorus co-doped carbon-based nonmetal oxygen reduction/precipitation double-effect catalyst and preparation method thereof - Google Patents
Nitrogen and phosphorus co-doped carbon-based nonmetal oxygen reduction/precipitation double-effect catalyst and preparation method thereof Download PDFInfo
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Abstract
A nitrogen and phosphorus co-doped carbon-based nonmetal oxygen reduction/precipitation double-effect catalyst and a preparation method thereof belong to the technical field of catalysts. A covalent organic polymer rich in nitrogen and phosphorus is synthesized on a carbon carrier by a simple method, so that a nitrogen source and a phosphorus source are uniformly and regularly distributed on the surface of a carbon source, and a nitrogen-phosphorus co-doped porous carbon material is prepared by a one-step high-temperature calcination carbonization process. The material has low cost, is easy to prepare, not only has high-efficiency catalytic activity of oxygen reduction and oxygen precipitation reaction, but also has better stability. Has wide application prospect in the fields of rechargeable metal-air batteries, renewable fuel batteries and the like.
Description
Technical Field
The invention relates to a preparation method of a doped porous carbon-based non-metal oxygen reduction/precipitation double-effect catalytic material, in particular to a double-function carbon-based electrocatalytic material with oxygen reduction and oxygen precipitation catalytic performances, which is obtained by using a carbon, nitrogen and phosphorus-containing porous material as a precursor reactant and then performing one-step high-temperature calcination pyrolysis.
Background
The rechargeable metal-air battery is a kind of chemical power source with oxygen in air as positive electrode active material, active metal as negative electrode active material and neutral salt solution or alkaline solution as electrolyte. During discharge, the metal on the negative electrode loses electrons and is oxidized into corresponding metal ions, and the oxygen on the positive electrode is reduced (reduced into OH under the alkaline condition)-) And reversible reaction occurs during charging. The metal-air battery has the advantages of high energy density, high power density, environmental friendliness, high reliability and the like, and must occupy an important position in the future world energy pattern.
At present, the anode oxygen electrode catalyst of the metal-air battery mainly comprises noble metals such as Pt, Ru, Pd, Au, Ag and the like and alloys thereof. The current commercial noble metal catalyst is Pt/C, IrO2and/C, etc. However, the noble metal catalyst is generally expensive, and the noble metal resource is limited, and the development and application of the noble metal catalyst are limited by the defects. Research shows that the functionalized carbon material can catalyze oxygen reductionOr oxygen precipitation reaction is carried out, the carbon-based non-metal catalyst prepared by doping nitrogen, phosphorus and sulfur heteroatoms can even achieve good double-effect catalytic effect, meanwhile, the catalyst is prepared from non-metal raw materials, the cost is reduced, the stability is improved, the carbon-based heteroatom co-doping catalyst becomes an important research direction of the double-effect catalyst, however, the doping source and the carbon source are not uniformly mixed, the doping sites and the number are few, and the further improvement of the performance of the carbon-based catalyst is restricted.
Disclosure of Invention
The technical problem solved by the invention is as follows: the problems of the prior art such as improving the mixing uniformity between a doping source and a carbon source are solved, a covalent organic polymer rich in nitrogen and phosphorus is synthesized on a carbon carrier through a simple method, the nitrogen and the phosphorus are uniformly distributed in the polymer and tightly combined on the carbon carrier, and the nitrogen and phosphorus co-doped carbon-based catalytic material which has high-efficiency oxygen reduction/oxygen precipitation reaction catalytic performance and good stability is obtained through high-temperature carbonization. The material has the advantages of simple preparation process, easy operation and low cost, and solves the problems of low catalytic performance, poor stability, high cost and difficult large-scale popularization of the secondary metal air battery catalyst.
The invention is realized by the following method, and the preparation method of the nitrogen and phosphorus co-doped carbon-based non-metal oxygen reduction/precipitation double-effect catalyst is characterized by comprising the following steps:
step 1) directly synthesizing a covalent organic polymer material containing nitrogen and phosphorus on the surface of a carbon material by using a phosphorus source and a nitrogen source, weighing a certain amount of the nitrogen source, the phosphorus source and the carbon material, mixing and dissolving the nitrogen source, the phosphorus source and the carbon material in an organic solvent, transferring the mixture to a reaction kettle, heating and maintaining the reaction kettle for a period of time, washing and filtering a generated product for a plurality of times by using a washing solution, and drying to obtain the carbon-based material containing nitrogen and phosphorus.
And 2) transferring the synthesized carbon-based material containing nitrogen and phosphorus into a porcelain boat, putting the porcelain boat into a high-temperature tube furnace for high-temperature calcination and pyrolysis for a certain time, carbonizing the porcelain boat in protective gas, and naturally cooling to obtain the nitrogen and phosphorus co-doped carbon-based non-metal oxygen reduction/precipitation double-effect catalyst.
Further preferably:
the mass ratio of the phosphorus source to the nitrogen source to the carbon source in the step 1) is (1-2.6):1 (1-1.6), preferably (1-1.8):1 (1-1.3), more preferably (1-1.6):1 (1-1.3).
Step 1), heating the reaction kettle to 100-. The reaction time is 7 to 30 hours, preferably 18 to 24 hours, more preferably 20 to 24 hours.
The organic solvent in the step 1) can be one or more than two of tetrahydrofuran, dimethylformamide and ethanol.
In the step 1), vacuum filtration is adopted in the washing, filtering and drying step, and the washing liquid is one or two of deionized water, ethanol and methanol solution. The vacuum drying temperature is 65-150 deg.C, preferably 60-100 deg.C, and more preferably 60-80 deg.C.
And 2) the protective gas used in the calcining pyrolysis process is high-purity nitrogen or argon, and the purity is more than or equal to 99.99%. The flow rate of the inert gas used in the calcination process in the step 2) is 100-200mL min-1。
Step 2) the pyrolysis process: heating to 430 ℃ at the rate of 5-10 ℃/min, preserving the heat for 0.5-5.0 hours, heating to 1100 ℃ at the rate of 5-10 ℃/min, and preserving the heat for 0.5-5.0 hours.
Further preferred is a pyrolysis process: heating to 380 ℃ at the speed of 5-8 ℃/min, preserving the heat for 0.5-3.0 hours, heating to 1000 ℃ at the speed of 5-8 ℃/min, and preserving the heat for 0.5-3.0 hours.
Further, the phosphorus-containing compound is preferably one or more of triphenylphosphine, phytic acid, and hexachlorotriphosphazene.
Further, the nitrogen-containing compound is preferably one or two or more of melamine, urea, cyanamide, and thiourea.
Further, the carbon material is preferably one or more of graphite, carbon nanotubes, graphene, and graphene oxide.
The invention has the advantages that:
the invention synthesizes the nitrogen and phosphorus co-doped carbon-based non-metal oxygen reduction/precipitation double-effect catalytic material by adopting a simple and convenient method, has mild synthesis conditions and simple experimental operation, and the prepared carbon-based electrocatalyst not only has high-efficiency catalytic performance of oxygen reduction and oxygen precipitation reaction, but also has good stability. Provides a new idea for the design of preparing the high-efficiency bifunctional electrocatalytic material of the secondary metal-air battery. Compared with the prior art, the invention has the following advantages.
1) The nitrogen and phosphorus co-doped carbon-based electrocatalyst is prepared by one-time synthesis reaction and one-time pyrolysis reaction, the adopted raw materials are cheap and easy to obtain, the reaction condition is mild, the operation is simple and convenient, no pollution emission exists in the process, the method is environment-friendly, and the method is easy for large-scale production.
2) The invention takes graphene, carbon nano tubes and other materials as carbon sources, generates more active sites by uniformly doping nitrogen and phosphorus atoms in the carbon materials, increases the conductivity by utilizing the carbon materials, promotes the transfer of electrons from a catalyst to oxygen molecules, accelerates the processes of oxygen reduction and oxygen precipitation,
3) according to the invention, a nitrogen and phosphorus co-doped carbon material is formed through a high-temperature reaction, the synergistic effect of nitrogen and phosphorus promotes the reaction processes of oxygen reduction and oxygen precipitation, and the catalytic performance is better than that of a single heteroatom doped structure.
4) The carbon-based non-metal oxygen reduction/precipitation double-effect catalyst has good double-effect electrocatalysis performance and excellent stability, and is very suitable for the fields of secondary metal air batteries and the like.
Drawings
FIG. 1 shows cyclic voltammetry curves of nitrogen-phosphorus co-doped carbon-based dual-effect catalysts at different sweep rates;
FIG. 2 shows constant current charge and discharge curves of nitrogen and phosphorus co-doped carbon-based double-effect catalyst at different current densities.
Detailed Description
The present invention will be further described with reference to the following examples and drawings, but the present invention is not limited to the following examples.
Example 1
0.238g (0.907mmol) of triphenylphosphine, 0.180g (1.428mmol) of melamine and 0.060g of graphene oxide are weighed into 20ml of tetrahydrofuran, uniformly mixed by ultrasound, then transferred into a 50ml reaction kettle, heated to 110 ℃ and reacted for 24 hours.
And (3) carrying out suction filtration and washing on the generated product for a plurality of times by using deionized water and ethanol, drying in an oven, and drying for 12h at the temperature of 60 ℃. Obtaining the carbon-based material containing nitrogen and phosphorus. Transferring the synthesized carbon-based material containing nitrogen and phosphorus into a high-temperature furnace for calcination with the flow rate of 100mL min-1And heating the high-temperature furnace to 350 ℃ at the speed of 5-10 ℃/min, preserving the heat for 2 hours, heating to 900 ℃, preserving the heat for 2 hours, and naturally cooling to obtain the nitrogen-phosphorus co-doped carbon-based double-effect catalyst.
Example 2
0.190g (0.546mmol) of hexachlorotriphosphazene, 0.200g (1.587mmol) of melamine and 0.060g of carbon nanotubes are weighed into 20ml of tetrahydrofuran, evenly mixed by ultrasonic, then transferred into a 50ml reaction kettle, heated to 120 ℃ and reacted for 24 hours.
And (3) carrying out suction filtration and washing on the generated product for a plurality of times by using deionized water and ethanol, putting the product into an oven for drying, and drying the product for 12h at 70 ℃. Obtaining the carbon-based material containing nitrogen and phosphorus. Transferring the synthesized carbon-based material containing nitrogen and phosphorus into a high-temperature furnace for calcination with the flow rate of 100mL min-1And heating the high-temperature furnace to 350 ℃ at the speed of 5-10 ℃/min, preserving the heat for 3 hours, heating to 950 ℃, preserving the heat for 2 hours, and naturally cooling to obtain the nitrogen-phosphorus co-doped carbon-based double-effect catalyst.
Comparative example 1
0.190g (0.546mmol) of hexachlorotriphosphazene and 0.060g of graphene oxide are weighed and added into 20ml of tetrahydrofuran, and the mixture is ultrasonically mixed uniformly, then transferred into a 50ml reaction kettle, heated to 110 ℃ and reacted for 24 hours.
And (3) carrying out suction filtration and washing on the generated product for a plurality of times by using deionized water and ethanol, drying in an oven, and drying for 12h at the temperature of 60 ℃. Obtaining the phosphorus-containing carbon-based material. Transferring the synthesized phosphorus-containing carbon-based material into a high-temperature furnace for calcination with the flow rate of 100mL min-1And then the temperature of the high-temperature furnace is increased to 350 ℃ at the speed of 5-10 ℃/min, the temperature is maintained for 2 hours, the temperature is increased to 900 ℃, and the temperature is maintained for 2 hours and then the temperature is naturally reduced to obtain the phosphorus-doped carbon-based double-effect catalyst.
Comparative example 2
0.200g (1.587mmol) of melamine and 0.060g of graphene oxide are weighed and added into 20ml of tetrahydrofuran, the mixture is evenly mixed by ultrasonic, then the mixture is transferred into a 50ml reaction kettle, the temperature is raised to 110 ℃, and the reaction is carried out for 24 hours.
And (3) carrying out suction filtration and washing on the generated product for a plurality of times by using deionized water and ethanol, drying in an oven, and drying for 12h at the temperature of 60 ℃. Obtaining the carbon-based material containing nitrogen. And transferring the synthesized nitrogen-containing carbon-based material into a high-temperature furnace for calcination, introducing argon with the flow rate of 100mL min < -1 >, heating the high-temperature furnace to 350 ℃ at the speed of 5-10 ℃/min, preserving the heat for 2 hours, heating to 900 ℃, preserving the heat for 2 hours, and naturally cooling to obtain the nitrogen-doped carbon-based double-effect catalyst.
Claims (10)
1. A preparation method of a nitrogen and phosphorus co-doped carbon-based nonmetal oxygen reduction/precipitation double-effect catalyst is characterized by comprising the following steps:
step 1) directly synthesizing a covalent organic polymer material containing nitrogen and phosphorus on the surface of a carbon material by using a phosphorus source and a nitrogen source, weighing a certain amount of the nitrogen source, the phosphorus source and the carbon material, mixing and dissolving the nitrogen source, the phosphorus source and the carbon material in an organic solvent, transferring the mixture to a reaction kettle, heating and maintaining the reaction kettle for a period of time, synthesizing a covalent organic polymer rich in nitrogen and phosphorus on a carbon carrier, uniformly and tightly combining the nitrogen and the phosphorus in the polymer on the carbon carrier, washing and filtering a generated product for several times by using a washing solution, and drying to obtain a carbon-based material containing nitrogen and phosphorus;
step 2) transferring the synthesized carbon-based material containing nitrogen and phosphorus into a porcelain boat, putting the porcelain boat into a high-temperature tube furnace for high-temperature calcination and pyrolysis for a certain time, carbonizing the porcelain boat in protective gas, and naturally cooling to obtain the nitrogen and phosphorus co-doped carbon-based non-metal oxygen reduction/precipitation double-effect catalyst;
step 1), heating the reaction kettle to 100-; the phosphorus-containing compound is one or more than two of triphenylphosphine, phytic acid and hexachlorotriphosphazene; the nitrogen-containing compound is one or more than two of melamine, urea, cyanamide and thiourea; in the step 1), the mass ratio of the phosphorus source to the nitrogen source to the carbon source is (1-2.6) to (1-1.6).
2. The preparation method of the nitrogen and phosphorus co-doped carbon-based non-metal oxygen reduction/precipitation double-effect catalyst according to claim 1, wherein the mass ratio of the phosphorus source, the nitrogen source and the carbon source in the step 1) is (1-1.8) to (1-1.3).
3. The preparation method of the nitrogen and phosphorus co-doped carbon-based nonmetal oxygen reduction/precipitation double-effect catalyst according to claim 1, wherein the mass ratio of the phosphorus source, the nitrogen source and the carbon source in the step 1) is (1-1.6) to (1-1.3).
4. The preparation method of the nitrogen and phosphorus co-doped carbon-based non-metal oxygen reduction/precipitation double-effect catalyst as claimed in claim 1, wherein the reaction temperature of the reaction kettle in the step 1) is raised to 100 ℃ and 130 ℃ and the reaction time is 18-24 hours.
5. The preparation method of the nitrogen and phosphorus co-doped carbon-based non-metal oxygen reduction/precipitation double-effect catalyst as claimed in claim 1, wherein the reaction temperature of the reaction kettle in the step 1) is raised to 110-120 ℃; the reaction time is 20-24 hours.
6. The preparation method of the nitrogen and phosphorus co-doped carbon-based non-metal oxygen reduction/precipitation double-effect catalyst according to claim 1, wherein the organic solvent in the step 1) is one or more than two of tetrahydrofuran, dimethylformamide and ethanol;
in the step of washing, filtering and drying, vacuum filtration is adopted, and the washing liquid is one or two of deionized water, ethanol and methanol solution; vacuum drying at 65-150 deg.C;
and 2) the protective gas used in the calcining pyrolysis process is high-purity nitrogen or argon, and the purity is more than or equal to 99.99%.
7. The preparation method of the nitrogen and phosphorus co-doped carbon-based non-metal oxygen reduction/precipitation double-effect catalyst according to claim 1, characterized in that the pyrolysis process in the step 2): heating to 430 ℃ at the rate of 5-10 ℃/min, preserving the heat for 0.5-5.0 hours, heating to 1100 ℃ at the rate of 5-10 ℃/min, and preserving the heat for 0.5-5.0 hours.
8. The preparation method of the nitrogen and phosphorus co-doped carbon-based non-metal oxygen reduction/precipitation double-effect catalyst according to claim 7, characterized in that the pyrolysis process comprises the following steps: heating to 380 ℃ at the speed of 5-8 ℃/min, preserving the heat for 0.5-3.0 hours, heating to 1000 ℃ at the speed of 5-8 ℃/min, and preserving the heat for 0.5-3.0 hours.
9. The preparation method of the nitrogen and phosphorus co-doped carbon-based non-metal oxygen reduction/precipitation double-effect catalyst according to claim 1, wherein the carbon material is one or more of graphite, carbon nanotubes, graphene and graphene oxide.
10. The nitrogen and phosphorus co-doped carbon-based non-metallic oxygen reduction/precipitation double-effect catalyst prepared by the method of any one of claims 1 to 9.
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