CN105457666A - Nitrogen and phosphorus co-doped porous carbon catalyst and preparation method thereof - Google Patents
Nitrogen and phosphorus co-doped porous carbon catalyst and preparation method thereof Download PDFInfo
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- CN105457666A CN105457666A CN201510888720.0A CN201510888720A CN105457666A CN 105457666 A CN105457666 A CN 105457666A CN 201510888720 A CN201510888720 A CN 201510888720A CN 105457666 A CN105457666 A CN 105457666A
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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 provides a preparation method and an application of a nitrogen and phosphorus co-doped porous carbon catalyst and belongs to the field of oxygen reduction catalysts for a fuel cell cathode. Nitrogen and phosphorus are introduced with an in-situ doping method, and the nitrogen and phosphorus doping amount is changed by adjusting the content of a nitrogen and phosphorus precursor. Besides, nitrogen and phosphorus co-doped porous carbon is prepared with a hard template method, and controllability of pore diameters of the porous carbon is realized by adjusting a hard template. The method comprises steps as follows: an earlier polymer of aniline monomers, a phosphorus precursor, a silica-based hard template and non-precious metal salt is prepared; the earlier polymer is calcined, and solids are obtained; the solids are etched, cleaned and dried, and the carbon material is obtained. More importantly, the prepared nitrogen and phosphorus co-doped porous carbon material has an excellent oxygen reduction electro-catalytic property under the acid condition and has huge application potential.
Description
Technical field
The present invention relates to and belongs to fuel battery negative pole oxygen reduction catalyst field, is specifically related to the nitrogen co-doped porous carbon Catalysts and its preparation method of a kind of phosphorus.
Background technology
Fuel cell be a kind of the chemical energy of fuel efficiently and be environmentally friendly directly changed into the TRT of electric energy, it is high that it has energy conversion rate; Environmental pollution is little; Starting time is short; The advantages such as fuel variation, being described as is forth generation generation technology after waterpower, firepower, nuclear energy.Fuel battery negative pole oxygen reduction reaction speed is slow, must use the very high load of catalytic activity Pt nano particle on the carbon material in actual applications as catalyst to improve hydrogen reduction speed.But catalyst based expensive, the occurring in nature reserves of noble metal platinum used are rare, catalytic efficiency is low, poor stability, this limits large-scale commercial application of fuel cell largely.Therefore, develop cheap, material source is extensive, catalytic performance is high, the non-precious metal catalyst of excellent in stability is significant.The research of nitrogen-doped carbon material in recent years has made great progress, and phosphorus is as the element of the same clan with nitrogen, and the two has identical valence electron number, so chemical property is also similar.Phosphorus atoms radius is larger simultaneously, and electron supplying capacity is also stronger, and phosphorus atoms mixes and electron spin density can be caused asymmetric, so be also the hetero atom of doping type material with carbon element hot topic.Research finds, introduces the second active element phosphorus in nitrogen-doped carbon material, can be improved the cooperative effect of catalyst by the content, ratio etc. regulating and controlling phosphorus atoms, thus improves the activity of catalyst.But, under acid condition, the nitrogen co-doped material with carbon element of phosphorus is still in the starting stage as oxygen reduction catalyst, therefore be necessary to prepare different types of nitrogen-phosphor codoping material with carbon element, by regulating and controlling its structure, doped chemical content to improve the ability of its catalytic oxidation-reduction in acid medium.
Summary of the invention
The present invention aims to provide a kind of nitrogen-phosphor codoping porous carbon catalyst in order to oxygen reduction reaction under catalysis acid condition.Its component comprises aniline monomer, phosphorus presoma, oxidant, base metal salt, silica-based hard template.Nitrogen-phosphor codoping porous carbon method for preparing catalyst of the present invention, step is as follows:
(1) aniline monomer, phosphorus presoma, base metal salt, silica-based hard template are joined in acid flux material, the oxidant causing aniline monomer polymerization is added after ultrasonic 0.5 ~ 1h, at 0 ~ 80 DEG C, stir polymerization 8 ~ 24h, then round bottom sesame seed cake is proceeded to, at 80 ~ 120 DEG C, oil bath 8 ~ 24h obtains polymer 1 in early stage.
(2) by dry for polymer 1 in early stage, solid 1 is obtained, under nitrogen or argon atmosphere, solid 1 is carried out high-temperature calcination, is specially and is warming up to 700 ~ 1000 DEG C with the speed of 1 ~ 10 DEG C/min, keep 0.5 ~ 1h at this temperature, after dropping to room temperature, take out, obtain solid 2.
(3) solid 2 is ground, add the etching agent hydrogen fluoride amine aqueous solution of silica-based hard template, at room temperature stir 12 ~ 48h, after washing, centrifugal, drying, obtain nitrogen-phosphor codoping porous carbon catalyst of the present invention.
Phosphorus presoma described in step (1) be one in phosphoric acid, triphenyl phosphorus, tetran-butylphosphonium bromide phosphine, ferric phosphate and more than.
Base metal salt described in step (1) be one in ferric nitrate, cobalt nitrate, FePC, Cobalt Phthalocyanine, ferric phosphate and more than.
Silica-based hard template described in step (1) is the one in silica nanosphere and mesoporous silica molecular sieve material.
Described in step (1), acid medium is H
2sO
4one in solution and HCl solution.
The oxidant causing aniline monomer polymerization described in step (1) is H
2o
2solution and (NH
4)
2s
2o
8one in solution.
Described in step (1), the mass ratio of aniline monomer and phosphorus presoma is 1:(0.01 ~ 0.6).
Described in step (1), the mass ratio of aniline monomer and base metal salt is 1:(0.0125 ~ 0.5).
Described in step (1), the mass ratio of aniline monomer and silica-based hard template is 1:(0.25 ~ 5).
Described in step (1), the mol ratio of aniline monomer and acid flux material is 1:(1 ~ 8), the concentration range of acid flux material is 0.5 ~ 2mol/L.
The mol ratio of the oxidant of aniline monomer described in step (1) and its polymerization of initiation is 1:(1 ~ 5).
The mass content of the hydrogen fluoride amine aqueous solution added in step (3) is 1 ~ 63%, and addition is can fully dissolved solid 2 be as the criterion.
Described in step (3), baking temperature is 40 ~ 80 DEG C, and drying time is 12 ~ 48h.
Present invention also offers the application of oxygen reduction reaction under a kind of nitrogen-phosphor codoping porous carbon catalyst acid condition.Electrochemical results shows, prepared porous carbon materials is at 0.5MH
2sO
4show good electrocatalysis characteristic in solution, such as, in example one, resulting materials is at O
2saturated 0.5MH
2sO
4have obvious hydrogen reduction peak to occur in solution, and reduction peak current potential is 0.24V.
Beneficial effect:
The present invention adopts in-situ doped method to introduce nitrogen and phosphorus, nitrogen phosphorus doping amount is changed by the content of regulation and control nitrogen phosphorus precursor, make to occur defect near adjacent carbon atom in the porous carbon materials of synthesis, distribution of charges is uneven, is more conducive to the activated centre constructing oxygen molecule absorption and reduction.In addition, adopt hard template method to prepare nitrogen-phosphor codoping porous carbon, the aperture realizing porous carbon by regulation and control hard template is controlled, and suitable aperture is conducive to the transmission of reactant and product in hydrogen reduction process.Compared with nitrogen-phosphor codoping porous carbon in the past, preparation method of the present invention is simple, with low cost, and the nitrogen-phosphor codoping porous carbon materials of synthesis has good hydrogen reduction electrocatalysis characteristic in acid condition, has very large application potential.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the nitrogen-phosphor codoping porous carbon catalyst of preparation in example 2.
Fig. 2 is the transmission electron microscope picture of the nitrogen-phosphor codoping porous carbon catalyst of preparation in example 1.
Fig. 3 is the cyclic voltammetry result of the nitrogen-phosphor codoping porous carbon catalyst of preparation in example 1.
Detailed description of the invention
For making object of the present invention, technology, advantage definitely, below in conjunction with in the embodiment of the present invention, the technical scheme in the embodiment of the present invention being clearly and completely described, but being not limited thereto.For those skilled in the art, under the prerequisite not departing from embodiment of the present invention principle, can also make some improvements and modifications, these improvements and modifications are also considered as the protection domain of the embodiment of the present invention.
Embodiment 1
(1) 2g aniline monomer, 0.34g tetran-butylphosphonium bromide phosphine, 0.4g FePC, 5g silica nanosphere are joined in the hydrochloric acid solvent of 10mL, 2mol/L, ultrasonic 40min mixes, under agitation add the ammonium persulfate aqueous solution of 10mL, 1mol/L, and use ice-water bath to make temperature maintain 0 DEG C of stirring polymerization 24h, then round bottom sesame seed cake is proceeded to, at 100 DEG C, oil bath 12h.
(2) reactant is dry under 80 DEG C of water-baths, obtain solid product, under nitrogen atmosphere encloses, solid product is carried out high-temperature calcination, be specially and be warming up to 800 DEG C with the speed of 10 DEG C/min, keep 30min at this temperature, take out after naturally dropping to room temperature, obtain the mixture of nitrogen-phosphor codoping porous carbon materials and silica.
(3) the solid abrasive powdered of taking-up is weighed, and take 1g solid and join etching silicon dioxide nanosphere in the ammonium acid fluoride aqueous solution of 40m, 4mol/L, clean by washed with de-ionized water after at room temperature stirring 24h, dry 15h at 70 DEG C, obtains nitrogen-phosphor codoping porous carbon catalyst of the present invention.
Embodiment 2
(1) 2g aniline monomer, 0.1g ferric phosphate, 4g silica nanosphere are joined in the sulfuric acid solvent of 10mL, 0.5mol/L, ultrasonic 30min mixes, under agitation add the hydrogen peroxide solution of 20ml, 0.925mol/L, and be polymerized 24h at using ice-water bath to make temperature maintain 0 DEG C, then round bottom sesame seed cake is proceeded to, at 120 DEG C, oil bath 15h.
(2) reactant is dry under 80 DEG C of water-baths, obtain solid product, under nitrogen atmosphere encloses, solid product is carried out high-temperature calcination, be specially and be warming up to 700 DEG C with the speed of 5 DEG C/min, keep 1h at this temperature, take out after naturally dropping to room temperature, obtain the mixture of nitrogen-phosphor codoping porous carbon materials and silica.
(3) the solid abrasive powdered of taking-up is weighed, and take 1g solid and join etching silicon dioxide nanosphere in the ammonium acid fluoride aqueous solution of 40mL4mol/L, clean by washed with de-ionized water after at room temperature stirring 24h, dry 24h at 80 DEG C, obtains nitrogen-phosphor codoping porous carbon catalyst of the present invention.
Claims (10)
1. a preparation method for nitrogen-phosphor codoping porous carbon catalyst, comprises the following steps:
(1) aniline monomer, phosphorus presoma, base metal salt, silica-based hard template are joined in acid flux material, the oxidant causing aniline monomer polymerization is added after ultrasonic 0.5 ~ 1h, at 0 ~ 80 DEG C, stir polymerization 8 ~ 24h, then round bottom sesame seed cake is proceeded to, at 80 ~ 120 DEG C, oil bath 8 ~ 24h obtains polymer 1 in early stage.
(2) by dry for polymer 1 in early stage, solid 1 is obtained, under nitrogen or argon atmosphere, solid 1 is carried out high-temperature calcination, is specially and is warming up to 700 ~ 1000 DEG C with the speed of 1 ~ 10 DEG C/min, keep 0.5 ~ 1h at this temperature, after dropping to room temperature, take out, obtain solid 2.
(3) solid 2 is ground, adds the etching agent hydrogen fluoride amine aqueous solution of silica-based hard template, at room temperature stir 12 ~ 48h, washing, centrifugal, at 40 ~ 80 DEG C, after dry 12 ~ 48h, obtain nitrogen-phosphor codoping porous carbon catalyst of the present invention.
2. the preparation method of nitrogen-phosphor codoping porous carbon catalyst according to claim 1, is characterized in that: described phosphorus presoma be one in phosphoric acid, triphenyl phosphorus, tetran-butylphosphonium bromide phosphine, ferric phosphate and more than.
3. the preparation method of nitrogen-phosphor codoping porous carbon catalyst according to claim 1, is characterized in that: described base metal salt be one in ferric nitrate, cobalt nitrate, FePC, Cobalt Phthalocyanine, ferric phosphate and more than.
4. the preparation method of nitrogen-phosphor codoping porous carbon catalyst according to claim 1, it is characterized in that: described silica-based hard template is the one in silica nanosphere and mesoporous silica molecular sieve material, and the mass ratio of described aniline monomer and silica-based hard template is 1:(0.25 ~ 5).
5. the preparation method of nitrogen-phosphor codoping porous carbon catalyst according to claim 1, is characterized in that: described acid medium is H
2sO
4one in solution and HCl solution, the mol ratio of aniline monomer and acid flux material is 1:(1 ~ 8), the concentration range of acid flux material is 0.5 ~ 2mol/L.
6. the preparation method of nitrogen-phosphor codoping porous carbon catalyst according to claim 1, is characterized in that: the oxidant of described initiation aniline monomer polymerization is H
2o
2solution and (NH
4)
2s
2o
8one in solution, the mol ratio of the oxidant of aniline monomer and its polymerization of initiation is 1:(1 ~ 5).
7. the preparation method of nitrogen-phosphor codoping porous carbon catalyst according to claim 1, is characterized in that: the mass ratio of described aniline monomer and phosphorus presoma is 1:(0.01 ~ 0.6).
8. the preparation method of nitrogen-phosphor codoping porous carbon catalyst according to claim 1, is characterized in that: the mass ratio of described aniline monomer and base metal salt is 1:(0.0125 ~ 0.5).
9. the preparation method of nitrogen-phosphor codoping porous carbon catalyst according to claim 1, it is characterized in that: the mass content of the hydrogen fluoride amine aqueous solution added is 1 ~ 63%, addition is can fully dissolved solid 2 be as the criterion.
10. according to claim 1 the nitrogen-phosphor codoping porous carbon catalyst prepared of method as the application of oxygen reduction electro-catalyst under acid condition.
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| CN106006599A (en) * | 2016-05-11 | 2016-10-12 | 浙江工业大学 | Synthesizing method and application of high-S-content P-S-N-codoped mesoporous carbon material |
| CN106006549A (en) * | 2016-06-30 | 2016-10-12 | 上海电力学院 | Heteroatom doped hollow carbon sphere material loaded precious metal nano particle and preparation thereof |
| CN106207204A (en) * | 2016-09-19 | 2016-12-07 | 青岛科技大学 | Nitrogen sulfur difunctional VPO catalysts of codope material with carbon element and its preparation method and application |
| CN106328905A (en) * | 2016-11-04 | 2017-01-11 | 中南大学 | Preparation method for coralline nitrogen and phosphorus co-doped carbon composite material and application of composite material in sodium-ion battery |
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| CN113991093B (en) * | 2021-10-27 | 2023-09-22 | 重庆硕盈峰新能源科技有限公司 | Preparation of heteroatom in-situ doped porous carbon and application of heteroatom in high-rate sodium ion battery |
| CN113991094B (en) * | 2021-10-27 | 2023-09-22 | 重庆硕盈峰新能源科技有限公司 | Heteroatom in-situ doped porous carbon composite lithium anode and preparation method and application thereof |
| CN114308103A (en) * | 2021-12-24 | 2022-04-12 | 西安理工大学 | Preparation method of porous cellulose palladium-loaded composite material for sewage treatment |
| CN114959785A (en) * | 2022-05-06 | 2022-08-30 | 浙江大学衢州研究院 | Phosphorus-nitrogen co-doped carbon gel electrocatalyst and preparation method and application thereof |
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