CN113937313A - Preparation method of iron-sulfur-phosphorus co-doped nano porous graphite catalyst - Google Patents
Preparation method of iron-sulfur-phosphorus co-doped nano porous graphite catalyst Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 24
- 239000010439 graphite Substances 0.000 title claims abstract description 24
- YBCFASPYBHNQOC-UHFFFAOYSA-N [P].[S].[Fe] Chemical compound [P].[S].[Fe] YBCFASPYBHNQOC-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 27
- 229910052742 iron Inorganic materials 0.000 claims abstract description 23
- 239000002105 nanoparticle Substances 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 239000012159 carrier gas Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 8
- -1 iron ions Chemical class 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- 230000002572 peristaltic effect Effects 0.000 claims description 7
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical group S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical group [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 5
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical group C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 4
- 229930192474 thiophene Natural products 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- UXCDUFKZSUBXGM-UHFFFAOYSA-N phosphoric tribromide Chemical compound BrP(Br)(Br)=O UXCDUFKZSUBXGM-UHFFFAOYSA-N 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 10
- 239000001257 hydrogen Substances 0.000 abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- 239000001301 oxygen Substances 0.000 abstract description 8
- 238000010306 acid treatment Methods 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000009467 reduction Effects 0.000 abstract description 7
- 239000000446 fuel Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000007667 floating Methods 0.000 abstract description 4
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical group [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004523 catalytic cracking Methods 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 229910021524 transition metal nanoparticle Inorganic materials 0.000 abstract description 2
- 239000010411 electrocatalyst Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000002086 nanomaterial Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 2
- 229910021385 hard carbon Inorganic materials 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- HQYNSFAFYFMRLG-UHFFFAOYSA-N tribromo phosphite Chemical compound BrOP(OBr)OBr HQYNSFAFYFMRLG-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M4/9091—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
-
- 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
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
-
- 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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- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
The invention discloses a preparation method of an iron-sulfur-phosphorus co-doped nano porous graphite catalyst. According to the invention, nitrogen is used as carrier gas, a nanoparticle precursor is prepared by a chemical vapor deposition method, and iron particles in the precursor are changed into iron ions to be adsorbed on sulfur-phosphorus functional groups by acid treatment, so that iron-sulfur-phosphorus co-doped nano porous carbon particles are obtained. According to the invention, the catalytic effect of transition metal nanoparticles is utilized to carry out floating catalytic cracking reaction in a floating catalytic reaction furnace to form nanoparticles with the diameter of 15-110 nm, the wall thickness of 0.79-5 nm and the number of graphite layers of 3-20, and the formed nanoparticles are wrapped by a graphite carbon layer. The nano-particles prepared by the method have the characteristics of adjustable size and shape, higher electrochemical activity and oxygen reduction catalytic activity, and can be used as an electrocatalyst of a hydrogen fuel cell. The preparation method has the advantages of low cost, fewer preparation procedures and simple operation, and is suitable for industrial production.
Description
Technical Field
The invention relates to a synthesis method of a hydrogen fuel cell cathode oxygen reduction catalyst, in particular to a preparation method of an iron-sulfur-phosphorus co-doped nano porous graphite catalyst, and belongs to the technical field of electrochemistry.
Background
With the development of the technology, the non-noble metal carbon material is approaching to the platinum catalyst rapidly in terms of catalytic activity and stability, and meanwhile, has the advantages of excellent conductivity, low cost and the like, and is increasingly favored by researchers. The mesoporous structure and the high specific surface area are reasonable structures of the catalyst material for improving the catalytic activity, wherein the mesoporous structure can provide more gas transmission channels, and the high specific surface area can provide more active center attachment points (New J.chem 41(2017) 15236-. The carbon nano material containing doping elements (such as boron, nitrogen, phosphorus, sulfur and the like) can improve the inherent structure of the carbon material due to introduction of heteroatoms such as N, B, P, S and the like, can form a p-type or n-type structure, breaks through the electroneutrality of the p-type or n-type structure, improves the porosity and the specific surface area of the material to a certain extent, generates more oxygen reduction catalytic active sites, enhances the adsorption capacity of oxygen, enhances the catalytic activity of the catalyst, improves the conductivity of the material, and can be applied to the fields of related electronic device materials or battery materials, so that the carbon nano material has important application value. The iron-sulfur-phosphorus co-doped carbon nano material is a relatively novel carbon nano material, is widely researched by researchers, and has important research significance in developing a simple, efficient and environment-friendly iron-sulfur-phosphorus co-doped nano material.
Referring to the existing literature, "sulfurous and phosphorous co-processed hard carbon derived from the slag of coal feedstock" published by Juan Ding et al in Journal of Alloys and Compounds (2021,851,156791) mentions a method for preparing a Sulfur-phosphorus co-doped carbon material, oak seed as a carbon source, washing oak seed with ethanol, drying at 100 deg.C, then carbonizing in a nitrogen atmosphere, pulverizing the sample, HF acidifying, synthesizing S/P co-doped hard carbon. Because the oak seeds contain impurities, and the sample needs to be ground in the preparation process, the heat treatment time is long, the loss of products is easily caused, the continuity and large-scale production of the phosphorus-nitrogen co-doped carbon nano material are restricted, and the method is not beneficial to realizing industrialization.
Disclosure of Invention
The technical problem solved by the invention is as follows: how to obtain a nano porous carbon particle catalyst which has excellent electrochemical activity, excellent stability and low cost.
In order to solve the technical problems, the invention provides a preparation method of an iron-sulfur-phosphorus co-doped nano porous graphite catalyst, which comprises the following steps:
step 1: preparing precursor nano particles by a chemical vapor deposition method: firstly, sequentially putting a carbon source, a sulfur source, a phosphorus source and an iron source into a flask for mixing to obtain a raw material mixture, inputting the raw material mixture into an ejector inside a vertical tubular furnace through an electronic peristaltic pump by taking nitrogen as carrier gas, then spraying the raw material mixture into a heating area of the vertical tubular furnace for chemical vapor deposition to obtain precursor nano particles, and enabling the precursor nano particles to leave the heating area of the tubular furnace along with the nitrogen, enter a receiving device connected with the vertical tubular furnace and be collected;
step 2: and (2) carrying out acid washing treatment on the precursor nano-particles collected in the step (1), converting iron particles in the precursor nano-particles into iron ions, filtering and washing, and freeze-drying the obtained product to obtain the iron-sulfur-doped nano-porous graphite catalyst.
Preferably, the carbon source in step 1 is acetone or ethanol, the sulfur source is carbon disulfide or thiophene, the phosphorus source is phosphorous acid or phosphorus oxybromide, and the iron source is iron acetylacetonate.
Preferably, the mass ratio of the carbon source, the sulfur source, the phosphorus source and the iron source is 10:2:1: 1-2: 2:1:2 in sequence.
Preferably, the nitrogen gas introducing rate in the step 1 is 40-300L/h; the input speed of the raw material mixture through an electronic peristaltic pump is 18-180 ml/h.
Preferably, the temperature of the vertical tube furnace in the step 1 is set to be 600-1200 ℃.
Preferably, the acid washing treatment in step 2 is carried out under the following conditions: the hydrochloric acid with the molar concentration of 4-12 mol/L is adopted for treatment, the treatment temperature is 50-90 ℃, and the treatment time is 2-8 hours.
Preferably, the conditions for freeze-drying in step 2 are: the temperature is-50 to-30 ℃, and the time is 2 to 4 days.
Compared with the prior art, the invention has the following beneficial effects:
1. firstly, fully mixing an iron source, a sulfur source and a carbon source, then respectively placing the mixture and a phosphorus source in a reaction chamber, taking nitrogen as a carrier gas, introducing the iron source, the sulfur source and the carbon source into another reaction chamber in a gaseous state, and finally introducing the raw materials into a high-temperature area of a vertical tubular furnace along with gas flow. The shape of a reaction product can be controlled by regulating the flow rate of gas, and a continuous preparation process that raw materials are input at one end of the tube furnace and the obtained product is collected at the other end is realized, so that the preparation efficiency is greatly improved; the device adopted by the invention has simple structure, is easy to operate and is suitable for continuous and industrial large-scale production;
2. the method adopts nitrogen as carrier gas, utilizes the catalytic effect of transition metal nano particles, performs floating catalytic cracking reaction in a floating catalytic reaction furnace, wraps the formed nano particles by a graphite carbon layer to form the nano particles with the diameter of 15-110 nm, detects that the wall thickness of the nano particles is 0.79-5 nm, and the number of graphite layers is 3-20; the catalyst is used for a hydrogen fuel cell cathode catalyst, the oxygen reduction initial potential reference reversible hydrogen electrode is 0.87-0.95V, and the dynamic current density Jk is 4-6.5 mA/cm2。
Detailed Description
In order that the invention may be more fully understood, preferred embodiments are now described in detail.
Example 1
Placing the carbon source which is ethanol, the sulfur source which is thiophene, the phosphorus source which is phosphorous acid and the iron source which is iron acetylacetonate into a flask for mixing according to the mass ratio of 10:2:1: 1; the nitrogen serves as a carrier gas, the raw material solution is input into an ejector in the vertical tube furnace through an electronic peristaltic pump at the input speed of 180 ml/h, and then is sprayed into a high-temperature area of the tube furnace, the temperature of the vertical furnace is set at 600 ℃, after chemical vapor deposition, the obtained precursor nanoparticles leave the high-temperature area of the tube furnace along with the nitrogen, are taken out by the carrier gas, and are collected by a device connected outside the furnace; and (3) carrying out acid washing treatment on the obtained precursor to change iron particles in the precursor nano particles into iron ions, wherein hydrochloric acid with the molar concentration of 12mol/L is adopted as an acid treatment solution. The temperature of the acid treatment was controlled at 90 ℃ for 8 hours. Followed by filtration and washing 1 time; freeze-drying at-30 deg.C for 4 days to obtain iron sulfur phosphorus co-doped nano porous graphite catalyst.
The implementation effect is as follows: forming hollow carbon spheres with the diameter of 15nm, and detecting to obtain hollow carbon spheres with the wall thickness of 0.79nm and 3 graphite layers; the catalyst is used for a cathode catalyst of a hydrogen fuel cell, the oxygen reduction initial potential reference reversible hydrogen electrode is 0.93V, and the dynamic current density Jk is 5mA/cm2。
Example 2
Placing the carbon source which is acetone, the sulfur source which is carbon disulfide, the phosphorus source which is tribromooxyphosphorus and the iron source which is iron acetylacetonate in a flask for mixing according to the mass ratio of 2:2:1: 2; the nitrogen serves as a carrier gas, the raw material solution is input into an ejector in the vertical tube furnace through an electronic peristaltic pump at the input speed of 18 ml/h, and then is sprayed into a high-temperature area of the tube furnace, the temperature of the vertical furnace is set at 1200 ℃, after chemical vapor deposition, the obtained precursor nanoparticles leave the high-temperature area of the tube furnace along with the nitrogen, are taken out by the carrier gas, and are collected by a device connected outside the furnace; and (3) carrying out acid washing treatment on the obtained precursor to change iron particles in the precursor nano particles into iron ions, wherein hydrochloric acid with the molar concentration of 4mol/L is adopted as an acid treatment solution. The temperature of the acid treatment was controlled at 50 ℃ for 2 hours. Followed by filtration and washing 1 time; freeze-drying at-50 deg.C for 2 days to obtain iron sulfur phosphorus co-doped nano porous graphite catalyst.
The implementation effect is as follows: is formed to have a diameter ofDetecting 110nm hollow carbon spheres to obtain hollow carbon spheres with the wall thickness of 5nm and 20 graphite layers; the catalyst is used for a cathode catalyst of a hydrogen fuel cell, the oxygen reduction initial potential reference reversible hydrogen electrode is 0.87V, and the dynamic current density Jk is 4mA/cm2。
Example 3
Placing the carbon source which is acetone, the sulfur source which is carbon disulfide, the phosphorus source which is phosphorous acid and the iron source which is iron acetylacetonate in a flask for mixing according to the mass ratio of 3:1:1: 3; the nitrogen serves as a carrier gas, the raw material solution is input into an ejector in the vertical tube furnace through an electronic peristaltic pump at the input speed of 60 ml/h, and then is sprayed into a high-temperature area of the tube furnace, the temperature of the vertical furnace is set at 750 ℃, after chemical vapor deposition, the obtained precursor nanoparticles leave the high-temperature area of the tube furnace along with the nitrogen, are taken out by the carrier gas, and are collected by a device connected outside the furnace; and (3) carrying out acid washing treatment on the obtained precursor to change iron particles in the precursor nano particles into iron ions, wherein hydrochloric acid with the molar concentration of 8mol/L is adopted as an acid treatment solution. The temperature of the acid treatment was controlled at 70 ℃ for 6 hours. Followed by filtration and washing 1 time; freeze-drying at-40 deg.C for 3 days to obtain iron sulfur phosphorus co-doped nano porous graphite catalyst.
The implementation effect is as follows: forming hollow carbon spheres with the diameter of 30nm, and detecting to obtain hollow carbon spheres with the wall thickness of 1.5nm and 5-7 graphite layers; the catalyst is used for a cathode catalyst of a hydrogen fuel cell, the oxygen reduction initial potential reference reversible hydrogen electrode is 0.95V, and the dynamic current density Jk is 6.5mA/cm2。
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.
Claims (7)
1. The preparation method of the iron-sulfur-phosphorus co-doped nano porous graphite catalyst is characterized by comprising the following steps of:
step 1: preparing precursor nano particles by a chemical vapor deposition method: firstly, sequentially putting a carbon source, a sulfur source, a phosphorus source and an iron source into a flask for mixing to obtain a raw material mixture, inputting the raw material mixture into an ejector inside a vertical tubular furnace through an electronic peristaltic pump by taking nitrogen as carrier gas, then spraying the raw material mixture into a heating area of the vertical tubular furnace for chemical vapor deposition to obtain precursor nano particles, and enabling the precursor nano particles to leave the heating area of the tubular furnace along with the nitrogen, enter a receiving device connected with the vertical tubular furnace and be collected;
step 2: and (2) carrying out acid washing treatment on the precursor nano-particles collected in the step (1), converting iron particles in the precursor nano-particles into iron ions, filtering and washing, and freeze-drying the obtained product to obtain the iron-sulfur-doped nano-porous graphite catalyst.
2. The method for preparing the iron-sulfur-phosphorus co-doped nano porous graphite catalyst according to claim 1, wherein the carbon source in the step 1 is acetone or ethanol, the sulfur source is carbon disulfide or thiophene, the phosphorus source is phosphorous acid or phosphorus oxybromide, and the iron source is iron acetylacetonate.
3. The preparation method of the iron-sulfur-phosphorus co-doped nano porous graphite catalyst according to claim 2, wherein the mass ratio of the carbon source to the sulfur source to the phosphorus source to the iron source is 10:2:1: 1-2: 2:1:2 in sequence.
4. The preparation method of the iron-sulfur-phosphorus co-doped nano porous graphite catalyst according to claim 1, wherein the nitrogen gas is introduced at a rate of 40-300 l/h in the step 1; the input speed of the raw material mixture through an electronic peristaltic pump is 18-180 ml/h.
5. The preparation method of the iron-sulfur-phosphorus co-doped nano porous graphite catalyst according to claim 1, wherein the temperature of the vertical tube furnace in the step 1 is set to 600-1200 ℃.
6. The preparation method of the iron-sulfur-phosphorus co-doped nano porous graphite catalyst according to claim 1, wherein the acid washing in the step 2 is performed under the following conditions: the hydrochloric acid with the molar concentration of 4-12 mol/L is adopted for treatment, the treatment temperature is 50-90 ℃, and the treatment time is 2-8 hours.
7. The preparation method of the iron-sulfur-phosphorus co-doped nano porous graphite catalyst according to claim 1, wherein the freeze-drying conditions in the step 2 are as follows: the temperature is-50 to-30 ℃, and the time is 2 to 4 days.
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