CN107661772B - A kind of Nonmetal oxygen reduction catalyst and the preparation method and application thereof - Google Patents
A kind of Nonmetal oxygen reduction catalyst and the preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- 239000001301 oxygen Substances 0.000 title claims abstract description 71
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 71
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052755 nonmetal Inorganic materials 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011574 phosphorus Substances 0.000 claims abstract description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 13
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 7
- 239000011591 potassium Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- FENRSEGZMITUEF-ATTCVCFYSA-E [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].OP(=O)([O-])O[C@@H]1[C@@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H]1OP(=O)([O-])[O-] Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].OP(=O)([O-])O[C@@H]1[C@@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H]1OP(=O)([O-])[O-] FENRSEGZMITUEF-ATTCVCFYSA-E 0.000 claims abstract description 4
- 229940083982 sodium phytate Drugs 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000012298 atmosphere Substances 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 8
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229940068041 phytic acid Drugs 0.000 claims description 7
- 239000000467 phytic acid Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 abstract description 14
- 239000000446 fuel Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 229910000510 noble metal Inorganic materials 0.000 abstract description 7
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 abstract 3
- 238000006722 reduction reaction Methods 0.000 description 70
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000002083 X-ray spectrum Methods 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000036228 toxication Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of Nonmetal oxygen reduction catalysts and the preparation method and application thereof.The Nonmetal oxygen reduction catalyst is the porous carbon materials of nitrogen phosphorus codope, preparation method includes the following steps: 1) under non-oxidizing conditions, a kind of in calcining POTASSIUM PHYTATE, sodium phytate, and then centrifugal drying is washed by acid or aqueous solution, phosphorus doping porous carbon materials are prepared.2) it is heat-treated after mixing the phosphorus doping porous carbon materials of preparation with nitrogen source, then nitrogen phosphorus codope porous carbon materials is obtained by washing and drying.Nonmetal oxygen reduction catalyst provided by the present invention, that is, nitrogen phosphorus codope porous carbon materials can be used as oxygen reduction catalyst, and hydrogen reduction catalytic performance is close to business platinum carbon catalyst.Preparation method of the present invention is simple, it is low in cost, have excellent performance, be suitable for large-scale production fuel cell non noble metal oxygen reduction catalyst, the potential replacer as fuel cell oxygen reduction noble metal catalyst.
Description
Technical field
The invention belongs to catalyst field, it is related to a kind of Nonmetal oxygen reduction catalyst and the preparation method and application thereof.
Background technique
Fuel cell is a kind of device for directly converting chemical energy to electric energy.It has energy conversion efficiency height, environment
The outstanding features such as close friend, low operation temperature, specific power and specific energy height, it is considered to be the following electric car and other civilian occasions
Most promising electrochmical power source.Noble metal is reacted usually as fuel battery cathod catalyst with catalytic oxidation-reduction, but its reserves
Rare, at high price, stability is poor and the low disadvantage of selectivity hinders the scale of fuel cell significantly and uses.Therefore, it opens
Hair it is cheap, sustainable, high performance non noble metal oxygen reduction catalyst has very the commercialization process of fuel cell
Important meaning.
Recent domestic has carried out a large amount of research to non-noble metal preparation, and non-precious metal catalyst can generally divide
For following several classes: carbon material, the oxide based on transition metal or the sulfide or nitride or nitrogen oxides of Heteroatom doping,
The carbon material modified based on iron/cobalt and nitrogen.Wherein non-metallic catalyst shows preferable hydrogen reduction catalytic performance, still
Most of Nonmetal oxygen reduction catalyst preparation method is all complex, expends a large amount of manpower and material resources, and preparation process item
Part is not easy to control, and single preparation can only obtain a small amount of catalyst, is unfavorable for the large-scale production of catalyst.Therefore it develops a kind of low
Cost, high activity, simple process, the Nonmetal oxygen reduction catalyst suitable for large-scale production, the industrialization for fuel cell
It is of great significance.
Summary of the invention
The object of the present invention is to provide a kind of Nonmetal oxygen reduction catalysts and the preparation method and application thereof.
The preparation method of preparation Nonmetal oxygen reduction catalyst provided by the invention, includes the following steps:
1) under non-oxidizing conditions, calcining phytic acid metal salt obtains predecessor, and after acid processing, washing, it is heavy to be collected by centrifugation
It forms sediment, it is dry, obtain phosphorus doping porous carbon materials；
2) it is heat-treated after mixing phosphorus doping porous carbon materials obtained by step 1) with nitrogen source, obtains the nonmetallic oxygen
Reducing catalyst.
In the step 1) of the above method, in the above method, the phytic acid metal salt in POTASSIUM PHYTATE and sodium phytate extremely
Few one kind.
The non-oxidizing conditions are by being passed through at least one of nitrogen, argon gas, hydrogen and helium into reaction system
What gas obtained.
The condition of the calcining are as follows: calcination temperature is 300 DEG C -1500 DEG C, and calcination time is -10 hours 0.5 hour, heating
Rate is 0.5 DEG C/min-100 DEG C/min；
The calcination condition is concretely: calcination temperature is 600 DEG C -1000 DEG C, more specifically can for 800 DEG C or 900 DEG C or
1000℃；Calcination time is -3 hours 1 hour or -2 hours 1 hour, and heating rate is 3 DEG C/min-15 DEG C/min.
The method also includes following steps: after the calcining step, to calcined product successively with acid processing, water
It washes, precipitating is collected by centrifugation, it is dry.
The acid is selected from least one of hydrochloric acid, sulfuric acid, nitric acid and aqueous solution of hydrofluoric acid；The item with acid processing
Part are as follows: 5 DEG C -200 DEG C are handled -100 hours 0.1 hour；The concentration of the acid is specially 0.5-1.5mol/L, more specifically can be
1mol/L；Oxide impurity subsidiary in calcined product can be removed with acid processing.
Described to use the sour condition handled concretely: 20 DEG C -80 DEG C are handled -24 hours 12 hours, more specifically can be room temperature
Processing -24 hours 18 hours；
The purpose of washing and centrifugation is for further removing oxide impurity subsidiary in calcined product.
In the drying steps, dry atmosphere is vacuum or air or is passed through in following gases into reaction system extremely
It is few a kind of to obtain: nitrogen, argon gas, helium and carbon dioxide.
The drying is concretely 12 hours dry in air atmosphere or vacuum atmosphere；Dry temperature is concretely
70-90 DEG C, more specifically can be 80 DEG C；
In the vacuum atmosphere, vacuum degree is specifically les than < 105Pa。
In the step 2), the nitrogen source is selected from least one of melamine, cyanamide and dicyandiamide；
In the heat treatment step, the atmosphere of heat treatment is selected from least one of nitrogen, argon gas, hydrogen and helium gas
Body.
In the step 2) mixing step, mixed mode is grinding；The phosphorus doping porous carbon materials and the nitrogen source
The mass ratio that feeds intake can be for 1:1-1:50, concretely 1:5-1:40, more specifically can be 1:20；
In the step 2) heat treatment step, the temperature of heat treatment is 700 DEG C -1000 DEG C, concretely 800 DEG C -1000
℃；The heat treatment time can be -8 hours 0.5 hour, concretely 2 hours.
The method also includes following steps: after the step 2) heat treatment step, washing, is centrifuged to system
And drying；
The actual conditions of the centrifugation are as follows: revolving speed is 8000-1000 revolutions per seconds；Time is 3-10 minutes；
The actual conditions of the drying are 12 hours dry in air atmosphere or vacuum atmosphere；
Dry temperature is specially 70-90 DEG C or 80 DEG C；
In the vacuum atmosphere, vacuum degree is specifically les than < 105Pa。
In addition, a kind of Nonmetal oxygen reduction catalyst is also claimed in the present invention, which contains
The carbon material of nitrogen and P elements doping, and there is micropore and meso-hole structure；
The specific surface area of the Nonmetal oxygen reduction catalyst is 910~1294cm2/g；Pore volume be 2.99~
3.46cm3/g；Aperture is 0.5nm-20nm.
Specifically, the Nonmetal oxygen reduction catalyst being prepared according to the method described above, also belongs to protection model of the invention
It encloses.
In addition, above-mentioned Nonmetal oxygen reduction catalyst as in oxygen reduction catalyst application and the nonmetallic oxygen also
Application of the raw catalyst in oxygen reduction reaction or the application in catalytic oxidation-reduction reaction, also belong to protection model of the invention
It encloses.
Preparation method provided by the invention is mainly direct high-temperature calcination phytic acid metal salt, and wherein phytic acid root can be directly as
Carbon source, carbonization forms carbon material at high temperature；Metal is reduced into metallic state simple substance at high temperature, and the metallic state simple substance is in high temperature
The carbon material being formed in situ can be corroded down, to realize porous structure；P elements in phytic acid metal salt can be used as phosphorus source,
Original position phosphorus doping carbon can be achieved in carbon material forming process；Gained phosphorus doping porous carbon materials are mixed with nitrogen source, in tube furnace
In under certain temperature be heat-treated a period of time, to obtain Nonmetal oxygen reduction catalyst of the invention.
The present invention has the following characteristics that compared with other prior arts
1, the cost of raw material provided in the present invention is cheap, from a wealth of sources.
2, the Nonmetal oxygen reduction catalyst that preparation method employed in the present invention obtains is compared to other porous carbons
Expect specific surface area with higher, biggish hole appearance and micropore and meso-hole structure.
3, preparation method of the present invention uses cheap melamine, cyanamide etc. for nitrogen source, with other nitrogen sources such as ammonia, hydrogen
Cyanic acid is compared, and doping process is relatively safe, and inventory is easily controllable.
4, Nonmetal oxygen reduction catalyst catalytic performance prepared by the present invention is excellent, other nonmetallic urges with reported in the literature
Agent, which is compared, has higher oxygen reduction activity.Its hydrogen reduction catalytic performance is close to business platinum carbon catalyst.It is a kind of cheap, high
Effect, the oxygen reduction catalyst of noble metal can be substituted, therefore can be applied in fuel cell field.
5, preparation method simple process of the present invention, economy, operate conveniently, be suitable for large-scale production the nonmetallic oxygen of fuel cell
Reducing catalyst, the potential replacer as fuel cell noble metal oxygen reduction catalyst, while in many industrial catalysts
Or other scientific domains have huge potential using value.
Detailed description of the invention
Fig. 1 is the X-ray powder diffraction curve (a) of Nonmetal oxygen reduction catalyst prepared by the embodiment of the present invention 1 and swashs
Light Raman spectrum analysis curve (b).
Fig. 2 is electron scanning micrograph (Fig. 2 of Nonmetal oxygen reduction catalyst prepared by the embodiment of the present invention 1
And transmission electron microscope photo (Fig. 2 (b-d)) (a)).
Fig. 3 is the energy dispersion X ray spectrum elemental map of Nonmetal oxygen reduction catalyst prepared by the embodiment of the present invention 1
Figure.
Fig. 4 is nitrogen adsorption-desorption isotherm curve of Nonmetal oxygen reduction catalyst prepared by the embodiment of the present invention 1
(Fig. 4 (a)) and pore-size distribution test curve (Fig. 4 (b)).
Fig. 5 is Nonmetal oxygen reduction catalyst prepared by the embodiment of the present invention 1 and the platinum carbon catalyst being commercially used
Hydrogen reduction empirical curve.
Fig. 6 is Nonmetal oxygen reduction catalyst prepared by the embodiment of the present invention 1 and the platinum carbon catalyst being commercially used
Stability test empirical curve.
Fig. 7 is Nonmetal oxygen reduction catalyst prepared by the embodiment of the present invention 1 and the platinum carbon catalyst being commercially used
Methanol tolerance test experiments curve.
Specific embodiment
The present invention is further elaborated combined with specific embodiments below, but the present invention is not limited to following embodiments.Institute
State method is conventional method unless otherwise instructed.The raw material can obtain unless otherwise instructed from public commercial source.
Embodiment 1
1) 2g POTASSIUM PHYTATE being put into tube furnace, carries out high-temperature calcination in a nitrogen atmosphere, heating rate is 3 DEG C/min,
Calcination temperature is 800 DEG C, and calcination time is 1 hour, and cooled to room temperature obtains predecessor；The predecessor is every with 1 mole
It is handled 18 hours under the hydrochloric acid room temperature risen, then centrifugation is washed with deionized and collects precipitating to neutral for several times, obtained wet phosphorus and mix
Miscellaneous porous carbon, finally, under vacuum conditions by the wet phosphorus doping porous carbon, 80 DEG C drying 12 hours, both phosphorus doping is porous
Carbon material；
2) it after taking phosphorus doping porous carbon materials obtained by 0.1g step 1) and 2g melamine ground and mixed uniform again, is transferred to
It in crucible, is placed in the quartz ampoule of tube furnace, air half an hour is removed with nitrogen, then be warming up to 1000 DEG C, in nitrogen protection
Under carry out heat treatment 2 hours after, the product that is heat-treated；Heat-treated products are collected, centrifugation and the vacuum at 60 DEG C is washed with water
After drying, Nonmetal oxygen reduction catalyst is obtained.
Shown in X-ray powder diffraction curve such as Fig. 1 (a) of Nonmetal oxygen reduction catalyst manufactured in the present embodiment, Fig. 1
It (b) is the laser Raman spectroscopy curve of the present embodiment, as seen from the figure, Nonmetal oxygen reduction catalyst manufactured in the present embodiment
ID/IGRatio is 1.039, illustrates catalyst graphite degree with higher.
The electron scanning micrograph and transmission electron microscope of Nonmetal oxygen reduction catalyst manufactured in the present embodiment
For photo as shown in Fig. 2, wherein Fig. 2 (a) is electron scanning micrograph, Fig. 2 (b-d) is transmission electron microscope photo.
As seen from the figure, Nonmetal oxygen reduction catalyst manufactured in the present embodiment is in three-dimensional porous structure, and mesoporous pore size is 15nm or so, figure
The carbonization structure of the high-resolution lattice fringe 0.34nm energy corresponding diagram 1 (a) of 2 (d) carbon.
Energy dispersion X ray spectrum Element area profile such as Fig. 3 institute of Nonmetal oxygen reduction catalyst manufactured in the present embodiment
Show, it can be seen that nitrogen and phosphorus element is successfully adulterated in the catalyst.
Nitrogen adsorption-the desorption isotherm and graph of pore diameter distribution of Nonmetal oxygen reduction catalyst manufactured in the present embodiment are as schemed
Shown in 4: wherein (a) is nitrogen adsorption-desorption curve figure, (b) is pore size distribution curve figure.By scheming (a) it is found that the present embodiment institute
The specific surface area of the Nonmetal oxygen reduction catalyst of preparation is 1294cm2/g.By scheming (b) it is found that non-gold manufactured in the present embodiment
Belonging to oxygen reduction catalyst has micropore and meso-hole structure, and wherein micropore size is 0.5nm or so, and mesoporous pore size is 15nm or so.
The hydrogen reduction of Nonmetal oxygen reduction catalyst manufactured in the present embodiment and the platinum carbon catalyst being commercially used is tested
Curve is as shown in Figure 5.Specific experiment method are as follows: hydrogen-oxygen of the hydrogen reduction empirical curve rotating ring disk electrode (r.r.d.e) at 0.1 mole every liter
Change and measured in potassium solution, the revolving speed of rotating ring disk electrode (r.r.d.e) is 1600 rpms, and curved scanning rate is 10 millivolts per second；Test
Ring electrode current potential is constant at 0.5 volt relative to silver/silver chloride reference electrode (Klorvess Liquid that electrolyte is saturation) in the process.
The control platinum carbon catalyst being commercially used is that purchase is urged from Zhuan Xinwan rich (Johnson-Matthey) (Shanghai)
The business platinum carbon catalyst that the platinum weight percent content of agent Co., Ltd is 20%.
Compare two curves, it can be seen that the Nonmetal oxygen reduction catalyst that the present embodiment is prepared is in hydrogen reduction reality
The half wave potential for testing middle performance is 0.828 volt (relative to standard hydrogen electrode), and the half wave potential of platinum carbon catalyst is only used than business
0.85 volt low 22 millivolts, and between 0.3 volt to 0.8 volt, the yield of the hydrogen peroxide on ring-disc electrode is below 10%, right
The electron transfer number answered shows good hydrogen reduction catalytic performance also close to 4.
The stability test of Nonmetal oxygen reduction catalyst and the platinum carbon catalyst being commercially used prepared by the present embodiment 1
Empirical curve is as shown in Figure 6.Specific experiment method are as follows: chrono-amperometric empirical curve rotating disk electrode (r.d.e) is saturated in oxygen
It is measured in 0.1 mole every liter of potassium hydroxide solution, the revolving speed of rotating disk electrode (r.d.e) is 1600 rpms, constant potential 0.7
Volt, curved scanning rate are 10 millivolts per second, and the testing time is 20000 seconds.
Compare two curves, it can be seen that the Nonmetal oxygen reduction catalyst and business platinum carbon that the present embodiment is prepared
Catalyst passes through 20000 seconds 0.7 volt of (relative to mark hydrogen electrode) constant potential aging, and the present embodiment is prepared nonmetallic
The kinetic current of oxygen reduction catalyst was the 75% of beginning kinetic current after 20000 seconds, was higher than business platinum carbon catalyst
58%, this shows that Nonmetal oxygen reduction catalyst that the present embodiment is prepared has preferably compared to business with platinum carbon catalyst
Stability.
The methanol tolerance of Nonmetal oxygen reduction catalyst manufactured in the present embodiment and the platinum carbon catalyst being commercially used is surveyed
It is as shown in Figure 7 to try empirical curve.Specific experimental method are as follows: in 0.1 mole every liter of potassium hydroxide solution and be mixed with 0.5 mole
Hydrogen reduction empirical curve is measured in 0.1 mole every liter of potassium hydroxide solution of every liter of methanol, the revolving speed of rotating disk electrode (r.d.e) is
1600 rpms, curved scanning rate is 10 millivolts per second.
Compare the curve in figure it is found that the Nonmetal oxygen reduction catalyst that is prepared of the present embodiment is relative to commercially using platinum
C catalyst has fabulous anti methanol toxication performance.
Embodiment 2
Nonmetal oxygen reduction catalyst is prepared basically according to method same as Example 1, is a difference in that: by step
(1) POTASSIUM PHYTATE is changed to sodium phytate, and obtained Nonmetal oxygen reduction catalyst is in 0.1 mole every liter of potassium hydroxide solution
The half wave potential phase that the Nonmetal oxygen reduction catalyst that the half wave potential that test hydrogen reduction curve obtains is obtained with embodiment 1 obtains
When.
Embodiment 3
Nonmetal oxygen reduction catalyst is prepared basically according to method same as Example 1, is a difference in that: by step
1) 800 DEG C of calcination temperature are changed to 900 DEG C, potassium hydroxide of the obtained Nonmetal oxygen reduction catalyst at 0.1 mole every liter
The half-wave that the Nonmetal oxygen reduction catalyst that the half wave potential that hydrogen reduction curve obtains is obtained with embodiment 1 obtains is tested in solution
Current potential is suitable.
Embodiment 4
Nonmetal oxygen reduction catalyst is prepared basically according to method same as Example 1, is a difference in that: by step
(1) 800 DEG C of calcination temperature are changed to 1000 DEG C, hydroxide of the obtained Nonmetal oxygen reduction catalyst at 0.1 mole every liter
The half wave potential that hydrogen reduction curve the obtains and Nonmetal oxygen reduction catalyst that embodiment 1 obtains obtains half is tested in potassium solution
Wave current potential is suitable.
Embodiment 5
Nonmetal oxygen reduction catalyst is prepared basically according to method same as Example 1, is a difference in that: by step
(2) nitrogen source melamine is changed to cyanamide, and obtained Nonmetal oxygen reduction catalyst is molten in 0.1 mole every liter of potassium hydroxide
The half wave potential that hydrogen reduction curve obtains and the half-wave electricity that the Nonmetal oxygen reduction catalyst that embodiment 1 obtains obtains are tested in liquid
Position is quite.
Embodiment 6
Nonmetal oxygen reduction catalyst is prepared basically according to method same as Example 1, is a difference in that: by step
(2) nitrogen source melamine is changed to dicyandiamide, potassium hydroxide of the obtained Nonmetal oxygen reduction catalyst at 0.1 mole every liter
The half-wave that the Nonmetal oxygen reduction catalyst that the half wave potential that hydrogen reduction curve obtains is obtained with embodiment 1 obtains is tested in solution
Current potential is suitable.
Claims (14)
1. a kind of method for preparing Nonmetal oxygen reduction catalyst, includes the following steps:
1) under non-oxidizing conditions, phytic acid metal salt is calcined, obtains phosphorus doping porous carbon materials, it is right after the calcining step
Calcined product acid processing；
In the step 1), phytic acid metal salt is selected from least one of POTASSIUM PHYTATE and sodium phytate；
2) it is heat-treated after mixing phosphorus doping porous carbon materials obtained by step 1) with nitrogen source, obtains the nonmetallic hydrogen reduction
Catalyst；
The nitrogen source is selected from least one of melamine, cyanamide and dicyandiamide；
The phosphorus doping porous carbon materials and the mass ratio that feeds intake of the nitrogen source are 1:1-1:50.
2. according to the method described in claim 1, it is characterized by: in the step 1), the non-oxidizing conditions be pass through to
It is passed through what at least one of nitrogen, argon gas, hydrogen and helium gas obtained in reaction system；
The condition of the calcining are as follows: calcination temperature is 300 DEG C -1500 DEG C；Calcination time is -10 hours 0.5 hour；Heating rate
For 0.5 DEG C/min-100 DEG C/min；
The method also includes following steps: after the calcining step, after the calcined product acid processing, and washing,
Precipitating is collected by centrifugation, it is dry.
3. according to the method described in claim 2, it is characterized by: the calcination condition are as follows: calcination temperature is 600 DEG C -1000
℃；Calcination time is -3 hours 1 hour；Heating rate is 3 DEG C/min-15 DEG C/min；
The acid is selected from least one of hydrochloric acid, sulfuric acid, nitric acid and aqueous solution of hydrofluoric acid.
4. according to the method described in claim 3, it is characterized by: the calcination condition are as follows: calcination temperature is 800-900 DEG C；
Calcination time is -2 hours 1 hour.
5. according to the method described in claim 1, it is characterized by: the condition with acid processing are as follows: 5 DEG C of -200 DEG C of processing
- 100 hours 0.1 hour.
6. according to the method described in claim 5, it is characterized by: the concentration of the acid is 0.5-1.5mol/L；
The condition with acid processing are as follows: 20 DEG C -80 DEG C are handled -24 hours 12 hours.
7. according to the method described in claim 2, it is characterized by: dry atmosphere is vacuum or sky in the drying steps
Gas at least one of is passed through following gases into reaction system and obtains: nitrogen, argon gas, helium and carbon dioxide；
The condition of the drying are as follows: 12 hours dry in air atmosphere or vacuum atmosphere.
8. according to the method described in claim 7, it is characterized by: dry temperature is 70-90 DEG C in the drying steps；
In the vacuum atmosphere, vacuum degree is less than < 105Pa。
9. according to the method described in claim 1, being characterized in that: in the step 2), in the heat treatment step, heat treatment
Atmosphere is selected from least one of nitrogen, argon gas, hydrogen and helium gas.
10. according to the method described in claim 1, being characterized in that: in the step 2) mixing step, mixed mode is to grind
Mill.
11. according to the method described in claim 1, it is characterized by: the throwing of the phosphorus doping porous carbon materials and the nitrogen source
Material mass ratio is 1:5-1:40.
12. according to the method described in claim 1, being characterized in that: in the step 2) heat treatment step, the temperature of heat treatment is
700℃-1000℃；Time is -8 hours 0.5 hour.
13. any method in -12 according to claim 1, it is characterised in that: the method also includes following steps:
After the step 2) heat treatment step, system is washed, is centrifuged and dries.
14. according to the method for claim 13, it is characterised in that: the condition of the centrifugation are as follows: revolving speed 8000-1000
Revolutions per second；Time is 3-10 minutes；
The condition of the drying is 12 hours dry in air atmosphere or vacuum atmosphere；
Dry temperature is 70-90 DEG C；
In the vacuum atmosphere, vacuum degree is less than < 105Pa。
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