CN107661772A - A kind of Nonmetal oxygen reduction catalyst and preparation method and application - Google Patents
A kind of Nonmetal oxygen reduction catalyst and preparation method and application Download PDFInfo
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- CN107661772A CN107661772A CN201710982699.XA CN201710982699A CN107661772A CN 107661772 A CN107661772 A CN 107661772A CN 201710982699 A CN201710982699 A CN 201710982699A CN 107661772 A CN107661772 A CN 107661772A
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- oxygen reduction
- reduction catalyst
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- nonmetal
- nonmetal oxygen
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- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- 239000001301 oxygen Substances 0.000 title claims abstract description 82
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 82
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910052755 nonmetal Inorganic materials 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 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
- 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
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 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
- 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
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 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
- 230000001590 oxidative effect Effects 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
- 239000002253 acid Substances 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 238000006722 reduction reaction Methods 0.000 claims description 83
- 238000000034 method Methods 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000012298 atmosphere Substances 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 238000010306 acid treatment 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
- 238000005119 centrifugation Methods 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
- 239000011148 porous material 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
- 239000000203 mixture Substances 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
- 238000000227 grinding Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 230000033116 oxidation-reduction process Effects 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000012545 processing Methods 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
- 229910000510 noble metal Inorganic materials 0.000 abstract description 7
- 238000005406 washing Methods 0.000 abstract description 3
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 abstract 3
- 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
- 238000012360 testing method Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 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
- 239000000463 material Substances 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
- 238000005516 engineering process Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 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
- 206010013786 Dry skin Diseases 0.000 description 1
- 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
- 235000021050 feed intake Nutrition 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
- 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
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003863 metallic catalyst 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
- 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
- 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 catalyst and preparation method and application.The Nonmetal oxygen reduction catalyst is the porous carbon materials of nitrogen phosphorus codope, its preparation method, is comprised the following steps：1) it is a kind of in calcining POTASSIUM PHYTATE, sodium phytate under non-oxidizing conditions, and then centrifugal drying is washed by acid or the aqueous solution, phosphorus doping porous carbon materials are prepared.2) it is heat-treated after the phosphorus doping porous carbon materials of preparation are mixed 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 is that the nitrogen phosphorus codope porous carbon materials can be used as oxygen reduction catalyst, and its hydrogen reduction catalytic performance is close to business platinum carbon catalyst.Preparation method of the present invention is simple, cost is cheap, excellent performance, suitable for mass produce 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, is related to a kind of Nonmetal oxygen reduction catalyst and preparation method and application.
Background technology
Fuel cell is a kind of device that chemical energy is directly converted into electric energy.It has energy conversion efficiency height, environment
It is friendly, operation temperature is low, specific power and the outstanding feature such as higher than energy, it is considered to be following electric automobile 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
It is rare, price is high, stability is poor and the low shortcoming of selectivity hinders the scale of fuel cell and used significantly.Therefore, open
The commercialization process that hair is cheap, sustainable, high performance non noble metal oxygen reduction catalyst is to fuel cell has very
Important meaning.
Recent domestic has carried out substantial amounts of research to non-noble metal preparation, and non-precious metal catalyst can generally divide
For following several classes：The carbon material of Heteroatom doping, the oxide based on transition metal or sulfide or nitride or nitrogen oxides,
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 substantial amounts of manpower and materials, and preparation technology bar
Part is difficult to control, and prepared by single can only obtain a small amount of catalyst, be unfavorable for the large-scale production of catalyst.Therefore develop a kind of low
Cost, high activity, technique are simple, the Nonmetal oxygen reduction catalyst suitable for large-scale production, the industrialization for fuel cell
It is significant.
The content of the invention
It is an object of the invention to provide a kind of Nonmetal oxygen reduction catalyst and preparation method and application.
The preparation method provided by the invention for preparing Nonmetal oxygen reduction catalyst, comprises the following steps：
1) under non-oxidizing conditions, calcining phytic acid metal salt obtains predecessor, and after acid treatment, washing, it is heavy to be collected by centrifugation
Form sediment, dry, obtain phosphorus doping porous carbon materials；
2) it is heat-treated after phosphorus doping porous carbon materials obtained by step 1) are mixed 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 is：Calcining heat is 300 DEG C -1500 DEG C, and calcination time is -10 hours 0.5 hour, heating
Speed is 0.5 DEG C/min-100 DEG C/min；
The calcination condition is concretely：Calcining heat be 600 DEG C -1000 DEG C, more specifically can be 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.
Methods described also comprises the following steps：After the calcining step, acid treatment, water are used successively to calcined product
Wash, precipitation is collected by centrifugation, dry.
At least one of the described aqueous solution of acid selected from hydrochloric acid, sulfuric acid, nitric acid and hydrofluoric acid；The bar with acid treatment
Part is：5 DEG C -200 DEG C are handled -100 hours 0.1 hour；The sour concentration is specially 0.5-1.5mol/L, more specifically can be
1mol/L；Oxide impurity subsidiary in calcined product can be removed with acid treatment.
The condition with acid treatment is concretely：20 DEG C -80 DEG C are handled -24 hours 12 hours, more specifically can be normal 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 into reaction system in following gases extremely
It is few a kind of to obtain：Nitrogen, argon gas, helium and carbon dioxide.
The drying is concretely dried 12 hours 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 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) blend step, the mode of mixing is grinding；The phosphorus doping porous carbon materials and the nitrogen source
Feed intake mass ratio can be 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
℃；Described heat treatment time can be -8 hours 0.5 hour, concretely 2 hours.
Methods described also comprises the following steps：After the step 2) heat treatment step, system is washed, centrifuged
And drying；
The actual conditions of the centrifugation is：Rotating speed is 8000-1000 revolutions per seconds；Time is 3-10 minutes；
The actual conditions of the drying is to be dried 12 hours in air atmosphere or vacuum atmosphere；
Dry temperature is specially 70-90 DEG C or 80 DEG C；
In the vacuum atmosphere, vacuum is specifically les than<105Pa。
In addition, a kind of Nonmetal oxygen reduction catalyst is also claimed in the present invention, the Nonmetal oxygen reduction catalyst contains
Nitrogen and the carbon material of 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, falls within protection model of the invention
Enclose.
In addition, above-mentioned Nonmetal oxygen reduction catalyst as the application in oxygen reduction catalyst and the nonmetallic oxygen also
Application of the raw catalyst in oxygen reduction reaction or the application in catalytic oxidation-reduction reaction, fall within the protection model of the present invention
Enclose.
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, at high temperature carbonization form carbon material；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, so as to realize loose structure；P elements in phytic acid metal salt can be used as phosphorus source,
Phosphorus doping carbon in situ 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, so as to obtain the present invention Nonmetal oxygen reduction catalyst.
It is of the invention compared with other prior arts, have the characteristics that：
1st, the cost of raw material provided in the present invention is cheap, wide material sources.
2nd, the Nonmetal oxygen reduction catalyst that the preparation method employed in the present invention obtains is compared to other porous carbons
Material has higher specific surface area, larger pore volume and micropore and meso-hole structure.
3rd, preparation method of the present invention uses cheap melamine, cyanamide etc. as 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.
4th, the Nonmetal oxygen reduction catalyst catalytic performance for preparing of the present invention is excellent, and other with document report nonmetallic urge
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
Oxygen reduction catalyst effect, that noble metal can be substituted, therefore can be applied in fuel cell field.
5th, preparation method technique of the present invention is simple, economic, operation facility, suitable for mass producing 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.
Brief description of the drawings
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 swashed
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.
Embodiment
With reference to specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Institute
It is conventional method unless otherwise instructed to state method.The raw material can obtain from open commercial sources unless otherwise instructed.
Embodiment 1
1) 2g POTASSIUM PHYTATEs being put into tube furnace, carries out high-temperature calcination in a nitrogen atmosphere, heating rate is 3 DEG C/min,
Calcining heat is 800 DEG C, and calcination time is 1 hour, naturally cools to room temperature, obtains predecessor；The predecessor is every with 1 mole
Handled 18 hours under the hydrochloric acid normal temperature risen, then centrifugation is washed with deionized and is precipitated for several times to neutral collect, obtained wet phosphorus and mix
Miscellaneous porous carbon, finally, by the wet phosphorus doping porous carbon under vacuum, 80 DEG C of dryings 12 hours, both phosphorus doping is porous
Carbon material；
2) after taking 0.1g steps 1) gained phosphorus doping porous carbon materials and 2g melamine ground and mixeds uniform again, it is transferred to
In crucible, it 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, is protected in nitrogen
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
(b) it 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 that the catalyst has higher graphite degree.
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, is schemed
The carbonization structure of the high-resolution lattice fringe 0.34nm energy corresponding diagrams 1 (a) of 2 (d) carbon.
Energy dispersion X ray spectrum Element area profile such as Fig. 3 institutes 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, and (b) is pore size distribution curve figure.From scheming (a), the present embodiment institute
The specific surface area of the Nonmetal oxygen reduction catalyst of preparation is 1294cm2/g.From scheming (b), non-gold manufactured in the present embodiment
Category 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 experiment of Nonmetal oxygen reduction catalyst manufactured in the present embodiment and the platinum carbon catalyst being commercially used
Curve is as shown in Figure 5.Specific experiment method is：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 rotating speed of rotating ring disk electrode (r.r.d.e) is 1600 rpms, and curved scanning speed is 10 millivolts per second；Test
During ring electrode current potential it is constant at 0.5 volt relative to the silver/silver chloride reference electrode Klorvess Liquid of saturation (electrolyte be).
Control is that purchase believes that ten thousand rich (Johnson-Matthey) (Shanghai) are urged from the village with the platinum carbon catalyst being commercially used
The platinum weight percent content of agent Co., Ltd is 20% business platinum carbon catalyst.
Compare two curves, it can be seen that the Nonmetal oxygen reduction catalyst that the present embodiment is prepared is real in hydrogen reduction
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.
Nonmetal oxygen reduction catalyst and the stability test for the platinum carbon catalyst being commercially used prepared by the present embodiment 1
Empirical curve is as shown in Figure 6.Specific experiment method is：Chrono-amperometric empirical curve rotating disk electrode (r.d.e) is in oxygen saturation
Measured in 0.1 mole every liter of potassium hydroxide solution, the rotating speed of rotating disk electrode (r.d.e) is 1600 rpms, constant potential 0.7
Volt, curved scanning speed 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 is prepared nonmetallic by 20000 seconds 0.7 volt of (relative to mark hydrogen electrode) constant potential aging, the present embodiment
The kinetic current of oxygen reduction catalyst had been the 75% of beginning kinetic current after 20000 seconds, higher than business platinum carbon catalyst
58%, this shows that the Nonmetal oxygen reduction catalyst that the present embodiment is prepared has preferably compared to business 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.Specifically experimental method is：In 0.1 mole every liter of potassium hydroxide solution and it is 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 rotating speed of rotating disk electrode (r.d.e) is
1600 rpms, curved scanning speed is 10 millivolts per second.
Compare curve in figure to understand, the Nonmetal oxygen reduction catalyst that the present embodiment is prepared 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 resulting 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 obtains 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 calcining heat is changed to 900 DEG C, potassium hydroxide of the resulting 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 obtains 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 calcining heat is changed to 1000 DEG C, hydroxide of the resulting Nonmetal oxygen reduction catalyst at 0.1 mole every liter
The Nonmetal oxygen reduction catalyst that the half wave potential that hydrogen reduction curve obtains obtains with embodiment 1 obtains half is tested in potassium solution
Ripple 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 resulting Nonmetal oxygen reduction catalyst is molten in 0.1 mole every liter of potassium hydroxide
The half-wave electricity that the Nonmetal oxygen reduction catalyst that the half wave potential that hydrogen reduction curve obtains obtains with embodiment 1 obtains is 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 resulting 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 obtains with embodiment 1 obtains is tested in solution
Current potential is suitable.
Claims (10)
1. a kind of method for preparing Nonmetal oxygen reduction catalyst, comprises the following steps：
1) under non-oxidizing conditions, phytic acid metal salt is calcined, obtains phosphorus doping porous carbon materials；
2) it is heat-treated after phosphorus doping porous carbon materials obtained by step 1) are mixed with nitrogen source, obtains the nonmetallic hydrogen reduction
Catalyst.
2. according to the method for claim 1, it is characterised in that：In the step 1), phytic acid metal salt be selected from POTASSIUM PHYTATE and
At least one of sodium phytate；And/or
The non-oxidizing conditions are by being passed through at least one of nitrogen, argon gas, hydrogen and helium gas into reaction system
Obtain；And/or
The condition of the calcining is：Calcining heat 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；And/or
The calcination condition is specially：Calcining heat is 600 DEG C -1000 DEG C or 800-900 DEG C；Calcination time is 1 hour -3 small
When or -2 hours 1 hour；Heating rate is 3 DEG C/min-15 DEG C/min；And/or
Methods described also comprises the following steps：After the calcining step, acid treatment is used calcined product successively, is washed, from
The heart collects precipitation, dries；
Specifically,
At least one of the described aqueous solution of acid selected from hydrochloric acid, sulfuric acid, nitric acid and hydrofluoric acid；The sour concentration is specially
0.5-1.5mol/L or 1mol/L；And/or
It is described to be with the condition of acid treatment：5 DEG C -200 DEG C are handled -100 hours 0.1 hour；And/or
It is described to be specially with the condition of acid treatment：20 DEG C -80 DEG C handle -24 hours 12 hours or 20 DEG C of -80 DEG C of normal temperature processing 18
- 24 hours hours；And/or
In the drying steps, dry atmosphere is vacuum or air or be passed through into reaction system in following gases at least one
What kind obtained：Nitrogen, argon gas, helium and carbon dioxide；And/or
The condition of the drying is：Dried 12 hours in air atmosphere or vacuum atmosphere；And/or
Dry temperature is specially 70-90 DEG C or 80 DEG C；And/or
In the vacuum atmosphere, vacuum is specifically les than<105Pa。
3. method according to claim 1 or 2, is characterised by：In the step 2), the nitrogen source be selected from melamine,
At least one of cyanamide and dicyandiamide；And/or
In the heat treatment step, the atmosphere of heat treatment is selected from least one of nitrogen, argon gas, hydrogen and helium gas.
4. according to any described method in claim 1-3, it is characterised by：In the step 2) blend step, the side of mixing
Formula is grinding；
And/or the phosphorus doping porous carbon materials and the mass ratio that feeds intake of the nitrogen source are 1:1-1:50 or 1:5-1:40.
5. according to any described method in claim 1-4, it is characterised by：In the step 2) heat treatment step, heat treatment
Temperature be 700 DEG C -1000 DEG C；Time is -8 hours 0.5 hour.
6. according to any described method in claim 1-5, it is characterised in that：Methods described also comprises the following steps：Institute
After stating step 2) heat treatment step, system is washed, centrifuges and dries；
The actual conditions of the centrifugation is：Rotating speed is 8000-1000 revolutions per seconds；Time is 3-10 minutes；
The actual conditions of the drying is to be dried 12 hours in air atmosphere or vacuum atmosphere；
Dry temperature is specially 70-90 DEG C or 80 DEG C；
In the vacuum atmosphere, vacuum is specifically les than<105Pa。
A kind of 7. Nonmetal oxygen reduction catalyst, it is characterised in that：The Nonmetal oxygen reduction catalyst contains nitrogen and phosphorus
The carbon material of element 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 is 2.99~3.46cm3/g；
Aperture is 0.5nm-20nm.
8. Nonmetal oxygen reduction catalyst according to claim 7, it is characterised in that：The Nonmetal oxygen reduction catalyst
The Nonmetal oxygen reduction catalyst being prepared for any methods described in claim 1-6.
9. the Nonmetal oxygen reduction catalyst of claim 7 or 8 is as the application in oxygen reduction catalyst.
10. application or in catalytic oxidation-reduction anti-of the Nonmetal oxygen reduction catalyst of claim 7 or 8 in oxygen reduction reaction
Application in answering.
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