CN110054168A - A kind of preparation method of full pH value fuel battery negative pole oxygen reduction electro-catalyst - Google Patents
A kind of preparation method of full pH value fuel battery negative pole oxygen reduction electro-catalyst Download PDFInfo
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- CN110054168A CN110054168A CN201910332855.7A CN201910332855A CN110054168A CN 110054168 A CN110054168 A CN 110054168A CN 201910332855 A CN201910332855 A CN 201910332855A CN 110054168 A CN110054168 A CN 110054168A
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000001301 oxygen Substances 0.000 title claims abstract description 49
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 49
- 230000009467 reduction Effects 0.000 title claims abstract description 43
- 239000000446 fuel Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 17
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 96
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910052751 metal Inorganic materials 0.000 claims abstract description 70
- 239000002184 metal Substances 0.000 claims abstract description 70
- 238000005554 pickling Methods 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 26
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 20
- 235000009467 Carica papaya Nutrition 0.000 claims abstract description 18
- 238000000227 grinding Methods 0.000 claims abstract description 17
- 235000006264 Asimina triloba Nutrition 0.000 claims abstract description 14
- 235000013399 edible fruits Nutrition 0.000 claims abstract description 12
- 235000013311 vegetables Nutrition 0.000 claims abstract description 12
- 239000002699 waste material Substances 0.000 claims abstract description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 4
- 244000189799 Asimina triloba Species 0.000 claims abstract 2
- 238000010792 warming Methods 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 238000000498 ball milling Methods 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 12
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 12
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 12
- 239000011425 bamboo Substances 0.000 claims description 12
- 239000010902 straw Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 7
- 238000003763 carbonization Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims 3
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 48
- 238000000034 method Methods 0.000 abstract description 28
- 239000001257 hydrogen Substances 0.000 abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 13
- 239000002028 Biomass Substances 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000004913 activation Effects 0.000 abstract description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 3
- 238000005087 graphitization Methods 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- 239000012190 activator Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 53
- 239000000047 product Substances 0.000 description 49
- 241000219112 Cucumis Species 0.000 description 39
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 39
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 39
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 39
- 239000002023 wood Substances 0.000 description 39
- 229910001873 dinitrogen Inorganic materials 0.000 description 32
- 229910052593 corundum Inorganic materials 0.000 description 30
- 239000010431 corundum Substances 0.000 description 30
- 238000006722 reduction reaction Methods 0.000 description 30
- 238000009423 ventilation Methods 0.000 description 30
- 238000004502 linear sweep voltammetry Methods 0.000 description 27
- 238000003556 assay Methods 0.000 description 22
- 239000008367 deionised water Substances 0.000 description 22
- 229910021641 deionized water Inorganic materials 0.000 description 22
- 238000012360 testing method Methods 0.000 description 15
- 229920006395 saturated elastomer Polymers 0.000 description 14
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 240000006432 Carica papaya Species 0.000 description 12
- 241001330002 Bambuseae Species 0.000 description 11
- 230000006837 decompression Effects 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 10
- 238000003760 magnetic stirring Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 150000007974 melamines Chemical class 0.000 description 10
- 229910052700 potassium Inorganic materials 0.000 description 10
- 239000011591 potassium Substances 0.000 description 10
- 238000000967 suction filtration Methods 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 238000000840 electrochemical analysis Methods 0.000 description 9
- 239000011148 porous material Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 238000003775 Density Functional Theory Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 241000219173 Carica Species 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002574 poison Substances 0.000 description 4
- 231100000614 poison Toxicity 0.000 description 4
- 238000002336 sorption--desorption measurement Methods 0.000 description 4
- 239000003826 tablet Substances 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 3
- 238000000970 chrono-amperometry Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000005255 carburizing Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 1
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 210000003097 mucus Anatomy 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- -1 oxo transition metal Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 238000005406 washing 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of method using abandoned biomass as raw material preparation without metal nitrogen-doped porous carbon material and in full pH range fuels cell cathode oxygen reduction electro-catalyst.Using the agricultural such as pawpaw skin fruit/vegetable waste as raw material, saleratus carries out N doping in 300 DEG C of relative low temperature as nitrogen source as activator, melamine, in 900 DEG C of progress carbon material activation and increases degree of graphitization again later.Using grinding before being carbonized simultaneously at second, the validity of reactivity and nitrogen atom doping is improved.It is made through pickling, drying, which can be used as the cathodic oxygen reduction catalyst of full pH range fuels battery.The present invention is converted into the agricultural fruit/vegetable waste of low cost the energy and material of high value.Its electro-catalysis can compare favourably with hydrogen reduction Pt/C catalyst performance, and have very strong resistance to methanol, and cyclical stability is preferable, with the application prospect of larger potentiality in full pH range fuels cell cathode hydrogen reduction electro-catalysis.
Description
Technical field
The invention belongs to inorganic nano material and electrochemical fields, are related to a kind of no metal nitrogen-doped porous carbon material, tool
Body is related to a kind of preparation method without metal N doping porous carbon based on discarded agricultural fruit/vegetable waste and its firing in full pH range
Expect the catalytic applications in cell cathode hydrogen reduction.
Background technique
Oxygen reduction reaction (ORR) is cathode reaction crucial in fuel cell, has been widely studied and applied for many years.By
In having slowly dynamic (dynamical) multistep electrochemical reaction (especially in acid and neutral electrolyte), oxygen reduction reaction may also
Undergo our undesirable 2 electron transfers and hydrogen peroxide (H2O2) and peroxide hydrogen radical (HO2 -) by-product generate.Consider
To high activity and direct 4 electron transfer, platinum and its alloy are considered as the business oxygen reduction electro-catalyst of superior performance.
However, expensive, low selectivity, vulnerable to poison with the scarcity of platinum-base material hinder fuel cell it is a large amount of commercialization answer
With.Therefore, these New technology commercializations are most important to promotion for the oxygen reduction electro-catalyst of development high activity and high stability.
Biomass is a kind of ideal raw material, usually very cheap, renewable and environmentally friendly.In addition, biomass is rich in carbon atom
With hetero atom such as nitrogen.Therefore, the carbon that Heteroatom doping can be obtained by the controlled thermolysis of biomass can be reasonably expected that.Make
To be a kind of widely available, reproducible green carbon matrix precursor, biomass derived carbon causes the extensive concern of many researchers,
But there are also some problems needs to overcome before business application.The carbon of most of biomass deriveds to the performance of hydrogen reduction still
So it is lower than platinum carbon catalyst.
In order to solve these problems, other materials such as oxo transition metal, sulphur, carbide and carbon nanomaterial be all have very much it is uncommon
The candidate material of prestige.Wherein, no metal heteroatom doping (such as boron, nitrogen, sulphur and phosphorus) carbon nanomaterial mainly has excellent oxygen
Reduction catalysts performance not only provides big surface area, but also provides more activation polarization sites and adsorb or divide for oxygen.
However, most of which is primarily upon the electro-catalysis behavior under alkaline condition.Currently, without metal carbon material it is acid and in
Hydrogen reduction electrocatalysis characteristic in property medium is also very low, this is also the key points and difficulties (L. of area research world wide Nei
Yang, J. Shui, L. Du, Y. Shao, J. Liu, L. Dai, Z. Hu, Adv. Mater.,2019,
1804799).Due to durability difference and electroactive deterioration, only minority is without metal carbon nanomaterial in acid and neutral medium
Catalyst can be born.However, most of room temperature fuel cells use proton exchange membrane, i.e. acidic electrolyte bath at present.In addition,
There is the carbon nanomaterial of benign behavior metal impurities or complex compound usually to be used to be functionalized in acid condition for those, this can not keep away
It increases cost with exempting from, also reduces the catalytic stability of material.In order to cater to current commercial market, exploitation is suitable for full pH
Range environment adulterates carbon nanomaterial without metal heteroatom, so that nitrogen-doped carbon material is in acid, neutral and alkaline medium
Hydrogen reduction electrocatalysis characteristic meet or exceed business platinum carbon, be a huge challenge.
Summary of the invention
It is that raw material is prepared without metal N doping porous carbon that the object of the present invention is to provide one kind based on agricultural fruit/vegetable waste
The method of material.
It is porous without metal N doping using agricultural fruit/vegetable waste as raw material preparation that it is a further object of the present invention to provide above-mentioned
Carbon material fuel battery negative pole oxygen reduction catalyst and its catalytic applications.
To achieve the above object, The technical solution adopted by the invention is as follows: a kind of full pH value fuel battery negative pole electro-catalysis
The preparation method of agent, comprising the following steps:
(1) agricultural fruit/vegetable waste is collected, cleaning is dried, and using heating equipment, is warming up to 300 ~ 500 under inert gas protection
DEG C, and 1 ~ 3 h is kept, it is cooled to 100 ~ 350 DEG C later, obtains pre- carbonized product A.
(2) it is that 1:3 weighs melamine with the pre- carbonized product A of mass ratio and melamine, mixes, ball milling, after ball milling
Mixture be warming up to 250 ~ 350 DEG C under inert gas protection using heating equipment, and keep 1 ~ 3 h, be cooled to later
50 ~ 150 DEG C, the product B after obtaining N doping.
(3) saleratus is weighed with mass ratio pre- carbonized product A: saleratus 1:3, by itself and the production after N doping
Object B mixing, grinding by the mixture after grinding, using heating equipment, are warming up to 800 ~ 950 DEG C under inert gas protection,
And 1 ~ 3 h is kept, it is cooled to 100 ~ 350 DEG C later, obtains porous carbon materials C.
(4) by porous carbon materials C, with dilute hydrochloric acid solution, 2 h of pickling, pickling temperature are 50 DEG C in a water bath, are filtered, washing
To neutrality, drying obtains electrocatalyst for cathode D.
Preferred scheme is:
(1) by agricultural fruit/vegetable waste, especially pawpaw skin is collected, and cleaning is dried, be placed in tube furnace, in inertia
With 5 DEG C of min under gas nitrogen protection-1Rate be warming up to 400 DEG C, and 2 h are kept, later with 5 DEG C of min-1It is cooled to
300 DEG C, obtain pre- carbonized product A.
(2) it is that 1:3 weighs melamine with the ratio of the pre- carbonized product A of mass ratio and melamine, is subsequently placed in ball milling
In machine, the mixture after ball milling is placed in tube furnace by 20 min of mechanical ball mill, with 3 DEG C under inert nitrogen gas protection
min-1Rate be warming up to 250 ~ 350 DEG C, and 2 h are kept, later with 3 DEG C of min-1100 DEG C are cooled to, N doping is obtained
Product B afterwards.
(3) with the pre- carbonized product A of mass ratio: saleratus is that 1:3 weighs saleratus, by itself and the product after N doping
B mixing is placed in mortar, is fully ground 10min, then the mixture after grinding is placed in tube furnace, in inert nitrogen gas
With 3 DEG C of min under protection-1Rate be warming up to 800 ~ 950 DEG C, and 2 h are kept, later with 3 DEG C of min-1It is cooled to 300
DEG C, obtain porous carbon materials C.
(4) by porous carbon materials C, with dilute hydrochloric acid solution, 2 h of pickling, the concentration of dilute hydrochloric acid solution are 1 mol in a water bath
L-1, pickling temperature is 50 DEG C, and pickling rate is 300 rpm, and decompression filters later, is washed to filtrate and is in neutrality, and drying obtains nothing
Metal wood melon skin nitrogen-doped porous carbon material D.
Preferably, in step (2), the temperature of the carbonization is 300 DEG C.
Preferably, in step (2), 300 rpm of rotational speed of ball-mill, Ball-milling Time is each 10 min of positive and negative rotation.
Preferably, in step (3), the temperature of the carbonization is 900 DEG C.
The present invention also provides made from above-mentioned preparation method without metal nitrogen-doped porous carbon material in fuel battery negative pole oxygen
The catalytic applications of reduction.
The no metal nitrogen-doped porous carbon material D can be used for preparing the cathodic oxygen reduction catalyst of fuel cell.Method
It is as follows: to weigh 3 mg and be placed in centrifuge tube without metal nitrogen-doped porous carbon material D, 170 microlitres of deionized water, isopropanol 70 is added
Microlitre and 5 % perfluorinated sulfonic acid -10 microlitres of solution of teflon-copolymers (Nafion), be uniformly mixed, it is super with ultrasonic cleaning machine
Sound 1 hour, finely dispersed black dispersion liquid is formed, 10 microlitres of mixed solutions is taken with liquid-transfering gun, drips the rotation in 5 mm of diameter
On disk electrode (RDE), then naturally dry in air, is made working electrode.
The present invention also using discarded straw, bamboo shoots root, cabbage root, adds pawpaw skin etc., belongs to that " agricultural vegetables and fruits are discarded
The different types of biomass of object " obtains no metal straw N doping porous carbon as raw material, using above-mentioned preparation method respectively
Material, without metal bamboo shoots root nitrogen-doped porous carbon material, without metal castock nitrogen-doped porous carbon material, these three materials tool
There is the hydrogen reduction electrocatalysis characteristic of full pH range, illustrates that the preparation method has universality.
Compared with prior art, the invention has the following beneficial effects:
1, the present invention is converted into the biomass castoffs such as pawpaw skin of low cost the energy and material of high value, preparation without metal
Nitrogen-doped porous carbon material can be applied in fuel battery negative pole hydrogen reduction electro-catalysis, meanwhile, this method is raw to other types
After substance (agricultural fruit/vegetable waste, such as straw, bamboo shoots root, castock) is handled, it can also reach electrocatalysis characteristic
The effect of promotion, has universality, and green non-pollution meets environment and energy demand.
2, no metal wood melon skin nitrogen-doped porous carbon material preparation method provided by the invention is easy, and condition is controllable, and green
Colour circle is protected, and hydrogen reduction electrocatalysis characteristic is all excellent in alkalinity, neutral and acid medium, in silver/silver chloride reference electrode
Under, in 0.5 mol L-1Sulfuric acid solution in, initial potential is close to 0.87 V(relative to reversible hydrogen electrode RHE), half wave potential
Close to 0.76 V(relative to RHE), limiting current density is about -5.15 mA cm-2；In 0.1 mol L-1Dipotassium hydrogen phosphate and
In the neutral solution of potassium dihydrogen phosphate (PBS solution, pH=7.0), initial potential is close to 0.88V(relative to RHE), half wave potential
Close to 0.73 V(relative to RHE), limiting current density is about -5.53 mA cm-2；And in 0.1 mol L-1Potassium hydroxide
In solution, initial potential is close to 1.00 V(relative to RHE), half wave potential is close to 0.87 V(relative to RHE), carrying current is close
Degree is about -5.89 mA cm-2No matter electrocatalysis characteristic, can be with business platinum carbon catalyst in acid, alkalinity or neutrality
Performance compares favourably, and this has a very strong resistance to methanol solution without metal nitrogen-doped porous carbon material, and cyclical stability compared with
It is good, there is larger potential application prospect in fuel battery negative pole hydrogen reduction catalysis.
3, the present invention changes the method that the carbonization of one step of conventional high-temperature is directly adulterated, and mixes in 300 DEG C of progress nitrogen of relative low temperature
It is miscellaneous, it prevents melamine from decomposing the organic matter for generating blocking porous carbon materials duct at high temperature, is carried out again at 900 DEG C later
Carbon material activation.Meanwhile before being carbonized second using grinding rather than the mode of ball milling, prevent from being attached to carbon material surface
So that the nitrogen-atoms of doping is fallen off under the physical action of the strong mechanical force of ball milling, improves the effective of reactivity and nitrogen atom doping
Property.For the present invention by adjusting doping and carburizing temperature, having without metal wood melon skin nitrogen-doped porous carbon material for preparation is biggish
Specific surface area (1670.86 m2 g-1), the higher nanometer laminated structure of degree of graphitization.
Detailed description of the invention
Fig. 1 is the high-resolution transmitted electron without metal wood melon skin nitrogen-doped porous carbon material made from the embodiment of the present invention 1
Microscope (HRTEM) figure；
Fig. 2 is that 1-5 of embodiment of the present invention isothermal (77 K) nitrogen obtained without metal wood melon skin nitrogen-doped porous carbon material is inhaled
Desorption curve；
Fig. 3 is the isothermal (77 without metal wood melon skin nitrogen-doped porous carbon material made from the embodiment of the present invention 1 and embodiment 9-10
K) nitrogen adsorption desorption curve；
Fig. 4 is without metal wood melon skin nitrogen-doped porous carbon material made from 1-5 of the embodiment of the present invention with density functional theory (DFT)
The pore size distribution curve that model calculates；
Fig. 5 is general with density without metal wood melon skin nitrogen-doped porous carbon material made from the embodiment of the present invention 1 and embodiment 9-10
The pore size distribution curve that letter theory (DFT) model calculates；
Fig. 6, which is that 1-5 of the embodiment of the present invention is obtained, is saturated 0.1 mol in oxygen without metal wood melon skin nitrogen-doped porous carbon material
L-1The linear sweep voltammetry curve (LSV) of 1600 rpm in KOH solution；
Fig. 7, which is that 1-5 of the embodiment of the present invention is obtained, is saturated 0.5 mol in oxygen without metal wood melon skin nitrogen-doped porous carbon material
L-1 H2SO4The linear sweep voltammetry curve (LSV) of 1600 rpm in solution；
Fig. 8, which is that 1-5 of the embodiment of the present invention is obtained, is saturated 0.1 mol in oxygen without metal wood melon skin nitrogen-doped porous carbon material
L-1The linear sweep voltammetry curve (LSV) of 1600 rpm in PBS solution；
Fig. 9 is that the embodiment of the present invention 1 and embodiment 9-10 are obtained full in oxygen without metal wood melon skin nitrogen-doped porous carbon material
With 0.1 mol L-1The linear sweep voltammetry curve (LSV) of 1600 rpm in KOH solution；
Figure 10 is that the embodiment of the present invention 1 and embodiment 9-10 are obtained full in oxygen without metal wood melon skin nitrogen-doped porous carbon material
With 0.5 mol L-1 H2SO4The linear sweep voltammetry curve (LSV) of 1600 rpm in solution；
Figure 11 is that the embodiment of the present invention 1 and embodiment 9-10 are obtained full in oxygen without metal wood melon skin nitrogen-doped porous carbon material
With 0.1 mol L-1The linear sweep voltammetry curve (LSV) of 1600 rpm in PBS solution；
Figure 12 is to mix made from the embodiment of the present invention 1 and embodiment 6-8 without metal papaya tablet, straw, bamboo shoots root, castock nitrogen
Miscellaneous porous carbon materials are saturated 0.1 mol L in oxygen-1 The linear sweep voltammetry curve (LSV) of 1600 rpm in KOH solution；
Figure 13 is to mix made from the embodiment of the present invention 1 and embodiment 6-8 without metal papaya tablet, straw, bamboo shoots root, castock nitrogen
Miscellaneous porous carbon materials are saturated 0.5 mol L in oxygen-1 H2SO4The linear sweep voltammetry curve (LSV) of 1600 rpm in solution；
Figure 14 is to mix made from the embodiment of the present invention 1 and embodiment 6-8 without metal papaya tablet, straw, bamboo shoots root, castock nitrogen
Miscellaneous porous carbon materials are saturated 0.1 mol L in oxygen-1 The linear sweep voltammetry curve (LSV) of 1600 rpm in PBS solution；
Figure 15, which is that the embodiment of the present invention 1 is obtained, to be saturated without metal wood melon skin nitrogen-doped porous carbon material and platinum carbon in oxygen
0.1 mol L-1 The cyclical stability figure of 400 rpm in KOH solution；
Figure 16, which is that the embodiment of the present invention 1 is obtained, to be saturated without metal wood melon skin nitrogen-doped porous carbon material and platinum carbon in oxygen
0.5 mol L-1 H2SO4The cyclical stability figure of 400 rpm in solution；
Figure 17, which is that the embodiment of the present invention 1 is obtained, to be saturated without metal wood melon skin nitrogen-doped porous carbon material and platinum carbon in oxygen
0.1 mol L-1 The cyclical stability figure of 400 rpm in PBS solution；
Figure 18, which is that the embodiment of the present invention 1 is obtained, to be saturated without metal wood melon skin nitrogen-doped porous carbon material and platinum carbon in oxygen
0.1 mol L-1 The methanol tolerance performance map of 400 rpm in KOH solution；
Figure 19, which is that the embodiment of the present invention 1 is obtained, to be saturated without metal wood melon skin nitrogen-doped porous carbon material and platinum carbon in oxygen
0.5 mol L-1 H2SO4The methanol tolerance performance map of 400 rpm in solution；
Figure 20, which is that the embodiment of the present invention 1 is obtained, to be saturated without metal wood melon skin nitrogen-doped porous carbon material and platinum carbon in oxygen
0.1 mol L-1 The methanol tolerance performance map of 400 rpm in PBS solution.
Specific embodiment
Invention is further described in detail in the following with reference to the drawings and specific embodiments.
Embodiment 1
(1) discarded pawpaw skin is collected, is cleaned and is dried with deionized water, weighed 3 g and be put into corundum boat, be placed in tubular type
Furnace, under the protection of inert nitrogen gas, Ventilation Rate is 80 mL min-1, with 5 DEG C of min-1Rate be warming up to 400
DEG C, and 2 h are kept, later with 5 DEG C of min-1300 DEG C are cooled to, pre- carbonized product A1 is obtained.
(2) the pre- carbonized product A1 of 0.6 g and 1.8 g melamines are weighed with mass ratio 1:3 with assay balance, are subsequently placed in
In ball mill, 300 rpm of rotational speed of ball-mill, Ball-milling Time is each 10 min of positive and negative rotation, altogether 20 min of mechanical ball mill, after ball milling
Mixture is put into corundum boat, is placed in tube furnace, and under the protection of inert nitrogen gas, Ventilation Rate is 80 mL min-1, with 3
℃ min-1Rate be warming up to 300 DEG C, and 2 h are kept, later with 3 DEG C of min-1It is cooled to 100 DEG C, after obtaining N doping
Product B1.
(3) with assay balance with mass ratio 1:3(A: saleratus) 1.8 g of saleratus is weighed, first it is fully ground carbonic acid
Hydrogen potassium is blended into N doping product B1, is fully ground 10 min, the mixture after grinding is then put into corundum boat to powdered
In, it is placed in tube furnace, under the protection of inert nitrogen gas, Ventilation Rate is 80 mL min-1, with 3 DEG C of min-1Rate
900 DEG C are warming up to, and keeps 2 h, later with 3 DEG C of min-1300 DEG C are cooled to, porous carbon materials C1 is obtained.
(4) porous carbon materials C1 is put into beaker, is put into magneton, with the 1 mol L of 120 mL in magnetic stirring apparatus-1
2 h of pickling, pickling bath temperature are 50 DEG C to dilute hydrochloric acid solution in a water bath, and magneton stirring rate is 300 rpm, later with true
Sky pump carries out decompression suction filtration, and deionized water is washed to filtrate and is in neutrality, and is placed in 80 DEG C of baking ovens and dries, and obtains no metal pawpaw
Skin nitrogen-doped porous carbon material D1.
Sample made from the method is named as HNPC-2-900.
3 mg are weighed with assay balance to be placed in centrifuge tube without metal wood melon skin nitrogen-doped porous carbon material D1, addition go from
170 microlitres of sub- water, 70 microlitres of isopropanol and 5 % perfluorinated sulfonic acid -10 microlitres of solution of teflon-copolymers (Nafion), mixing
Uniformly, with ultrasonic cleaning machine ultrasound 1 hour, finely dispersed black dispersion liquid is formed, takes 8 microlitres of mixed solutions with liquid-transfering gun,
Drop is in the rotating disk electrode (r.d.e) (RDE) of 5 mm of diameter, and then naturally dry in air, is made working electrode.With the electrode
For working electrode, platinum filament is to electrode, 3.5 mol L-1Klorvess Liquid in, silver/silver chloride electrode be reference electrode composition
Three-electrode system, in 0.1 mol L of oxygen saturation-1Potassium hydroxide solution and 0.5 mol L-1Sulfuric acid solution in respectively
Scan cycle volt-ampere curve and linear sweep voltammetry curve, sweeping speed is respectively 5 mV s-1With 10 mV s-1。
Embodiment 2
(1) discarded pawpaw skin is collected, is cleaned and is dried with deionized water, weighed 3 g and be put into corundum boat, be placed in tubular type
Furnace, under the protection of inert nitrogen gas, Ventilation Rate is 80 mL min-1, with 5 DEG C of min-1Rate be warming up to 400
DEG C, and 2 h are kept, later with 5 DEG C of min-1300 DEG C are cooled to, pre- carbonized product A2 is obtained.
(2) the pre- carbonized product A2 of 0.6 g and 1.8 g melamines are weighed with mass ratio 1:3 with assay balance, are subsequently placed in
In ball mill, 300 rpm of rotational speed of ball-mill, Ball-milling Time is each 10 min of positive and negative rotation, altogether 20 min of mechanical ball mill, after ball milling
Mixture is put into corundum boat, is placed in tube furnace, and under the protection of inert nitrogen gas, Ventilation Rate is 80 mL min-1, with 3
℃ min-1Rate be warming up to 300 DEG C, and 2 h are kept, later with 3 DEG C of min-1It is cooled to 100 DEG C, after obtaining N doping
Product B2.
(3) with assay balance with mass ratio 1:3(A: saleratus) 1.8 g of saleratus is weighed, first it is fully ground carbonic acid
Hydrogen potassium is blended into N doping product B2, is fully ground 10min, the mixture after grinding is then put into corundum boat to powdered
In, it is placed in tube furnace, under the protection of inert nitrogen gas, Ventilation Rate is 80 mL min-1, with 3 DEG C of min-1Rate
750 DEG C are warming up to, and keeps 2 h, later with 3 DEG C of min-1300 DEG C are cooled to, porous carbon materials C2 is obtained.
(4) porous carbon materials C2 is put into beaker, is put into magneton, with the 1 mol L of 120 mL in magnetic stirring apparatus-1
2 h of pickling, pickling bath temperature are 50 DEG C to dilute hydrochloric acid solution in a water bath, and pickling rate is 300 rpm, uses vacuum pump later
Decompression suction filtration is carried out, deionized water is washed to filtrate and is in neutrality, and is placed in 80 DEG C of baking ovens and dries, and obtains no metal wood melon skin nitrogen and mixes
Miscellaneous porous carbon materials D2.
Sample made from the method is named as HNPC-2-750.
It is above-mentioned without metal nitrogen pawpaw skin doped porous carbon material HNPC-2-750 as fuel cell oxygen reduction catalyst
Working electrode production method and electrochemical test method it is same as Example 1.
Embodiment 3
(1) discarded pawpaw skin is collected, is cleaned and is dried with deionized water, weighed 3 g and be put into corundum boat, be placed in tubular type
Furnace, under the protection of inert nitrogen gas, Ventilation Rate is 80 mL min-1, with 5 DEG C of min-1Rate be warming up to 400
DEG C, and 2 h are kept, later with 5 DEG C of min-1300 DEG C are cooled to, pre- carbonized product A3 is obtained.
(2) the pre- carbonized product A3 of 0.6 g and 1.8 g melamines are weighed with mass ratio 1:3 with assay balance, are subsequently placed in
In ball mill, 300 rpm of rotational speed of ball-mill, Ball-milling Time is each 10 min of positive and negative rotation, altogether 20 min of mechanical ball mill, after ball milling
Mixture is put into corundum boat, is placed in tube furnace, and under the protection of inert nitrogen gas, Ventilation Rate is 80 mL min-1, with 3
℃ min-1Rate be warming up to 300 DEG C, and 2 h are kept, later with 3 DEG C of min-1It is cooled to 100 DEG C, after obtaining N doping
Product B3.
(3) with assay balance with mass ratio 1:3(A: saleratus) 1.8 g of saleratus is weighed, first it is fully ground carbonic acid
Hydrogen potassium is blended into N doping product B3, is fully ground 10 min, the mixture after grinding is then put into corundum boat to powdered
In, it is placed in tube furnace, under the protection of inert nitrogen gas, Ventilation Rate is 80 mL min-1, with 3 DEG C of min-1Rate
800 DEG C are warming up to, and keeps 2 h, later with 3 DEG C of min-1300 DEG C are cooled to, porous carbon materials C3 is obtained.
(4) porous carbon materials C3 is put into beaker, is put into magneton, with the 1 mol L of 120 mL in magnetic stirring apparatus-1
2 h of pickling, pickling bath temperature are 50 DEG C to dilute hydrochloric acid solution in a water bath, and pickling rate is 300 rpm, uses vacuum pump later
Decompression suction filtration is carried out, deionized water is washed to filtrate and is in neutrality, and is placed in 80 DEG C of baking ovens and dries, and obtains no metal wood melon skin nitrogen
Doped porous carbon material D3.
Sample made from the method is named as HNPC-2-800.
It is above-mentioned without metal wood melon skin nitrogen-doped porous carbon material HNPC-2-800 as fuel cell oxygen reduction catalyst
Working electrode production method and electrochemical test method it is same as Example 1.
Embodiment 4
(1) discarded pawpaw skin is collected, is cleaned and is dried with deionized water, weighed 3 g and be put into corundum boat, be placed in tubular type
Furnace, under the protection of inert nitrogen gas, Ventilation Rate is 80 mL min-1, with 5 DEG C of min-1Rate be warming up to 400
DEG C, and 2 h are kept, later with 5 DEG C of min-1300 DEG C are cooled to, pre- carbonized product A4 is obtained.
(2) the pre- carbonized product A4 of 0.6 g and 1.8 g melamines are weighed with mass ratio 1:3 with assay balance, are subsequently placed in
In ball mill, 300 rpm of rotational speed of ball-mill, Ball-milling Time is each 10 min of positive and negative rotation, altogether 20 min of mechanical ball mill, after ball milling
Mixture is put into corundum boat, is placed in tube furnace, and under the protection of inert nitrogen gas, Ventilation Rate is 80 mL min-1, with 3
℃ min-1Rate be warming up to 300 DEG C, and 2 h are kept, later with 3 DEG C of min-1It is cooled to 100 DEG C, after obtaining N doping
Product B4.
(3) with assay balance with mass ratio 1:3(A: saleratus) 1.8 g of saleratus is weighed, first it is fully ground carbonic acid
Hydrogen potassium is blended into N doping product B4, is fully ground 10 min, the mixture after grinding is then put into corundum boat to powdered
In, it is placed in tube furnace, under the protection of inert nitrogen gas, Ventilation Rate is 80 mL min-1, with 3 DEG C of min-1Rate
850 DEG C are warming up to, and keeps 2 h, later with 3 DEG C of min-1300 DEG C are cooled to, porous carbon materials C4 is obtained.
(4) porous carbon materials C4 is put into beaker, is put into magneton, with the 1 mol L of 120 mL in magnetic stirring apparatus-1
2 h of pickling, pickling bath temperature are 50 DEG C to dilute hydrochloric acid solution in a water bath, and pickling rate is 300 rpm, uses vacuum pump later
Decompression suction filtration is carried out, deionized water is washed to filtrate and is in neutrality, and is placed in 80 DEG C of baking ovens and dries, and obtains no metal wood melon skin nitrogen
Doped porous carbon material D4.
Sample made from the method is named as HNPC-2-850.
It is above-mentioned without metal wood melon skin nitrogen-doped porous carbon material HNPC-2-850 as fuel cell oxygen reduction catalyst
Working electrode production method and electrochemical test method it is same as Example 1.
Embodiment 5
(1) discarded pawpaw skin is collected, is cleaned and is dried with deionized water, weighed 3 g and be put into corundum boat, be placed in tubular type
Furnace, under the protection of inert nitrogen gas, Ventilation Rate is 80 mL min-1, with 5 DEG C of min-1Rate be warming up to 400
DEG C, and 2 h are kept, later with 5 DEG C of min-1300 DEG C are cooled to, pre- carbonized product A5 is obtained.
(2) the pre- carbonized product A5 of 0.6 g and 1.8 g melamines are weighed with mass ratio 1:3 with assay balance, are subsequently placed in
In ball mill, 300 rpm of rotational speed of ball-mill, Ball-milling Time is each 10 min of positive and negative rotation, altogether 20 min of mechanical ball mill, after ball milling
Mixture is put into corundum boat, is placed in tube furnace, and under the protection of inert nitrogen gas, Ventilation Rate is 80 mL min-1, with 3
℃ min-1Rate be warming up to 300 DEG C, and 2 h are kept, later with 3 DEG C of min-1It is cooled to 100 DEG C, after obtaining N doping
Product B5.
(3) with assay balance with mass ratio 1:3(A: saleratus) 1.8 g of saleratus is weighed, first it is fully ground carbonic acid
Hydrogen potassium is blended into N doping product B5, is fully ground 10 min, the mixture after grinding is then put into corundum boat to powdered
In, it is placed in tube furnace, under the protection of inert nitrogen gas, Ventilation Rate is 80 mL min-1, with 3 DEG C of min-1Rate
950 DEG C are warming up to, and keeps 2 h, later with 3 DEG C of min-1300 DEG C are cooled to, porous carbon materials C5 is obtained.
(4) porous carbon materials C5 is put into beaker, is put into magneton, with the 1 mol L of 120 mL in magnetic stirring apparatus-1
2 h of pickling, pickling bath temperature are 50 DEG C to dilute hydrochloric acid solution in a water bath, and pickling rate is 300 rpm, uses vacuum pump later
Decompression suction filtration is carried out, deionized water is washed to filtrate and is in neutrality, and is placed in 80 DEG C of baking ovens and dries, and obtains no metal wood melon skin nitrogen
Doped porous carbon material D5.
Sample made from the method is named as HNPC-2-950.
It is above-mentioned without metal wood melon skin nitrogen-doped porous carbon material HNPC-2-950 as fuel cell oxygen reduction catalyst
Working electrode production method and electrochemical test method it is same as Example 1.
Embodiment 6
(1) discarded straw is collected, is cleaned and is dried with deionized water, weighed 3 g and be put into corundum boat, be placed in tubular type
Furnace, under the protection of inert nitrogen gas, Ventilation Rate is 80 mL min-1, with 5 DEG C of min-1Rate be warming up to 400
DEG C, and 2 h are kept, later with 5 DEG C of min-1300 DEG C are cooled to, pre- carbonized product A6 is obtained.
(2) the pre- carbonized product A6 of 0.6 g and 1.8 g melamines are weighed with mass ratio 1:3 with assay balance, are subsequently placed in
In ball mill, 300 rpm of rotational speed of ball-mill, Ball-milling Time is each 10 min of positive and negative rotation, altogether 20 min of mechanical ball mill, after ball milling
Mixture is put into corundum boat, is placed in tube furnace, and under the protection of inert nitrogen gas, Ventilation Rate is 80 mL min-1, with 3
℃ min-1Rate be warming up to 300 DEG C, and 2 h are kept, later with 3 DEG C of min-1It is cooled to 100 DEG C, after obtaining N doping
Product B6.
(3) with assay balance with mass ratio 1:3(A: saleratus) 1.8 g of saleratus is weighed, first it is fully ground carbonic acid
Hydrogen potassium is blended into N doping product B6, is fully ground 10 min, the mixture after grinding is then put into corundum boat to powdered
In, it is placed in tube furnace, under the protection of inert nitrogen gas, Ventilation Rate is 80 mL min-1, with 3 DEG C of min-1Rate
950 DEG C are warming up to, and keeps 2 h, later with 3 DEG C of min-1300 DEG C are cooled to, porous carbon materials C6 is obtained.
(4) porous carbon materials C6 is put into beaker, is put into magneton, with the 1 mol L of 120 mL in magnetic stirring apparatus-1
2 h of pickling, pickling bath temperature are 50 DEG C to dilute hydrochloric acid solution in a water bath, and pickling rate is 300 rpm, uses vacuum pump later
Decompression suction filtration is carried out, deionized water is washed to filtrate and is in neutrality, and is placed in 80 DEG C of baking ovens and dries, and obtains no metal straw nitrogen and mixes
Miscellaneous porous carbon materials D6.
Sample made from the method is named as HNPC-3-900.
It is above-mentioned without metal straw nitrogen-doped porous carbon material HNPC-3-900 as fuel cell oxygen reduction catalyst
The production method of working electrode and electrochemical test method are same as Example 1.
Embodiment 7
(1) discarded bamboo shoots root is collected, is cleaned and is dried with deionized water, weighed 3 g and be put into corundum boat, be placed in tubular type
Furnace, under the protection of inert nitrogen gas, Ventilation Rate is 80 mL min-1, with 5 DEG C of min-1Rate be warming up to 400
DEG C, and 2 h are kept, later with 5 DEG C of min-1300 DEG C are cooled to, pre- carbonized product A7 is obtained.
(2) the pre- carbonized product A7 of 0.6 g and 1.8 g melamines are weighed with mass ratio 1:3 with assay balance, are subsequently placed in
In ball mill, 300 rpm of rotational speed of ball-mill, Ball-milling Time is each 10 min of positive and negative rotation, altogether 20 min of mechanical ball mill, after ball milling
Mixture is put into corundum boat, is placed in tube furnace, and under the protection of inert nitrogen gas, Ventilation Rate is 80 mL min-1, with 3
℃ min-1Rate be warming up to 300 DEG C, and 2 h are kept, later with 3 DEG C of min-1It is cooled to 100 DEG C, after obtaining N doping
Product B7.
(3) with assay balance with mass ratio 1:3(A: saleratus) 1.8 g of saleratus is weighed, first it is fully ground carbonic acid
Hydrogen potassium is blended into N doping product B7, is fully ground 10 min, the mixture after grinding is then put into corundum boat to powdered
In, it is placed in tube furnace, under the protection of inert nitrogen gas, Ventilation Rate is 80 mL min-1, with 3 DEG C of min-1Rate
950 DEG C are warming up to, and keeps 2 h, later with 3 DEG C of min-1300 DEG C are cooled to, porous carbon materials C7 is obtained.
(4) porous carbon materials C7 is put into beaker, is put into magneton, with the 1 mol L of 120 mL in magnetic stirring apparatus-1
2 h of pickling, pickling bath temperature are 50 DEG C to dilute hydrochloric acid solution in a water bath, and pickling rate is 300 rpm, uses vacuum pump later
Decompression suction filtration is carried out, deionized water is washed to filtrate and is in neutrality, and is placed in 80 DEG C of baking ovens and dries, and obtains no metal bamboo shoots root nitrogen
Doped porous carbon material D7.
Sample made from the method is named as HNPC-4-900.
It is above-mentioned without metal bamboo shoots root nitrogen-doped porous carbon material HNPC-4-900 as fuel cell oxygen reduction catalyst
Working electrode production method and electrochemical test method it is same as Example 1.
Embodiment 8
(1) discarded castock is collected, is cleaned and is dried with deionized water, weighed 3 g and be put into corundum boat, be placed in pipe
Formula furnace, under the protection of inert nitrogen gas, Ventilation Rate is 80 mL min-1, with 5 DEG C of min-1Rate be warming up to 400
DEG C, and 2 h are kept, later with 5 DEG C of min-1300 DEG C are cooled to, pre- carbonized product A8 is obtained.
(2) the pre- carbonized product A8 of 0.6 g and 1.8 g melamines are weighed with mass ratio 1:3 with assay balance, are subsequently placed in
In ball mill, 300 rpm of rotational speed of ball-mill, Ball-milling Time is each 10 min of positive and negative rotation, altogether 20 min of mechanical ball mill, after ball milling
Mixture is put into corundum boat, is placed in tube furnace, and under the protection of inert nitrogen gas, Ventilation Rate is 80 mL min-1, with 3
℃ min-1Rate be warming up to 300 DEG C, and 2 h are kept, later with 3 DEG C of min-1It is cooled to 100 DEG C, after obtaining N doping
Product B8.
(3) with assay balance with mass ratio 1:3(A: saleratus) 1.8 g of saleratus is weighed, first it is fully ground carbonic acid
Hydrogen potassium is blended into N doping product B8, is fully ground 10 min, the mixture after grinding is then put into corundum boat to powdered
In, it is placed in tube furnace, under the protection of inert nitrogen gas, Ventilation Rate is 80 mL min-1, with 3 DEG C of min-1Rate
950 DEG C are warming up to, and keeps 2 h, later with 3 DEG C of min-1300 DEG C are cooled to, porous carbon materials C8 is obtained.
(4) porous carbon materials C8 is put into beaker, is put into magneton, with the 1 mol L of 120 mL in magnetic stirring apparatus-1
2 h of pickling, pickling bath temperature are 50 DEG C to dilute hydrochloric acid solution in a water bath, and pickling rate is 300 rpm, uses vacuum pump later
Decompression suction filtration is carried out, deionized water is washed to filtrate and is in neutrality, and is placed in 80 DEG C of baking ovens and dries, and obtains no metal castock
Nitrogen-doped porous carbon material D8.
Sample made from the method is named as HNPC-5-900.
It is above-mentioned to be catalyzed without metal castock nitrogen-doped porous carbon material HNPC-5-900 as fuel cell oxygen reduction
The production method of the working electrode of agent and electrochemical test method are same as Example 1.
Embodiment 9
(1) discarded pawpaw skin is collected, is cleaned and is dried with deionized water, weighed 3 g and be put into corundum boat, be placed in tubular type
Furnace, under the protection of inert nitrogen gas, Ventilation Rate is 80 mL min-1, with 5 DEG C of min-1Rate be warming up to 400
DEG C, and 2 h are kept, later with 5 DEG C of min-1300 DEG C are cooled to, pre- carbonized product A9 is obtained.
(2) the pre- carbonized product A9 of 0.6 g and 1.8 g melamines are weighed with mass ratio 1:3 with assay balance, are subsequently placed in
In ball mill, 300 rpm of rotational speed of ball-mill, Ball-milling Time is each 10 min of positive and negative rotation, altogether 20 min of mechanical ball mill, after ball milling
Mixture is put into corundum boat, is placed in tube furnace, and under the protection of inert nitrogen gas, Ventilation Rate is 80 mL min-1, with 3
℃ min-1Rate be warming up to 250 DEG C, and 2 h are kept, later with 3 DEG C of min-1It is cooled to 100 DEG C, after obtaining N doping
Product B9.
(3) with assay balance with mass ratio 1:3(A: saleratus) 1.8 g of saleratus is weighed, first it is fully ground carbonic acid
Hydrogen potassium is blended into N doping product B9, is fully ground 10 min, the mixture after grinding is then put into corundum boat to powdered
In, it is placed in tube furnace, under the protection of inert nitrogen gas, Ventilation Rate is 80 mL min-1, with 3 DEG C of min-1Rate
900 DEG C are warming up to, and keeps 2 h, later with 3 DEG C of min-1300 DEG C are cooled to, porous carbon materials C9 is obtained.
(4) porous carbon materials C9 is put into beaker, is put into magneton, with the 1 mol L of 120 mL in magnetic stirring apparatus-1
2 h of pickling, pickling bath temperature are 50 DEG C to dilute hydrochloric acid solution in a water bath, and pickling rate is 300 rpm, uses vacuum pump later
Decompression suction filtration is carried out, deionized water is washed to filtrate and is in neutrality, and is placed in 80 DEG C of baking ovens and dries, and obtains no metal wood melon skin nitrogen
Doped porous carbon material D9.
Sample made from the method is named as HNPC-6-900.
It is above-mentioned without metal wood melon skin nitrogen-doped porous carbon material HNPC-6-900 as fuel cell oxygen reduction catalyst
Working electrode production method and electrochemical test method it is same as Example 1.
Embodiment 10
(1) discarded pawpaw skin is collected, is cleaned and is dried with deionized water, weighed 3 g and be put into corundum boat, be placed in tubular type
Furnace, under the protection of inert nitrogen gas, Ventilation Rate is 80 mL min-1, with 5 DEG C of min-1Rate be warming up to 400
DEG C, and 2 h are kept, later with 5 DEG C of min-1300 DEG C are cooled to, pre- carbonized product A10 is obtained.
(2) the pre- carbonized product A10 of 0.6 g and 1.8 g melamines are weighed with mass ratio 1:3 with assay balance, then set
In ball mill, 300 rpm of rotational speed of ball-mill, Ball-milling Time is each 10 min of positive and negative rotation, altogether 20 min of mechanical ball mill, after ball milling
Mixture be put into corundum boat, be placed in tube furnace, under the protection of inert nitrogen gas, Ventilation Rate be 80 mL min-1,
With 3 DEG C of min-1Rate be warming up to 350 DEG C, and 2 h are kept, later with 3 DEG C of min-1100 DEG C are cooled to, nitrogen is obtained and mixes
Product B10 after miscellaneous.
(3) with assay balance with mass ratio 1:3(A: saleratus) 1.8 g of saleratus is weighed, first it is fully ground carbonic acid
Hydrogen potassium is blended into N doping product B10, is fully ground 10 min, the mixture after grinding is then put into corundum to powdered
In boat, it is placed in tube furnace, under the protection of inert nitrogen gas, Ventilation Rate is 80 mL min-1, with 3 DEG C of min-1Speed
Rate is warming up to 900 DEG C, and keeps 2 h, later with 3 DEG C of min-1300 DEG C are cooled to, porous carbon materials C10 is obtained.
(4) porous carbon materials C10 is put into beaker, is put into magneton, with 1 mol of 120 mL in magnetic stirring apparatus
L-12 h of pickling, pickling bath temperature are 50 DEG C to dilute hydrochloric acid solution in a water bath, and pickling rate is 300 rpm, uses vacuum later
Pump carries out decompression suction filtration, and deionized water is washed to filtrate and is in neutrality, and is placed in 80 DEG C of baking ovens and dries, and obtains no metal wood melon skin
Nitrogen-doped porous carbon material D10.
Sample made from the method is named as HNPC-7-900.
It is above-mentioned without metal wood melon skin nitrogen-doped porous carbon material HNPC-7-900 as fuel cell oxygen reduction catalyst
Working electrode production method and electrochemical test method it is same as Example 1.
1) high resolution transmission electron microscopy (HRTEM) is tested
No metal wood melon skin nitrogen-doped porous carbon material obtained is placed under high resolution transmission electron microscope (HRTEM) and is seen
It examines, as shown in Figure 1, it can be seen that many discontinuous cotton-shaped lattice fringes illustrate this without metal wood melon skin N doping porous carbon
Material has more micropore, the mesoporous hierarchical porous structure coexisted, main carbonization structure feature, wherein also including certain
Disordering structure.
2) nitrogen adsorption desorption is tested
Material specific surface area and hole are carried out to the sample in embodiment 1-5 and embodiment 9-10 using nitrogen physisorption adsorption desorption instrument
Structured testing.Sample HNPC-2-750, HNPC-2-800, HNPC-2-850, HNPC-2- according to test, in embodiment 1-5
900, the specific surface area of HNPC-2-950 is respectively 1885.60 m2 g-1、1501.45 m2 g-1、1189.92 m2 g-1、
1670.86 m2 g-1、1356.61 m2 g-1, total pore volume is respectively 1.020 cm3 g-1、0.828 cm3 g-1、0.887 cm3 g-1、1.134 cm3 g-1、0.939 cm3 g-1, micropore is respectively 0.641 cm3 g-1、0.520 cm3 g-1、0.285 cm3 g-1、
0.576 cm3 g-1、0.372 cm3 g-1；The specific surface of sample HNPC-6-900, HNPC-7-900 in embodiment 9-10 integrate
It Wei not 1353.04 m2 g-1、1629.91 m2 g-1, total pore volume is respectively 0.850 cm3 g-1、1.029 cm3 g-1, micropore point
It Wei not 0.435 cm3 g-1、0.537 cm3 g-1.Thus also find out different secondary carburizing temperature and ditto doping temperature can not
The actually active amount of melamine in carbon material is set to change, comparing surface area and pore structure has larger impact, excessive trimerization
Cyanamide generates blocking to carbon material pore structure.Fig. 2 and Fig. 3 is the nitrogen adsorption desorption curve graph of seven samples, by same in figure
It can be seen that material prepared by the method for the present invention specific surface area all with higher, and possess a large amount of micropore, Jie
Hole multistage pore size distribution.As shown in Figure 4 and Figure 5, pore-size distribution analysis is carried out by density functional theory (DFT) analysis model, into
One step demonstrates the hierarchical porous structure distribution of the material.
3) hydrogen reduction electrocatalysis characteristic is tested
With assay balance weigh 3 mg without metal wood melon skin nitrogen-doped porous carbon material (HNPC-2-750, HNPC-2-800,
HNPC-2-850、HNPC-2-900、HNPC-2-950、HNPC-3-900、HNPC-4-900、HNPC-5-900、HNPC-6-900、
HNPC-7-900 it) is respectively placed in centrifuge tube, it is poly- that 170 microlitres of deionized water, 70 microlitres of isopropanol and 5 % perfluorinated sulfonic acids-is added
10 microlitres of solution of TFE copolymer (Nafion) is uniformly mixed, and with ultrasonic cleaning machine ultrasound 1 hour, formation was uniformly dispersed
Black dispersion liquid, take 10 microlitres of mixed solutions with liquid-transfering gun, drip in the rotating disk electrode (r.d.e) (RDE) of 5 mm of diameter, then
Working electrode is made in naturally dry in air.
Using the electrode as working electrode, platinum filament is to electrode, 3.5 mol L-1Klorvess Liquid in, silver/silver chlorate electricity
Extremely reference electrode forms three-electrode system, in 0.1 mol L of oxygen saturation-1KOH solution, 0.5 mol L-1 H2SO4It is molten
Liquid and 0.1 mol L-1 Linear sweep voltammetry curve (LSV) is carried out in PBS solution, sweeping speed is 10 mV s-1.It is similar, by 20
% business platinum carbon catalyst (Pt/C) according to above-mentioned preparation method be made black mucus and drip in dried in rotating disk electrode (r.d.e) carry out
Test, and compared with material prepared by the present invention carries out electrocatalysis characteristic, wherein Pt/C catalyst is in rotating disk electrode (r.d.e)
Load capacity is maintained at 50 μ g cm-2Left and right.
Fig. 6, Fig. 7 and Fig. 8 are respectively embodiment 1 and embodiment 2-5 in 0.1 mol L of oxygen saturation-1 KOH solution, 0.5
mol L-1 H2SO4Solution and 0.1 mol L-1 The linear sweep voltammetry curve (LSV) of 1600 rpm, can see in PBS solution
Out, the initial potential, half wave potential of embodiment 1 and limiting current density are all substantially better than embodiment 2-5, can be with the oxygen of business
Reduction platinum carbon catalyst performance compares favourably, and has the application prospect of preferably substitution platinum carbon business.
Fig. 9, Figure 10 and Figure 11 are porous without metal wood melon skin N doping made from the embodiment of the present invention 1 and embodiment 9-10
Carbon material is saturated 0.1 mol L in oxygen-1KOH solution, 0.5 mol L-1 H2SO4Solution and 0.1 mol L-1 In PBS solution
The linear sweep voltammetry curve (LSV) of 1600 rpm, can intuitively find out from figure, carry out melamine by adulterating before 300 DEG C
The electro-chemical activity of the HNPC-2-900 of amine nitrating processing is substantially better than other two contrast samples.
Figure 12, Figure 13 and Figure 14 are that the embodiment of the present invention 1 and embodiment 6-8 are obtained without metal papaya tablet, straw, bamboo shoots
Root, castock nitrogen-doped porous carbon material are saturated 0.1 mol L in oxygen respectively-1KOH solution, 0.5 mol L-1 H2SO4
Solution and 0.1 mol L-1 The linear sweep voltammetry curve (LSV) of 1600 rpm, curve show four kinds of differences in PBS solution
Hydrogen reduction electrocatalysis characteristic of the species matter after method processing of the invention compared with business is with Pt/C all more not
Mistake, wherein HNPC-2-900 has optimal hydrogen reduction electrocatalysis characteristic, in 0.5 mol L-1 H2SO4In solution, HNPC-2-
900 initial potentials are close to 0.87 V(relative to RHE), half wave potential is close to 0.76 V(relative to RHE), limiting current density is about
For -5.15 mA cm-2；In 0.1 mol L-1 In KOH solution, initial potential is close to 1.00 V(relative to RHE), half wave potential
Close to 0.87 V(relative to RHE), limiting current density is about -5.89 mA cm-2；In 0.1 mol L-1PBS solution (pH=
7.0) in, initial potential is close to 0.88V(relative to RHE), half wave potential is close to 0.73 V(relative to RHE), carrying current is close
Degree is about -5.53 mA cm-2No matter electrocatalysis characteristic, can be with business platinum carbon catalyst in acid, alkalinity or neutrality
Performance compares favourably.Meanwhile this method is to other species matter (agricultural fruit/vegetable wastes, such as straw, bamboo shoots root, castock
Deng) handled after, can also achieve the effect that electrocatalysis characteristic promoted, have universality.
4) cyclical stability is tested
By the HNPC-2-900 in embodiment 1 in 0.1 mol L-1In KOH electrolyte, turn in 400 rpm of rotating disk electrode (r.d.e)
Speed is lower to carry out the test of i-t chronoamperometry, while Pt/C carries out test under identical condition and compares, as shown in figure 15, can
To find out, HNPC-2-900 electric current after the circulation of 50000 s is almost unchanged, and conservation rate is 99 %, much higher than 75 %'s of Pt/C
Stability.
By the HNPC-2-900 in embodiment 1 in 0.5 mol L-1 H2SO4In electrolyte, in rotating disk electrode (r.d.e) 400
The test of i-t chronoamperometry is carried out under rpm revolving speed, while Pt/C carries out test under identical condition and compares, such as Figure 16 institute
Show, it can be seen that HNPC-2-900 electric current after the circulation of 50000 s almost keeps stable, and conservation rate is 99 %, is much higher than
The stability of 54 % of Pt/C.
Similarly, by the HNPC-2-900 in embodiment 1 in 0.1 mol L-1In PBS electrolyte, in rotating disk electrode (r.d.e)
The test of i-t chronoamperometry is carried out under 400 rpm revolving speeds, while Pt/C carries out test under identical condition and compares, and such as schemes
Shown in 17, it can be seen that HNPC-2-900 electric current conservation rate after the circulation of 50000 s is 90 %, much higher than 48 %'s of Pt/C
Stability.
5) methanol tolerance is tested
By the HNPC-2-900 in embodiment 1 in 0.1 mol L-1 In 400 rpm revolving speed of rotating disk electrode (r.d.e) in KOH electrolyte
Lower progress methanol tolerance test, while Pt/C carries out test under identical condition and compares, as shown in figure 18.It can be seen by Figure 18
Out, in 200 s by 1 mol L-1Methanol be injected into electrolyte, the catalytic activity of HNPC-2-900 catalyst is kept substantially
It is constant, and the catalytic activity of Pt/C catalyst experienced violent decline, illustrate mixing without metal wood melon skin nitrogen for invention preparation
Miscellaneous carbon material in alkaline environment there is superior methanol tolerance to poison performance.
By the HNPC-2-900 in embodiment 1 in 0.5 mol L-1 H2SO4In rotating disk electrode (r.d.e) 400 in electrolyte
Methanol tolerance test is carried out under rpm revolving speed, while Pt/C carries out test under identical condition and compares, as shown in figure 19.By scheming
19 as can be seen that in 200 s by 1 mol L-1Methanol be injected into electrolyte, the current density of HNPC-2-900 catalyst
Fluctuate very little, and the current density after methanol is added of Pt/C catalyst fluctuation acutely, illustrate the invention prepare without metal wood
Melon skin nitrogen-doped carbon material equally there is superior methanol tolerance to poison performance in acid condition.
Similarly, by the HNPC-2-900 in embodiment 1 in 0.1 mol L-1In rotating disk electrode (r.d.e) 400 in PBS electrolyte
Methanol tolerance test is carried out under rpm revolving speed, while Pt/C carries out test under identical condition and compares, as shown in figure 20.By scheming
20 as can be seen that in 200 s by 1 mol L-1Methanol be injected into electrolyte, the current density of HNPC-2-900 catalyst
Restore normal quickly after minor swing, and the current disturbing after methanol is added of Pt/C catalyst is very big, activity constantly decline.
Illustrate invention preparation without metal wood melon skin nitrogen-doped carbon material, to poison performance also preferable for methanol tolerance in neutral conditions.
Claims (10)
1. a kind of preparation method of full pH value fuel battery negative pole oxygen reduction electro-catalyst, which comprises the following steps:
(1) agricultural fruit/vegetable waste is collected, cleaning is dried, and using heating equipment, is warming up to 300 ~ 500 under inert gas protection
DEG C, and 1 ~ 3 h is kept, it is cooled to 100 ~ 350 DEG C later, obtains pre- carbonized product A；
(2) it is that 1:3 weighs melamine with the pre- carbonized product A of mass ratio and melamine, mixes, ball milling, it will be mixed after ball milling
Object is closed, using heating equipment, is warming up to 250 ~ 350 DEG C under inert gas protection, and keeps 1 ~ 3 h, it is cooled to 50 later ~
150 DEG C, the product B after obtaining N doping；
(3) saleratus is weighed with mass ratio pre- carbonized product A: saleratus 1:3, it is mixed with the product B after N doping
It closes, grinding by the mixture after grinding, using heating equipment, is warming up to 800 ~ 950 DEG C, and keep under inert gas protection
1 ~ 3 h is cooled to 100 ~ 350 DEG C later, obtains porous carbon materials C；
(4) by porous carbon materials C dilute hydrochloric acid solution 2 h of pickling in a water bath, pickling temperature is 50 DEG C, filtering, is washed to
Property, drying obtains electrocatalyst for cathode D.
2. the preparation method of full pH value fuel battery negative pole oxygen reduction electro-catalyst according to claim 1, feature exist
In in step (2), the temperature of the carbonization is 300 DEG C.
3. the preparation method of full pH value fuel battery negative pole oxygen reduction electro-catalyst according to claim 1, feature exist
In in step (2), 300 rpm of rotational speed of ball-mill, Ball-milling Time is each 10 min of positive and negative rotation.
4. the preparation method of full pH value fuel battery negative pole oxygen reduction electro-catalyst according to claim 1, feature exist
In in step (3), the temperature of the carbonization is 900 DEG C.
5. the preparation method of full pH value fuel battery negative pole oxygen reduction electro-catalyst according to claim 1, feature exist
In step (1) heating and cooling speed are 5 DEG C of min-1。
6. the preparation method of full pH value fuel battery negative pole oxygen reduction electro-catalyst according to claim 1, feature exist
In step (2) heating and cooling speed are 3 DEG C of min-1。
7. the preparation method of full pH value fuel battery negative pole oxygen reduction electro-catalyst according to claim 1, feature exist
In step (3) heating and cooling speed are 3 DEG C of min-1。
8. the preparation method of full pH value fuel battery negative pole oxygen reduction electro-catalyst according to claim 1, feature exist
It is that pawpaw skin, straw, bamboo shoots root, castock are one or more in, the agricultural fruit/vegetable waste.
9. the preparation method of full pH value fuel battery negative pole oxygen reduction electro-catalyst according to claim 1, feature exist
In the heating equipment is tube furnace, and the inert gas is nitrogen.
10. made from the preparation method of full pH value fuel battery negative pole oxygen reduction electro-catalyst described according to claim 1 ~ 9
Full pH value fuel battery negative pole elctro-catalyst, which is characterized in that the catalyst includes no metal nitrogen-doped porous carbon material
D。
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