CN107026273B - Nitrating carbon ball/graphene/platinum nano particle trielement composite material and its preparation method and application - Google Patents
Nitrating carbon ball/graphene/platinum nano particle trielement composite material and its preparation method and application Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 265
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 167
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 230000000802 nitrating effect Effects 0.000 title claims abstract description 131
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 114
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 49
- 229910021397 glassy carbon Inorganic materials 0.000 claims abstract description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000004070 electrodeposition Methods 0.000 claims abstract description 27
- 239000003792 electrolyte Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000007853 buffer solution Substances 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 229940075397 calomel Drugs 0.000 claims abstract description 14
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000011521 glass Substances 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 8
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 16
- 229920001690 polydopamine Polymers 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 11
- 230000005611 electricity Effects 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001103 potassium chloride Substances 0.000 claims description 8
- 235000011164 potassium chloride Nutrition 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 239000000446 fuel Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 235000013339 cereals Nutrition 0.000 claims description 4
- 239000002077 nanosphere Substances 0.000 claims description 4
- 229920001661 Chitosan Polymers 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 3
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 239000011324 bead Substances 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 239000007974 sodium acetate buffer Substances 0.000 claims description 2
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 claims description 2
- LEAHFJQFYSDGGP-UHFFFAOYSA-K trisodium;dihydrogen phosphate;hydrogen phosphate Chemical compound [Na+].[Na+].[Na+].OP(O)([O-])=O.OP([O-])([O-])=O LEAHFJQFYSDGGP-UHFFFAOYSA-K 0.000 claims 2
- 238000004140 cleaning Methods 0.000 abstract description 4
- 239000011805 ball Substances 0.000 description 115
- 238000012360 testing method Methods 0.000 description 33
- 238000006722 reduction reaction Methods 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 15
- 229910052760 oxygen Inorganic materials 0.000 description 15
- 239000001301 oxygen Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 238000012986 modification Methods 0.000 description 13
- 230000004048 modification Effects 0.000 description 13
- 239000002245 particle Substances 0.000 description 11
- 238000012512 characterization method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 6
- 238000013461 design Methods 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- -1 graphite Alkene Chemical class 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000008055 phosphate buffer solution Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011807 nanoball Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000004832 voltammetry Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- HFEWAGKDZLEFCT-UHFFFAOYSA-L C(C)C(COP(=O)(OCC(CCCC)CC)[O-])CCCC.P(=O)(O)([O-])O.[Na+].[Na+] Chemical compound C(C)C(COP(=O)(OCC(CCCC)CC)[O-])CCCC.P(=O)(O)([O-])O.[Na+].[Na+] HFEWAGKDZLEFCT-UHFFFAOYSA-L 0.000 description 1
- 241000143432 Daldinia concentrica Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003001 depressive effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001595 flow curve Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- QLFFCLRSMTUBEZ-UHFFFAOYSA-N phosphoric acid;sodium Chemical compound [Na].[Na].OP(O)(O)=O QLFFCLRSMTUBEZ-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012353 t test Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8853—Electrodeposition
-
- 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)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Carbon And Carbon Compounds (AREA)
- Inert Electrodes (AREA)
Abstract
The invention discloses a kind of trielement composite materials and its preparation method and application of nitrating carbon ball/graphene/platinum nano particle;Method includes the following steps: 1) carbon containing nitrogen source is heat-treated to obtain nitrating carbon ball;2) nitrating carbon ball solution is then coated on glass carbon surface to form nitrating carbon ball modified glassy carbon electrode;3) it disperses graphene oxide in buffer solution to form graphene oxide solution, in graphene oxide solution, electrodeposition process is carried out so that graphene/nitrating carbon ball modified glassy carbon electrode is made by cyclic voltammetry (CV) using nitrating carbon ball modified glassy carbon electrode as working electrode, platinum electrode to be to electrode, calomel electrode be reference electrode;4) graphene/nitrating carbon ball modified glassy carbon electrode is soaked in platiniferous electrolyte through constant potential electrodeposition process so that nitrating carbon ball/graphene/platinum nano particle trielement composite material is made.This method cleaning, big lamellar structure efficient and that graphene will not be destroyed.
Description
Technical field
The present invention relates to composite materials, and in particular, to a kind of graphene/poly-dopamine/platinum composite material and its preparation
Method and application.
Background technique
Currently, the synthetic method of graphene mainly has mechanical spalling, chemical vapor deposition, electrochemical synthesis etc..Its
In, electrochemical synthesis is a kind of green, cleaning, effective, the quick and nondestructive method for preparing graphene, it can lead to
Toning nodal potential changes the fermi level of electrode surface material to change the electronic state of material, thus it is controllable to material into
Row modification and reduction.
The carbon atom that graphene is intensive by one layer, is wrapped in honeycomb crystal lattice forms, and thickness is only
0.35nm, C-C bond distance are 0.142nm.Because of its unique structure, and show many excellent electricity, optics, calorifics and machinery
Performance, such as large specific surface area, electroactive site abundant.The graphene film 2D planar geometry of single electron thickness degree is advantageous
In enhancing electronics transfer.Therefore, graphene is prepared into multi-element composite material as base material and combines graphene and other groups
The excellent properties divided, energy chemistry conveniently have a good application prospect.
Currently, fuel cell is popular as a kind of reproducible cleanable energy, but the cathode oxygen of fuel cell
Reduction catalysts reaction is the bottleneck for hindering fuel cell further to develop.According to the literature, nitrogen-doped graphene is to hydrogen reduction
Reaction has very high catalytic activity, but the dispersion of existing nitrogen-doped graphene material is bad, and nitrating is uneven;At present
For most of nitrogen-doped graphene material during as oxygen reduction catalyst, temperature, does not cause catalytic effect poor.
Summary of the invention
The object of the present invention is to provide the trielement composite materials and its system of a kind of nitrating carbon ball/graphene/platinum nano particle
Preparation Method and application, nitrating carbon ball/graphene/platinum nano particle trielement composite material being capable of efficient catalytic fuel cell yin
Pole oxygen reduction reaction, so that it can be catalyzed in reaction in hydrogen reduction is used as catalyst;And the system of the trielement composite material
Preparation Method has many advantages, such as green, cleaning, structure that is efficient and will not destroying graphene, keeps the original advantage of graphene.
To achieve the goals above, the present invention provides a kind of tri compounds of nitrating carbon ball/graphene/platinum nano particle
Material, wherein the compounding ingredients of trielement composite material are graphene, nitrating carbon ball and nano platinum particle.
The present invention also provides a kind of preparation method of the trielement composite material of nitrating carbon ball/graphene/platinum nano particle,
Wherein, preparation method the following steps are included:
1) carbon containing nitrogen source is heat-treated to obtain nitrating carbon ball;
2) nitrating carbon ball is dissolved in formation nitrating carbon ball solution in solvent, nitrating carbon ball solution is then coated on glass carbon
Surface is to form nitrating carbon ball modified glassy carbon electrode;
3) it disperses graphene oxide in buffer solution to form graphene oxide solution, it is molten in the graphene oxide
It is working electrode, platinum electrode to be to electrode, calomel electrode be reference electrode by following using nitrating carbon ball modified glassy carbon electrode in liquid
Ring voltammetry (CV) carries out electrodeposition process so that graphene/nitrating carbon ball modified glassy carbon electrode is made;
4) graphene/nitrating carbon ball modified glassy carbon electrode is soaked in platiniferous electrolyte through constant potential electrodeposition process
Nitrating carbon ball/graphene/platinum nano particle trielement composite material is made.
The present invention also provides a kind of as above-mentioned nitrating carbon ball/graphene/platinum nano particle trielement composite material exists
Application in the hydrogen reduction catalysis reaction of fuel battery negative pole.
In the above-mentioned technical solutions, the present invention then prepares nitrating carbon ball modification glass carbon electricity by first preparing nitrating carbon ball
Pole;Then CV method electro-deposition graphene is carried out on the basis of nitrating carbon ball modified glassy carbon electrode again graphene/nitrating is made
Carbon ball modified glassy carbon electrode;It is last to be received again on graphene/nitrating carbon ball modified glassy carbon electrode surface by constant potential platinum electrodeposition
Rice corpuscles has finally obtained nitrating carbon ball/graphene/platinum nano particle trielement composite material;The wherein nitrating in the present invention
Carbon ball/graphene/platinum nano particle trielement composite material be in the form of being supported on the surface of glass-carbon electrode existing for.The nitrating
Carbon ball/graphene/platinum nano particle trielement composite material is capable of the Cathodic oxygen reduction of efficient catalytic fuel cell.Meanwhile
Prepared in the present invention nitrating carbon ball/graphene/platinum nano particle trielement composite material method cleaning, efficiently and stone will not be destroyed
The big lamellar structure of black alkene.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the characterization result figure for detecting example 1;
Fig. 2 is the characterization result figure for detecting example 2;
Fig. 3 is the characterization result figure for detecting example 3;
Fig. 4 is the experimental result picture of application examples 1;
Fig. 5 is the experimental result picture of application examples 2;
Fig. 6 is the experimental result picture of application examples 3;
Fig. 7 is the Koutecky-Levich curve graph obtained according to Fig. 5;
Fig. 8 is the experimental result picture of application examples 4.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of trielement composite material of nitrating carbon ball/graphene/platinum nano particle, the tri compound materials
The compounding ingredients of material are graphene, nitrating carbon ball and nano platinum particle.It is to be supported on glass-carbon electrode table in the trielement composite material
The composite material in face;Firstly, nitrating carbon ball is coated in electrode surface, secondly, graphene is by being electrodeposited in the table of nitrating carbon ball
Face;Finally nano platinum particle is deposited on the surface of graphene to obtain trielement composite material.
In the trielement composite material, the nitrogen source in complex group minute nitrating carbon ball can be selected in a wide range
It selects, if nitrogen source used can be at least one in poly-dopamine ball, chitosan bead, polyaniline nano ball and polypyrrole nanosphere
Person.But in order to which that further improves trielement composite material prepares yield, since poly-dopamine has polymerization effect well
Fruit, therefore preferably, the nitrogen source in nitrating carbon ball used is poly-dopamine ball.
A kind of preparation side of the trielement composite material of nitrating carbon ball/graphene/platinum nano particle is additionally provided in the present invention
Method, wherein the preparation method the following steps are included:
1) carbon containing nitrogen source is heat-treated to obtain nitrating carbon ball;
2) nitrating carbon ball is dissolved in formation nitrating carbon ball solution in solvent, nitrating carbon ball solution is then coated on glass carbon
Surface is to form nitrating carbon ball modified glassy carbon electrode;
3) it disperses graphene oxide in buffer solution to form graphene oxide solution, in graphene oxide solution
In, it be to electrode, calomel electrode as working electrode, platinum electrode using nitrating carbon ball modified glassy carbon electrode is that reference electrode passes through circulation
Voltammetry (CV) carries out electrodeposition process so that graphene/nitrating carbon ball modified glassy carbon electrode is made;
4) graphene/nitrating carbon ball modified glassy carbon electrode is soaked in platiniferous electrolyte through constant potential electrodeposition process
Nitrating carbon ball/graphene/platinum nano particle trielement composite material is made.
In above-mentioned preparation method, in step 1), it is used containing carbon nitrogen source can in a wide range into selection,
Such as: nitrogen source used is can be at least one in poly-dopamine ball, chitosan bead, polyaniline nano ball and polypyrrole nanosphere
Person.But in order to improve the preparation efficiency of trielement composite material, therefore preferably, selection poly-dopamine ball is nitrogen source.
In addition, nitrating carbon ball can just be obtained by needing to be heat-treated carbon containing nitrogen source in step 1), wherein be heat-treated
Condition can select in a wide range, however, to ensure that being carbonized successfully and obtaining nitrating carbon ball, it is preferable that heat treatment used
Condition are as follows: in an inert atmosphere, first 700-900 DEG C is warming up to from 20-35 DEG C, then after 700-900 DEG C of maintenance 1-1.5h
It is cooled to 20-40 DEG C.
In the above technical solution, the heating of heat treatment and the rate of cooling can be selected in a wide range,
But in order to improve the catalytic performance of the preparation rate of nitrating carbon ball and nitrating carbon ball, it is preferable that the rate of heating is 3-5
DEG C/min, the rate of cooling is 5-10 DEG C/min.
In addition, in step 2), nitrating carbon ball is dissolved in formation nitrating carbon ball solution in solvent, and by nitrating obtained
Carbon ball solution is coated on glass carbon surface to form nitrating carbon ball modified glassy carbon electrode;Wherein, the solvent of nitrating carbon ball solution is prepared
It can select in a wide range, such as: naphthols, acetone, ethyl alcohol or water;But in order to be more advantageous to nitrating carbon ball to glass-carbon electrode
Modification and consider from economic level, therefore preferably, solvent for use is water.
Nitrating carbon ball is being coated on glassy carbon electrode surface so that nitrating carbon ball modified glassy carbon electrode, nitrating carbon used is made
The concentration and coated weight of ball can select in a wide range, still, prepare and mention to be more advantageous to the success of composite material
The catalytic effect of high composite material, it is preferable that the mass concentration of nitrating carbon ball is 3-5mg/mL in nitrating carbon ball solution;And with table
Area is 7.065mm2The glass carbon surface on the basis of, it is preferable that coated weight used be 3-6 μ L.
When preparing graphene oxide solution, buffer solution used can select in very wide in range range, such as phosphoric acid
Disodium hydrogen-sodium dihydrogen phosphate buffer, acetic acid-sodium acetate buffer solution or Tris-hydrochloric acid buffer solution;But in order into one
Step improves the electrodeposition effect of electro-deposition redox graphene, it is preferable that buffer solution used is disodium hydrogen phosphate-di(2-ethylhexyl)phosphate
Hydrogen sodium buffer solution, and the concentration of phosphate radical is 0.067-0.07mol/L in buffer solution, and the pH of buffer solution is
9.18-9.20。
On the basis of the above embodiment, in step 3), nitrating carbon ball modified glassy carbon electrode is placed in graphite oxide
CV electro-deposition is carried out in alkene solution so that graphene/nitrating carbon ball modified glassy carbon electrode is made.The quality of graphite oxide used is dense
Degree can change in wide in range range, but in order to improve the electrodeposition effect of graphene, it is preferable that graphene oxide used
The mass concentration of graphene oxide is 1-5mg/mL in solution;It and with surface area is 7.065mm2The glass carbon surface be base
Standard, the dosage of the graphene oxide solution are 3-5mL.
In addition, the condition of CV can select in a wide range, as long as graphene is deposited to the surface of nitrating carbon ball just
Can, but in order to improve the deposition efficiency of graphene and effect, it is preferable that the condition of the CV are as follows: current potential be -1.5V~
0.6V, circulating ring number are 5-15 circle, sweep speed 0.01-0.05V/s.
In the step 4) of above-mentioned preparation method, contain platinum source as long as meeting in the concrete component of platiniferous electrolyte used
, but in order to be more advantageous to platinum electrodeposition particle, it is preferable that the platiniferous electrolyte is the mixing of chloroplatinic acid and potassium chloride
Liquid.Wherein, the proportion of chloroplatinic acid and potassium chloride can select in a wide range, but in order to improve the deposition of nano platinum particle
Rate, it is preferable that the concentration of chloroplatinic acid is 2.0-2.5mmol/L, and the concentration of potassium chloride is 0.1-0.2mol/L.
In addition, the condition of constant potential platinum electrodeposition can select in a wide range, as long as platinum particles are deposited to nitrating
Carbon ball/graphene surface, but in order to improve the deposition efficiency of platinum particles and effect, it is highly preferred that constant potential electricity is heavy
Long-pending condition are as follows: current potential is -0.3~-0.2V, and sedimentation time 60-140s, preferably current potential are -0.25V.
It and with surface area is 7.065mm2The glass carbon surface on the basis of, the dosage of platinum electrolyte used is 3-5mL.
The present invention also provides a kind of above-mentioned nitrating carbon ball/graphene/platinum nano particle trielement composite materials to fire
Expect that there is good catalytic effect in the hydrogen reduction catalysis reaction of cell cathode.
The present invention will be described in detail by way of examples below.In following embodiment, Electrochemical Detection is in Shanghai occasion
It is carried out on the chem workstation of magnificent instrument company's model CHI6211E, scanning electron microscope detection elements analysis detection (EDS) exists
It is carried out in the scanning electron microscope of Japanese Hitachi model S-4800;Transmission electron microscope is JEOL- in Japanese Hitachi company model
It is carried out on 2010 transmission electron microscope;Rotating disk electrode (r.d.e) is the rotating disk electrode (r.d.e) device of U.S. Pine company MSR model.
Graphene oxide is the commercially available product of organic my 10mg/mL of institute's specification in Chengdu, and 20% business platinum carbon powder is purchased from lark
The prestige CAS platinum carbon powder for 7440-06-4.
Preparation example 1
According to document: Xiaoli Jiang, Yinling Wang*, Maoguo Li*, " Selecting Water-
Alcohol Mixed Solvent for Synthesis of Polydopamine Nano-spheres Using
Side documented by Solubility Parameter ", Scientific Reports2014,4, Article Number6070.
Method prepares poly-dopamine ball:
Poly-dopamine ball (PDAs) is synthesized in water-alcohol in the mixed solvent, the CH of 28mL is added in the ultrapure water of 112mL3OH is stirred
Mix mixing.At room temperature, the ammonium hydroxide (NH of different volumes is added into methanol/ultrapure water mixed solution4OH, 28-30%), respectively
For 0.6mL, 0.8mL.After being stirred 30min, the dopamine of 0.5g is added into mixed solution.Solution gradually becomes dark brown
30h is stirred at room temperature in color.It is finally centrifuged, ethyl alcohol and water are washed respectively, and obtained product is 60 DEG C under vacuum oven
It is dried overnight, obtain poly-dopamine ball.
Embodiment 1
1) poly-dopamine ball is placed in electric-type furnace, under inert gas flow, from 25 DEG C slowly according to the speed of 3 DEG C/min
Rate is warming up to 700 DEG C, calcining at constant temperature 1h, is then cooled to 20 DEG C with the rate of 5 DEG C/min and obtains the nitrating carbon ball of black;
2) nitrating carbon ball is dispersed in water to obtain the nitrating carbon ball solution that mass concentration is 3mg/mL;Take 4 μ L nitrating carbon
Ball solution is coated on surface (the surface area 7.065mm of glass-carbon electrode2), nitrating carbon ball modification glass carbon electricity is obtained after drying
Pole;
3) first by graphene oxide ultrasonic disperse in the phosphate buffer solution that phosphorus acid ion concentration is 0.067mol/L
(pH=9.18) graphene oxide solution that mass concentration is 3mg/mL is made in;Then, by nitrating carbon ball modified glassy carbon electrode
(surface area 7.065mm2) be working electrode be placed in the graphene oxide solution (electrolyte) of 3mL, select platinum electrode for
To electrode, calomel electrode is reference electrode, and CV electro-deposition graphene is carried out in three electrode test systems;Finally, obtaining graphite
Alkene/nitrating carbon ball modified glassy carbon electrode;Wherein, the design parameter setting of CV test are as follows: current potential selection -1.5V~0.6V, scanning
Rate is 0.01V/s, and circulating ring number is 5 circles.
4) it selects in the 4mL mixed electrolyte formed by chloroplatinic acid (2.0mmol/L) and potassium chloride (0.1mol/L), it will
Graphene/nitrating carbon ball modified glassy carbon electrode is working electrode, selects platinum electrode for electrode, calomel electrode is reference electrode,
Constant potential platinum electrodeposition nanoparticle is carried out in three electrode test systems, finally obtains nitrating carbon ball/graphene/platinum nano grain
Sub- trielement composite material, is denoted as A1;The design parameter of constant potential electro-deposition is arranged are as follows: current potential selection -0.25V deposits 60s.
Embodiment 2
1) poly-dopamine ball is placed in electric-type furnace, under inert gas flow, from 25 DEG C slowly according to the speed of 4 DEG C/min
Rate is warming up to 800 DEG C, calcining at constant temperature 1.2h, is then cooled to 30 DEG C with the rate of 8 DEG C/min and obtains the nitrating carbon ball of black;
2) nitrating carbon ball is dispersed in water to obtain the nitrating carbon ball solution that mass concentration is 4mg/mL;Take 5 μ L nitrating carbon
Ball solution is coated on surface (the surface area 7.065mm of glass-carbon electrode2), nitrating carbon ball modification glass carbon electricity is obtained after drying
Pole;
3) first by graphene oxide ultrasonic disperse in the phosphate buffer solution that phosphorus acid ion concentration is 0.067mol/L
(pH=9.18) graphene oxide solution that mass concentration is 4g/mL is made in;Then, by nitrating carbon ball modified glassy carbon electrode
(surface area 7.065mm2) be working electrode be placed in the graphene oxide solution (electrolyte) of 3mL, select platinum electrode for
To electrode, calomel electrode is reference electrode, and CV electro-deposition graphene is carried out in three electrode test systems;Finally, obtaining graphite
Alkene/glass-carbon electrode glass-carbon electrode;Wherein, the design parameter setting of CV test are as follows: current potential selection -1.5V~0.6V, sweep speed
For 0.03V/s, circulating ring number is 10 circles.
4) it selects in the 4mL mixed electrolyte formed by chloroplatinic acid (2.5mmol/L) and potassium chloride (0.1mol/L), it will
Graphene/nitrating carbon ball modified glassy carbon electrode is working electrode, selects platinum electrode for electrode, calomel electrode is reference electrode,
Constant potential platinum electrodeposition nanoparticle is carried out in three electrode test systems, finally obtains nitrating carbon ball/graphene/platinum nano grain
Sub- trielement composite material, is denoted as A2;Wherein, the design parameter setting of constant potential electro-deposition are as follows: current potential selection -0.25V, deposition
100s。
Embodiment 3
1) poly-dopamine ball is placed in electric-type furnace, under inert gas flow, from 35 DEG C slowly according to the speed of 5 DEG C/min
Rate is warming up to 900 DEG C, calcining at constant temperature 1h, is then cooled to 40 DEG C with the rate of 10 DEG C/min and obtains the nitrating carbon ball of black;
2) nitrating carbon ball is dispersed in water to obtain the nitrating carbon ball solution that mass concentration is 5mg/mL;Take 6 μ L nitrating carbon
Ball solution is coated on surface (the surface area 7.065mm of glass-carbon electrode2), nitrating carbon ball modification glass carbon electricity is obtained after drying
Pole;
3) first by graphene oxide ultrasonic disperse in the phosphate buffer solution that phosphorus acid ion concentration is 0.067mol/L
(pH=9.18) graphene oxide solution that mass concentration is 5mg/mL is made in;Then, by nitrating carbon ball modified glassy carbon electrode
(surface area 7.065mm2) be working electrode be placed in the graphene oxide solution (electrolyte) of 5mL, select platinum electrode for
To electrode, calomel electrode is reference electrode, and CV electro-deposition graphene is carried out in three electrode test systems;Finally, obtaining graphite
Alkene/nitrating carbon ball modified glassy carbon electrode;Wherein, the design parameter setting of CV test are as follows: current potential selection -1.5V~0.6V, scanning
Rate is 0.05V/s, and circulating ring number is 15 circles.
4) it selects in the 5mL mixed electrolyte formed by chloroplatinic acid (2.2mmol/L) and potassium chloride (0.1mol/L), it will
Graphene/nitrating carbon ball modified glassy carbon electrode is working electrode, selects platinum electrode for electrode, calomel electrode is reference electrode,
Constant potential platinum electrodeposition nanoparticle is carried out in three electrode test systems, finally obtains nitrating carbon ball/graphene/platinum nano grain
Sub- trielement composite material, is denoted as A3;Wherein, the design parameter setting of constant potential electro-deposition are as follows: current potential selection -0.22V, deposition
140s。
Comparative example 1
According to the method for embodiment 1, reduced graphene modified glassy carbon electrode is made, is denoted as B1;The difference is that only carrying out
The operation of step 3), and select pure glass-carbon electrode as working electrode.
Comparative example 2
According to the method for embodiment 1, graphene/platinum modified glassy carbon electrode is made, is denoted as B2;The difference is that only being walked
3) and 4) rapid operation, and selected pure glass-carbon electrode as working electrode in step 3).
Comparative example 3
According to the method for embodiment 1, platinum/nitrating carbon ball modification glass-carbon electrode is made, is denoted as B3;The difference is that not carrying out
The operation of step 3), and the glass-carbon electrode for selecting nitrating carbon ball to modify in step 4) is as working electrode.
Comparative example 4
According to the method for embodiment 1, the glass-carbon electrode of platinum particles modification is made, is denoted as B4;The difference is that only carrying out step 4)
Operation, and select pure glass-carbon electrode as working electrode in the step 4).
Comparative example 5
According to the method for step 2) in embodiment 1, platinum carbon powder is made with the business platinum carbon powder that commercially available platinum content is 20%
The glass-carbon electrode of modification, is denoted as B5.
Detect example 1
Embodiment 1 is made by the scanning electron microscope of Japanese Hitachi model S-4800 the shape of trielement composite material A1
Looks are characterized, and concrete outcome is shown in Fig. 1.
Detect example 2
Trielement composite material is made to embodiment 1 by the transmission electron microscope that Japanese Hitachi company model is JEOL-2010
A1 carries out morphology characterization, and concrete outcome is shown in Fig. 2.
Detect example 3
Embodiment 1 is made by the scanning electron microscope (having energy depressive spectroscopy EDX) of Japanese Hitachi model S-4800
The Elemental redistribution of trielement composite material A1 is analyzed and characterized, and concrete outcome is shown in Fig. 3.
It is characterization to nitrating carbon ball/graphene/platinum nano particle trielement composite material pattern, root that detection example 1, which is with 2,
Will be obvious that multiple uniform spheres exist according to Fig. 1 and Fig. 2 is nitrating carbon ball;In addition, can be clear that
It is that graphene deposits successfully that the graphene sheet layer of large stretch of accordion, which exists,;And multiple uniform nitrating carbon balls are coated;It removes
Other than this, moreover it is possible to will become apparent from being attached with numerous nanoparticles, i.e. nano platinum particle deposits successfully.It can be first according to Fig. 1 and Fig. 2
Step judges that nitrogen carbon ball/graphene/platinum nano particle trielement composite material is successfully prepared.
Fig. 3 is to carry out elemental analysis to composite material made from embodiment 1 as a result, will be obvious that this is multiple according to Fig. 3
There are Pt, N and C element, the result combination Fig. 1 and Fig. 3 further to demonstrate nitrating carbon ball/graphite in the present invention in condensation material
Alkene/nano platinum particle trielement composite material is successfully prepared.
Similarly, according to the product A2-A3 in above-mentioned method detection embodiment 2-3, the characterization result obtained and embodiment 1
In the characterization result of product be consistent substantially.
Application examples 1
Using embodiment 1 be made the glass-carbon electrode of nitrating carbon ball/graphene/platinum nano particle trielement composite material modification as
Working electrode, by the H of 0.5mol/L2SO4Solution selects platinum electrode for electrode, calomel electrode is reference electricity as electrolyte
Pole carries out CV test in three electrode test systems;Electrolyte is first led into nitrogen 30-40min, carries out CV test;It then will be electric
It solves liquid and leads to oxygen 30-40min, then carry out CV test.In above-mentioned CV test, current potential selection -0.2-1.0V, sweep speed is
0.01V/s.It tests obtained CV curve graph and sees Fig. 4.
Application examples 2
Using embodiment 1 be made the disk electrode of nitrating carbon ball/graphene/platinum nano particle trielement composite material modification as
Working electrode, by the H of 0.5mol/L2SO4Solution selects platinum electrode for electrode, calomel electrode is reference electricity as electrolyte
Pole carries out LSV test in three electrode test system of rotating circular disk;Electrolyte is first led into oxygen 30-40min, then carries out LSV survey
Examination.In above-mentioned LSV test, current potential selection -0.2-0.8V, sweep speed 0.01V/s, successively changing electrode revolving speed is
The LSV that 225rpm, 400rpm, 625rpm, 900rpm, 1225rpm, 1600rpm, 2025rpm and 2500rpm are tested
Curve graph is shown in Fig. 5, wherein each curve represents corresponding revolving speed and is from top to bottom sequentially increased in figure.
Application examples 3
It is work that nitrating carbon ball/graphene/platinum nano particle trielement composite material modification glass-carbon electrode, which is made, in embodiment 1
Make electrode, by the H of 0.5mol/L2SO4Solution selects platinum electrode for electrode, calomel electrode is reference electrode as electrolyte,
Chrono-amperometric (i-t) test is carried out in three electrode test systems;Electrolyte is first led into oxygen 30-40min and maintains logical oxygen condition,
I-t test is carried out again.And the timing electricity for testing obtained i-t and business platinum carbon powder modified electrode under same test condition
Flow curve superposition comparison, obtained comparative result figure are shown in Fig. 6.
Application examples 4
Select the H of 0.5mol/L2SO4As electrolyte, select platinum electrode for electrode, calomel electrode is reference electrode,
Electrolyte is first led to oxygen 30-40min by three electrode test system of rotating circular disk, then successively selects A1 and B1-B5 as work electricity
Pole carries out LSV test;Wherein, the current potential of LSV test is selected as -0.2-0.8V, sweep speed 0.01V/s, and electrode revolving speed is
1600rpm。
Finally, being overlapped obtained LSV test curve to obtain Fig. 8.
Fig. 4 is the CV test result that the trielement composite material in embodiment 1 is carried out in the case where nitrogen and oxygen are saturated
Superposition, pass through stack result, hence it is evident that find out under oxygen saturated conditions, nitrating carbon ball/graphene/platinum nano particle ternary is multiple
Condensation material has good catalytic effect to oxygen reduction reaction.
And Fig. 5 is that modification rotating disk electrode (r.d.e) is carried out to nitrating carbon ball/graphene/platinum nano particle trielement composite material simultaneously
The LSV of progress is tested, and test result again shows that nitrating carbon ball provided by the present application/graphene/platinum nano particle tri compound
Material has good catalytic effect to oxygen reduction reaction.In addition, Koutecky- can be drawn out according to the data of Fig. 5
Levich curve is shown in Fig. 7, and according to Koutecky-Levich (K-L) equation, calculating its electron transfer number is 4, (wherein, formula
Middle j is the current density of test;jKIt is dynamics Controlling current density;jLIt is diffusion control current density;C0It is that bulk phase concentration is
1.3×10-6mol·cm-3, D0Be diffusion coefficient be 1.8 × 10-5cm2s-1, ν is the dynamics viscosity 0.01cm of electrolyte2/ s, F
For 96500C/mol).Wherein, Levich (K-L) equation are as follows:
Above-mentioned Levich (K-L) equation can write 1/j=1/jL+1/jK=1/B ω1/2+1/jKForm, i.e. y=kx+
The form of b;With 1/ ω1/2For abscissa x, mapped using the current density inverse 1/j measured as ordinate y, as shown in Figure 7.Root
Slope k=1/B can be obtained according to Fig. 7.Again according to formula B=0.62nFC0D0 2/3ν-1/6Can calculate electron transfer number=
9.08*B=9.08/k therefore the electron transfer number for calculating A1 is 4.
In addition, Fig. 6 is to be catalyzed to nitrating carbon ball/graphene/platinum nano particle trielement composite material as oxygen reduction reaction
The test of the stability of agent, compared with the business platinum carbon powder of platiniferous 20%, nitrating carbon ball/graphene/platinum provided by the invention is received
Rice corpuscles trielement composite material has good stability in the reaction process of catalytic oxidation-reduction.
In addition, according to experimental result Fig. 8 of application examples 4 it is found that under same preparation condition and testing conditions, this hair
The nitrating carbon ball of bright offer/graphene/platinum nano particle trielement composite material shows optimal hydrogen reduction catalytic effect;By scheming
8 as it can be seen that the hydrogen reduction current potential of A1 most just and hydrogen reduction electric current is maximum, and is superior to modified electrode B1- obtained by comparative example 1-5
The catalytic effect of B5.
To sum up, nitrating carbon ball/graphene/platinum nano particle trielement composite material provided by the invention has oxygen reduction reaction
There is good catalytic effect, catalytic effect is substantially better than simple reduced graphene, graphene/platinum composite material, platinum/nitrating
Carbon ball composite material and pure platinum particles.In addition, nitrating carbon ball provided by the invention/graphene/platinum nano particle ternary is multiple
Condensation material shows good stability during catalytic oxidation-reduction.
Similarly, according to the product in the method detection embodiment 2-3 in application examples 1-4, the testing result and implementation obtained
The testing result of product in example 1 is consistent substantially.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (18)
1. a kind of preparation method of the trielement composite material of nitrating carbon ball/graphene/platinum nano particle, which is characterized in that described
Preparation method the following steps are included:
1) carbon containing nitrogen source is heat-treated to obtain nitrating carbon ball;
2) the nitrating carbon ball is dissolved in formation nitrating carbon ball solution in solvent, is then coated on the nitrating carbon ball solution
Glass carbon surface is to form nitrating carbon ball modified glassy carbon electrode;
3) it disperses graphene oxide in buffer solution to form graphene oxide solution, in the graphene oxide solution
In, it be to electrode, calomel electrode as working electrode, platinum electrode using the nitrating carbon ball modified glassy carbon electrode is that reference electrode passes through
Cyclic voltammetry carries out electrodeposition process so that graphene/nitrating carbon ball modified glassy carbon electrode is made;
4) graphene/nitrating carbon ball modified glassy carbon electrode is soaked in platiniferous electrolyte through constant potential electrodeposition process
Nitrating carbon ball/graphene/platinum nano particle trielement composite material is made.
2. preparation method according to claim 1, wherein the nitrogen source is poly-dopamine ball, chitosan bead, polyaniline are received
Rice at least one of ball and polypyrrole nanosphere.
3. preparation method according to claim 2, wherein the nitrogen source is poly-dopamine ball.
4. preparation method according to claim 1, wherein the condition of the heat treatment are as follows: in an inert atmosphere, first certainly
20-35 DEG C is warming up to 700-900 DEG C, is then cooled to 20-40 DEG C after 700-900 DEG C of maintenance 1-1.5h.
5. the preparation method according to claim 4, wherein the rate of the heating is 3-5 DEG C/min;The speed of the cooling
Rate is 5-10 DEG C/min.
6. preparation method according to claim 5, wherein the mass concentration of nitrating carbon ball is in the nitrating carbon ball solution
3-5mg/mL;It and with surface area is 7.065mm2The glass carbon surface on the basis of, the coated weight of the nitrating carbon ball solution is
3-6μL;
The pH of the buffer solution is 9.18-9.20.
7. preparation method according to claim 6, wherein the solvent is acetone, ethyl alcohol or water.
8. preparation method according to claim 7, wherein the solvent is water.
9. preparation method according to claim 8, wherein the buffer solution is slow for disodium hydrogen phosphate-sodium dihydrogen phosphate
Rush solution, acetic acid-sodium acetate buffer solution or Tris-hydrochloric acid buffer solution.
10. preparation method according to claim 9, wherein the buffer solution is slow for disodium hydrogen phosphate-sodium dihydrogen phosphate
Solution is rushed, and the concentration of phosphate radical is 0.067-0.07mol/L in the buffer solution.
11. preparation method according to claim 6, wherein the condition of the cyclic voltammetry are as follows: current potential be -1.5V~
0.6V, circulating ring number are 5-15 circle, sweep speed 0.01-0.05V/s.
12. preparation method according to claim 11, wherein the quality of graphene oxide in the graphene oxide solution
Concentration is 1-5mg/mL, and is 7.065mm with surface area2The glass carbon surface on the basis of, the graphene oxide solution
Dosage is 3-5mL.
13. the preparation method according to claim 6 or 11, wherein the platiniferous electrolyte is chloroplatinic acid and potassium chloride
Mixed liquor.
14. preparation method according to claim 13, wherein the concentration of the chloroplatinic acid is 2.0-2.5mmol/L, described
The concentration of potassium chloride is 0.1-0.2mol/L.
15. preparation method according to claim 14, wherein the condition of the constant potential electro-deposition are as follows: current potential is -0.3
~-0.2V, sedimentation time 60-140s.
16. preparation method according to claim 15, wherein the current potential of the constant potential electro-deposition is -0.25V.
17. a kind of nitrating carbon ball/graphene/platinum nano grain that the described in any item preparation methods of claim 1-16 are prepared
The trielement composite material of son, wherein the compounding ingredients of the trielement composite material are graphene, nitrating carbon ball and platinum nanoparticle
Son.
18. a kind of trielement composite material of nitrating carbon ball/graphene/platinum nano particle as claimed in claim 17 is in fuel electricity
Application in the hydrogen reduction catalysis reaction of pool cathode.
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