CN107746051A - A kind of nitrogen-doped graphene nanobelt nano-cobaltic-cobaltous oxide hybrid material and preparation method thereof - Google Patents
A kind of nitrogen-doped graphene nanobelt nano-cobaltic-cobaltous oxide hybrid material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 95
- 239000000463 material Substances 0.000 title claims abstract description 60
- 239000002127 nanobelt Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 56
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002105 nanoparticle Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 11
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 17
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- 230000008859 change Effects 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical group NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 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 claims description 2
- 241000549556 Nanos Species 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000000502 dialysis Methods 0.000 claims 1
- 238000006722 reduction reaction Methods 0.000 abstract description 17
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 239000007809 chemical reaction catalyst Substances 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 10
- 230000009467 reduction Effects 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 7
- 235000013495 cobalt Nutrition 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000010757 Reduction Activity Effects 0.000 description 3
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004502 linear sweep voltammetry Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
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- 235000013339 cereals Nutrition 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 238000000840 electrochemical analysis Methods 0.000 description 2
- -1 graphite Alkene Chemical class 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
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- 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
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Abstract
The invention belongs to technical field of nano material, specially a kind of nitrogen-doped graphene nanobelt nano-cobaltic-cobaltous oxide hybrid material and preparation method thereof.The nitrogen-doped graphene nanobelt nano-cobaltic-cobaltous oxide hybrid material of the present invention growth in situ cobaltosic oxide nanoparticles and realizes that its N doping is prepared using cobalt salt and ammoniacal liquor on stannic oxide/graphene nano band；Its preparation process includes：Stannic oxide/graphene nano band is prepared by chemical radial shear CNT；The N doping of graphene nanobelt growth in situ cobaltosic oxide nanoparticles and is realized on stannic oxide/graphene nano band by one step hydro thermal method.Stannic oxide/graphene nano band obtained by the present invention has larger draw ratio；Obtained cobaltosic oxide nanoparticles size is smaller and being evenly distributed on graphene nano band.The hybrid material of the present invention can be used as efficient oxygen reduction reaction catalyst material.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to a kind of nitrogen-doped graphene nanobelt-nanometer four aoxidizes
Three cobalt hybrid materials and preparation method thereof.
Background technology
Oxygen reduction reaction（ORR）Catalyst is the important component of fuel cell, and its catalytic activity directly determines this
The performance of a little devices.And the slow dynamics of ORR is exactly to influence the key issue of fuel cell energy conversion efficiency, therefore, hair
Open up development of the high performance ORR catalyst to fuel cell etc. and play vital effect.Current commercialized ORR catalyst
For metal platinum based catalyst, although such catalyst activity is higher, its stability and methanol tolerance poor-performing, and into
This is higher, still can not meet the requirement of large-scale application.
In recent years, nitrogen atom doping carbon material especially nitrogen-doped graphene and nitrogen-doped carbon nanometer pipe is because its is excellent
ORR catalytic activity and receive the extensive concern of people.Graphene can see the graphite of individual layer as, and it has high conductivity, high
Many advantages, such as specific surface area and chemical stability.Graphene nanobelt is a kind of derivative of graphene, compared with graphene,
Graphene nanobelt had both had the distinct chemical physical property of graphene, had the border largely containing a variety of chemical groups again,
So as to be more beneficial for the doping of nitrogen-atoms.And research work in recent years shows, compared with sheet surfaces, oxygen molecule is in boundary
Easily it is adsorbed, therefore the border of graphene has higher ORR activity than its sheet surfaces.
In addition, nitrogen-doped graphene not only oneself has certain oxygen reduction activity, its be also used as carrier with
Some metal oxides are compounded to form the oxygen reduction reaction catalyst of excellent performance.Such as《Naturally it is chemical》（Nature
Materials, 2011 volume 10 page 780）Report in nitrogen-doped graphene superficial growth cobaltosic oxide by obtaining hydridization material
Material, the hybrid material show excellent catalytic activity and stability under alkaline environment.Material has excellent electrocatalytic oxidation
The reason for reducing property is that the bonding between cobaltosic oxide and nitrogen-doped graphene is possible oxygen reduction activity site.
Some, receives it is contemplated that developing a kind of simple, low cost method to prepare nitrogen-doped graphene with reference to more than
Rice band-cobaltosic oxide hybrid material, as oxygen reduction reaction catalyst.The hybrid material has following advantage：First, stone is aoxidized
The abundant border of black alkene nanobelt provides substantial amounts of site for the doping of nitrogen-atoms；2nd, on the one hand N doping can assign graphite
Alkene nanobelt oxygen reduction activity, on the other hand it is also beneficial to form the cobaltosic oxide of nano-scale and helps it to be received in graphene
Rice takes dispersed；3rd, the synergy of cobaltosic oxide and nitrogen-doped graphene nanometer interband can further improve material
The hydrogen reduction performance of material.
The content of the invention
It is an object of the invention to provide a kind of preparation process is simple, mild condition, cost are low and the nitrogen of asepsis environment-protecting
Doped graphene nanobelt-cobaltosic oxide nanoparticles hybrid material and preparation method thereof.
Nitrogen-doped graphene nanobelt-cobaltosic oxide nanoparticles hybrid material provided by the present invention, it prepares former
Material composition includes：Original carbon nanotubes, cobalt salt, ammoniacal liquor.
Nitrogen-doped graphene nanobelt-cobaltosic oxide nanoparticles hybrid material provided by the present invention, it is to select cobalt
Salt and ammoniacal liquor realize growth in situ of the cobaltosic oxide on stannic oxide/graphene nano band, oxidation by a step hydro-thermal reaction simultaneously
The reduction of graphene nanobelt and the N doping of graphene nanobelt obtain.
Nitrogen-doped graphene nanobelt-cobaltosic oxide nanoparticles hybrid material provided by the present invention, it was prepared
Journey includes：Stannic oxide/graphene nano band is arrived by chemical radial shear original carbon nanotubes；It is prepared by ultrasonic disperse
Stannic oxide/graphene nano band aqueous dispersions；By one step hydro thermal method three are aoxidized in stannic oxide/graphene nano belt surface growth in situ four
Cobalt nanometer particle simultaneously realizes N doping.Comprise the following steps that：
（1）First, stannic oxide/graphene nano band aqueous dispersions are obtained by chemical radial shear original carbon nanotubes.It specifically flows
Cheng Wei：A diameter of 20 ~ 50 nm of 100 ~ 200 mg original carbon nanotubes are scattered in 35 ~ 40 mL concentrated sulfuric acid solution, magnetic
Power stirs 0.5 ~ 1.5 h to well mixed；2 ~ 6 mL 85% phosphoric acid is added dropwise, continues the min of stirring 20 ~ 60；Weigh 500 ~
1000 mg potassium permanganate, and be slowly added in batches in reaction solution（Added in general 40-60 minutes）, then start to warm up
To 60 ~ 80 DEG C, and continue the h of reaction 1.5 ~ 2.5；Natural cooling, the mixture is slowly poured into containing the peroxidating of 5 ~ 10 mL 30%
In the frozen water of hydrogen, and stir 1 ~ 4 h, then placement overnight；Supernatant is removed, bottom precipitation is filtered with 5 ~ 10% watery hydrochloric acid and washed
Wash 3-5 times, and dialyse to neutrality, dry, obtain stannic oxide/graphene nano band powder；By the stannic oxide/graphene nano of certain mass
With adding in the deionized water of certain volume, 0.5 ~ 2 h of ultrasound, the concentration for obtaining stable dispersion is 0.5 ~ 1.5 mg/mL oxygen
Graphite alkene nanobelt aqueous dispersions；
（2）15 ~ 25 mL stannic oxide/graphene nanos band aqueous dispersions are taken, are charged with 0.1 ~ 0.4 mmol cobalt salt, at ultrasound
30 ~ 60min is managed, then adds 2 ~ 4 mL ammoniacal liquor, and continues the min of stirring 10 ~ 15, obtains uniform mixed liquor；
（3）The mixed liquor configured is transferred in water heating kettle and carries out a step hydro-thermal reaction, reaction temperature is 150 ~ 180 DEG C, instead
It is 3 ~ 4 h between seasonable；
（4）The black precipitate in above-mentioned steps is taken, is washed with deionized 3-5 times, and final production is dried to obtain in baking oven
Thing：Nitrogen-doped graphene nanobelt-cobaltosic oxide nanoparticles hybrid material；Wherein, size is 5 ~ 10 nm oxygen of nanometer four
Change three cobalt particles to be evenly distributed on nitrogen-doped graphene nanobelt.
In the present invention, step（2）Described cobalt salt is selected from cobalt acetate；The sulfosalt is selected from thiocarbamide, vulcanized sodium.
Fig. 1 is the preparation process schematic diagram of graphene nanobelt-nano-cobaltic-cobaltous oxide hybrid material.
Use SEM（SEM）, transmission electron microscope（TEM）, laser Raman spectrometer, X x ray diffractions
Instrument, electrochemical workstation characterize the pattern of graphene nanobelt-nano-cobaltic-cobaltous oxide hybrid material that the present invention is obtained
Structure and the chemical property as electrocatalytic oxidation reduction catalyst, its result are as follows：
（1）SEM and TEM test result shows：Pass through radial direction chemical shearing original carbon nanotubes in the present invention（Diameter：20~
50 nm）The width of resulting stannic oxide/graphene nano band is 80 ~ 150 nm.Obvious piece is not observed in low power TEM figures
Layer stacks, and illustrates that the stannic oxide/graphene nano band is with individual layer or lacked existing for layer state, referring to accompanying drawing 2.
（2）TEM test results are also demonstrated that the nano-cobaltic-cobaltous oxide grain that the size prepared by the present invention is about 5 ~ 10 nm
Son is evenly distributed on nitrogen-doped graphene nanobelt, and the nano-cobaltic-cobaltous oxide of this small size can carry for oxygen reduction reaction
For more avtive spots.High-resolution TEM shows in hybrid material, nitrogen-doped graphene nanobelt be still with individual layer or
Few layer state is present, and this can greatly improve the specific surface area of hybrid material, and this is allowed between hybrid material and oxygen molecule
There is bigger contact area, so as to be advantageous to the quick generation of reaction.
（3）Raman test result shows, compared with original carbon nanotubes, graphene nanobelt has higher D/G ratios, says
There is more borders and defect in bright graphene nanobelt.And N doping can further improve the D/G ratios of graphene nanobelt,
More borders and defect are obtained, this is advantageous to the oxygen reduction reaction activity for improving material.XRD test results show, by water
After thermal response, (002) crystal face of stannic oxide/graphene nano band is moved to 2q=26.1 ° from 2q=10.2 °, illustrates its quilt
Successfully graphene nanobelt has been reduced into it.Prepared nitrogen-doped graphene nanobelt-nano-cobaltic-cobaltous oxide hydridization material
Characteristic peak of the material with typical spinel-type cobaltosic oxide, it was demonstrated that cobaltosic oxide is successfully generated.
（4）Electrochemical workstation test result shows that prepared nitrogen-doped graphene nanobelt-cobaltosic oxide exists
Have in 0.1 M KOH more excellent than N doping original carbon nanotubes-cobaltosic oxide and nitrogen-doped graphene-cobaltosic oxide
Hydrogen reduction performance, this demonstrate that the advantage of nitrogen-doped graphene nanobelt.And the nitrogen-doped graphene nanobelt of different component-
The performance of cobaltosic oxide difference, wherein the take-off potential of most excellent component only has 0.94 V（vs.RHE）, electric current
Density has then reached 6 mA/cm-2。
The present invention remarkable advantage be：
（1）Preparation process is simple and environmentally-friendly, easily operated, is a kind of Green Chemistry preparation method；
（2）Experimental design is rationally ingenious.
First, doping substrate and cobaltosic oxide nano grain using prepared stannic oxide/graphene nano band as nitrogen-atoms
The growing carrier of son, it has following advantage：More border, defect and abundant oxy radical, is advantageous to
The doping of nitrogen-atoms；Larger specific surface area is advantageous to the growth of cobaltosic oxide nanoparticles and ensures that its is dispersed, from
And provide substantial amounts of oxygen reduction reaction avtive spot.
Second, nitrogen-doped graphene nanobelt and cobaltosic oxide are carried out by hydridization by simple step hydro-thermal reaction,
With advantages below：Nitrogen-doped graphene nanobelt as matrix material has excellent electric conductivity, be advantageous to ion and
The quick transmission of electronics, and the absorption of oxygen molecule is easy on abundant border, and then be advantageous to the progress of reaction in next step；Four
The interaction of Co 3 O nano-particle and nitrogen-doped graphene nanometer interband provides substantial amounts of activity for oxygen reduction reaction
Site, gained hybrid material performance are significantly larger than single component catalyst, realize the effect of collaboration enhancing.
Brief description of the drawings
Fig. 1 is nitrogen-doped graphene nanobelt in the present invention-cobaltosic oxide hybrid material preparation process schematic diagram.
Fig. 2 is the electron microscope of stannic oxide/graphene nano band prepared in the present invention.Wherein,（a）For original carbon nanotubes
SEM figure,（b-c）Scheme for the TEM of original carbon nanotubes,（d）Scheme for the SEM of graphene nanobelt,（e-f）For graphene nano
The TEM figures of band.
Fig. 3 is the electron microscope of nitrogen-doped graphene nanobelt-cobaltosic oxide hybrid material prepared in the present invention.Its
In,（a-b）Scheme for the TEM of nitrogen-doped graphene nanobelt-cobaltosic oxide hybrid material,（c）For the high-resolution TEM of the material
Figure.
Fig. 4 is the Raman spectrogram and nitrogen-doped graphene nanometer of nitrogen-doped graphene nanobelt prepared in the present invention
The XRD diffraction patterns of band-cobaltosic oxide hybrid material.Wherein,（a）For nitrogen-doped graphene nanobelt, graphene nanobelt
And the Raman spectrogram of original carbon nanotubes,（b）For nitrogen-doped graphene nanobelt-cobaltosic oxide hybrid material, N doping
The XRD diffraction patterns of graphene nanobelt, graphene nanobelt and original carbon nanotubes.
Fig. 5 is nitrogen-doped graphene nanobelt-cobaltosic oxide hybrid material prepared by the present invention in 0.1 MKOH
Cyclic voltammetry curve and linear sweep voltammetry curve.Wherein,（a）The cyclic voltammetric for being different samples in 0.1 M KOH is bent
Line,（b）For different samples in 0.1 M KOH linear scan volt-ampere curve,（c）For different component nitrogen-doped graphene nanometer
The cyclic voltammetry curve of band-cobaltosic oxide hybrid material,（d）For the oxidation of different component nitrogen-doped graphene nanobelt-four three
The linear sweep voltammetry curve of cobalt hybrid material.
Embodiment
With reference to instantiation, the present invention is expanded on further, it should be appreciated that these embodiments be merely to illustrate the present invention and
It is not used in limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, those skilled in the art
Various changes or modification can be made to the present invention, these equivalent form of values equally fall within what the application appended claims were limited
Scope.
Embodiment 1, preparation process are：
（1）Stannic oxide/graphene nano band is arrived by chemical radial shear original carbon nanotubes first, is comprised the following steps that：
150 mg original carbon nanotubes are scattered in 36 mL concentrated sulfuric acid solutions, magnetic agitation 1 hour is to well mixed.Dropwise
The phosphoric acid of 4 mL 85% is added, continues to stir 30 min.750 mg potassium permanganate is weighed, and is slowly added in batches in reaction solution
（Add within 1 hour）, then gradually start to warm up to 70 DEG C and continue to react 2 h.It is after its natural cooling, the mixture is slow
In the slow 300 mL frozen water for pouring into the hydrogen peroxide containing 5 mL 30% and 2 h are stirred, then stop stirring and placement overnight.Remove
Supernatant, by bottom precipitation with 5% watery hydrochloric acid filtering and washing 3-5 all over and dialyse to neutrality, just obtain graphene oxide after drying
Nanobelt powder.The stannic oxide/graphene nano band of certain mass is added to 2 h of ultrasound in the deionized water of certain volume to obtain surely
Surely scattered stannic oxide/graphene nano band aqueous dispersions（1 mg/mL）；
（2）The mg/mL of 20 mL 1 graphene oxide-carbon nano tube dispersion liquid is taken, is charged with 0.1 mmol six hydrations
Cobalt acetate, 30 min are ultrasonically treated, then add 2 mL ammoniacal liquor and continue to stir 10min；
（3）The mixed liquor configured is transferred in 50 mL water heating kettles and carries out a step hydro-thermal reaction,
（4）Obtained black precipitate is washed with deionized 3-5 times and 12 h are dried in 60 DEG C of baking ovens and obtains final product
It is designated as N-GNR/0.1 Co3O4。
The material shows good oxygen reduction catalytic activity, and its take-off potential is 0.93 V（vs RHE）, current density
For 5.0 mA cm-2。
Embodiment 2
It is 0.2 mmol by the quantitative change of six acetate hydrate cobalts in embodiment 1, with embodiment 1, what is finally obtained is miscellaneous for remaining
Change material and be designated as N-GNR/0.2 Co3O4.The material shows good oxygen reduction catalytic activity, and its take-off potential is 0.93 V
（vs RHE）, current density is 5.9mA cm-2。
Embodiment 3
It is 0.3 mmol by the quantitative change of six acetate hydrate cobalts in embodiment 1, with embodiment 1, what is finally obtained is miscellaneous for remaining
Change material and be designated as N-GNR/0.3 Co3O4.The material shows good oxygen reduction catalytic activity, and its take-off potential is 0.93 V
（vs RHE）, current density is 5.2mA cm-2。
Embodiment 4
It is 0.4 mmol by the quantitative change of six acetate hydrate cobalts in embodiment 1, with embodiment 1, what is finally obtained is miscellaneous for remaining
Change material and be designated as N-GNR/0.4 Co3O4.The material shows good oxygen reduction catalytic activity, and its take-off potential is 0.93 V
（vs RHE）, current density is 4.7mA cm-2。
Embodiment 5
Stannic oxide/graphene nano band dispersion liquid in embodiment 2 is changed into original carbon nanotubes dispersion liquid, remaining same embodiment
2, the hybrid material finally obtained is designated as N-CNT/Co3O4.The material shows good oxygen reduction catalytic activity, and it is originated
Current potential is 0.88V（vs RHE）, current density is 4.6mA cm-2。
Embodiment 6
Stannic oxide/graphene nano band dispersion liquid in embodiment 2 is changed into graphene oxide dispersion, remaining with embodiment 2,
The hybrid material finally obtained is designated as N-rGO/Co3O4.The material shows good oxygen reduction catalytic activity, and it originates electricity
Position is 0.90V（vs RHE）, current density is 5.0 mA cm-2。
In electro-chemical test, using three electrode test systems, using the platinum carbon electrode that prepared hybrid material is modified as
Working electrode, silver/silver chloride electrode are reference electrode, and platinum filament is to electrode.Before testing, electrolyte is led into oxygen 30 in advance
Min is to oxygen saturation.Using the electricity of hybrid material prepared in cyclic voltammetry and the linear sweep voltammetry research present invention
Catalytic oxidation-reduction reactivity.
Related technological parameter is as follows in above-mentioned electrochemical test method：
The pretreatment of platinum carbon electrode：Platinum carbon electrode is polished with 1.0,0.3,0.05 microns of alumina powder successively, makes into minute surface.
Cleaned, then dried up with nitrogen standby with deionized water and EtOH Sonicate after polishing every time.
The preparation of modified electrode：It is made in the surface of the platinum carbon electrode by the pretreatment present invention using direct drop-coating
Standby hybrid material is modified.It is 1 that prepared hybrid material specially is dispersed in into deionized water and ethanol ratio:1 it is molten
In agent, 2 mg/mL solution is made, after being ultrasonically treated 1 h, takes 5mL solution to drop on platinum carbon electrode, is done in 70 DEG C of baking oven
Dry 0.5 h.
Claims (4)
1. a kind of preparation method of nitrogen-doped graphene nanobelt-nano-cobaltic-cobaltous oxide hybrid material, it is characterised in that specific
Step is as follows：
（1）First, stannic oxide/graphene nano band aqueous dispersions are obtained by chemical radial shear original carbon nanotubes；
（2）15 ~ 25 mL stannic oxide/graphene nanos band aqueous dispersions are taken, are charged with 0.1 ~ 0.4 mmol cobalt salt, at ultrasound
30 ~ 60min is managed, then adds 2 ~ 4 mL ammoniacal liquor, and continues the min of stirring 10 ~ 15, obtains uniform mixed liquor；
（3）The mixed liquor configured is transferred in water heating kettle and carries out a step hydro-thermal reaction, reaction temperature is 150 ~ 180 DEG C, instead
It is 3 ~ 4 h between seasonable；
（4）The black precipitate in above-mentioned steps is taken, is washed with deionized 3-5 times, and final production is dried to obtain in baking oven
Thing：Nitrogen-doped graphene nanobelt-cobaltosic oxide nanoparticles hybrid material；Wherein, size is 5 ~ 10 nm oxygen of nanometer four
Change three cobalt particles to be evenly distributed on nitrogen-doped graphene nanobelt.
2. the preparation side of nitrogen-doped graphene nanobelt-nano-cobaltic-cobaltous oxide hybrid material according to claim 1
Method, it is characterised in that step（1）Described in by chemical radial shear original carbon nanotubes obtain stannic oxide/graphene nano band
Idiographic flow is：A diameter of 20 ~ 50 nm of 100 ~ 200 mg original carbon nanotubes are scattered in 35 ~ 40 mL concentrated sulfuric acid solution
In, the h of magnetic agitation 0.5 ~ 1.5 is to well mixed；2 ~ 6 mL 85% phosphoric acid is added dropwise, continues the min of stirring 20 ~ 60；Weigh
500 ~ 1000 mg potassium permanganate, and be slowly added in batches in reaction solution, then start to warm up to 60 ~ 80 DEG C, and continue anti-
Answer 1.5 ~ 2.5 h；Natural cooling, the mixture is slowly poured into the frozen water of the hydrogen peroxide containing 5 ~ 10 mL 30%, and stir 1
~ 4 h, then placement overnight；Supernatant is removed, by bottom precipitation 5 ~ 10% watery hydrochloric acid filtering and washing 3-5 times, and dialysis is into
Property, dry, obtain stannic oxide/graphene nano band powder；The stannic oxide/graphene nano band of certain mass is added into going for certain volume
In ionized water, 0.5 ~ 2 h of ultrasound, the stannic oxide/graphene nano band moisture that the concentration for obtaining stable dispersion is 0.5 ~ 1.5 mg/mL
Dispersion liquid.
3. the preparation method of nitrogen-doped graphene nanobelt-nano-cobaltic-cobaltous oxide hybrid material according to claim 1,
Characterized in that, step（2）Described in cobalt salt select cobalt acetate；The sulfosalt is selected from thiocarbamide, vulcanized sodium.
4. the nitrogen-doped graphene nanobelt-nano-cobaltic-cobaltous oxide obtained by one of the claim 1-3 preparation methods is miscellaneous
Change material.
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| CN109473645A (en) * | 2018-10-26 | 2019-03-15 | 江苏大学 | A kind of zinc cobalt-manganese ternary spinelle/N doping redox graphene composite material and preparation method |
| CN109590008A (en) * | 2018-12-25 | 2019-04-09 | 天津大学 | The preparation method of Laser synthesizing Lacking oxygen is adjustable cobaltosic oxide nitrogen-doped graphene |
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| CN110155998A (en) * | 2019-05-13 | 2019-08-23 | 东南大学 | A kind of ribbon nitrogen-doped graphene and its preparation method and application |
| CN110155998B (en) * | 2019-05-13 | 2023-02-21 | 东南大学 | Strip-shaped nitrogen-doped graphene and preparation method and application thereof |
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