CN105161728A - Preparation of urea-modified boron-carbon hollow spheres and application of urea-modified boron-carbon hollow spheres in fuel cell - Google Patents
Preparation of urea-modified boron-carbon hollow spheres and application of urea-modified boron-carbon hollow spheres in fuel cell Download PDFInfo
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- CN105161728A CN105161728A CN201510490716.9A CN201510490716A CN105161728A CN 105161728 A CN105161728 A CN 105161728A CN 201510490716 A CN201510490716 A CN 201510490716A CN 105161728 A CN105161728 A CN 105161728A
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- PPWPWBNSKBDSPK-UHFFFAOYSA-N [B].[C] Chemical class [B].[C] PPWPWBNSKBDSPK-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000000446 fuel Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004202 carbamide Substances 0.000 claims abstract description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000005530 etching Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 5
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 229940018563 3-aminophenol Drugs 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- OPPWASLOVKWHCT-UHFFFAOYSA-N boric acid;phenol Chemical compound OB(O)O.OC1=CC=CC=C1 OPPWASLOVKWHCT-UHFFFAOYSA-N 0.000 claims description 4
- UHJFMAJYDZKDLJ-UHFFFAOYSA-N OBO.OC1=CC=CC=C1 Chemical compound OBO.OC1=CC=CC=C1 UHJFMAJYDZKDLJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000013049 sediment Substances 0.000 abstract 2
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 229910052796 boron Inorganic materials 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 238000006722 reduction reaction Methods 0.000 description 11
- 230000009467 reduction Effects 0.000 description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 230000001394 metastastic effect Effects 0.000 description 7
- 206010061289 metastatic neoplasm Diseases 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- 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
-
- 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
-
- B01J35/51—
-
- 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
-
- 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
-
- 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
- H01M4/96—Carbon-based electrodes
-
- 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
Abstract
The invention provides a preparation method of urea-modified boron-carbon hollow spheres and an application of the urea-modified boron-carbon hollow spheres in a fuel cell. The method comprises the following steps: firstly, preparing the boron-carbon hollow spheres according to the prior art; secondly, fully mixing the prepared boron-carbon hollow spheres with urea, putting the mixture in a tube furnace and carrying out high-temperature calcination at the temperature higher than 600 DEG C under nitrogen protection; and finally, etching the calcined product with a hydrofluoric acid, centrifuging the calcined product, taking sediments, and washing and drying the sediments, so as to obtain the urea-modified boron-carbon hollow spheres. The urea-modified boron-carbon hollow spheres prepared by the method provided by the invention have the advantages of high specific surface area, good conductivity and the like, and are a high-performance catalyst for an anode of a direct methanol fuel cell.
Description
Technical field
The present invention relates to a kind of urea that utilizes to the application in the reaction of catalysis direct methanol fuel cell O_2 cathodic reduction of the method for boron carbon hollow ball modification and prepared material.
Background technology
Fuel cell, as a kind of clean regenerative resource, can alleviate the global problem of environmental pollution that traditional fossil energy brings.As the new catalyst of fuel battery negative pole oxygen reduction reaction, boron material with carbon element is once replace traditional platinum based catalyst, then stability and the methanol tolerance that can improve catalyst poison performance, and reduce its cost, thus accelerates the commercialization process of fuel cell.Boron as electron acceptor combines with carbon, enters the graphite platelet structure of material with carbon element, can change the CHARGE DISTRIBUTION situation of carbon atom around, and activate the conjugated pi electron on graphite flake layer, thus be conducive to the absorbing and reducing of oxygen.The hollow ball structure of boron carbon can improve specific area and the conductivity of material further, therefore has huge potential using value in this field.Have report show in the boron material with carbon element of nitrogen modification, if boron, nitrogen can separately be close to carbon atom generation electro transfer, because of the impact of cooperative effect, more will can promote the absorbing and reducing of oxygen than boron material with carbon element.But, if form covalent bond B-N with between the nitrogen-atoms of lone pair electrons and the boron atom with unoccupied orbital, the density of electronics and unoccupied orbital can be caused to decline, make it can not carry out electro transfer with contiguous carbon atom, thus the pi-electron in graphite flake layer cannot be excited activation, be unfavorable for ORR catalytic reaction.Therefore, Control release condition, make boron nitrogen separately with the carbon atom Cheng Jian of surrounding, this is key of the present invention.
Before, chemical vapour deposition technique is mixed as a kind of synthesis generally the method for element doping material with carbon element, reaction condition is harsher, and the metallic catalyst used is difficult to remove completely, cause impact to a certain degree to the chemical property of material, therefore distance extensive use also has the distance of a section very long.Urea-modified boron carbon hollow ball prepared by the present invention, as a kind of new carbon, its specific area is large, structure morphology controllable, density are little, good conductivity, can be used as cathode in direct methanol fuel cells material.
Summary of the invention
Technical problem solved by the invention is:
There is provided a kind of urea-modified preparation method of boron carbon hollow ball and the application in cathode in direct methanol fuel cells, solve existing platinum C catalyst cost high, anti-poisoning ability is poor, the problem of poor stability.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:
The invention provides a kind of preparation method of urea-modified boron carbon hollow ball, its step is as follows:
A prepares boron carbon hollow ball according to prior art;
The boron carbon hollow ball prepared fully mixes with urea and is placed on tube furnace, under nitrogen protection, to carry out high-temperature calcination higher than 600 DEG C by b;
C by centrifugal after calcined product hf etching, get washing of precipitate, drying, obtain urea-modified boron carbon hollow ball.
Wherein, in above-mentioned steps a, the preparation method of boron carbon hollow ball is: be dissolved in 8 ~ 10mL water respectively by 0.6 ~ 0.8g m-aminophenol, 0.4 ~ 0.2g para hydroxybenzene boric acid, add in 4.25mL silicon dioxide core seed solution more successively, after stirring 1 ~ 3min, more slowly drip 1 ~ 1.4mL formalin, the stirring reaction time is 24h, gained solution is transferred to reactor, 100 DEG C of hydro-thermal reaction 24h, products therefrom is centrifugal, washing, dry, obtains boron carbon hollow ball.In addition, the mass ratio of above-mentioned m-aminophenol and para hydroxybenzene boronic acid monomer is 3:2 ~ 4:1, and m-aminophenol and formaldehyde mass ratio are 1:1 ~ 1:1.4.
Preferably, in above-mentioned steps b, described urea is 5:1 ~ 20:1 with the amount ratio of boron carbon hollow ball, and calcining heat is 600 ~ 1100 DEG C, and calcination time is 4h.Hydrofluoric acid mass fraction 10% in step c, etch period is 36h, and described centrifugal rotational speed is 8000rpm ~ 10000rpm, and the time is 5 ~ 10min; Described washing is that distilled water, ethanol respectively wash 3 times; Described baking temperature is 60 DEG C ~ 70 DEG C, and drying time is 20 ~ 24h.
In addition, the present invention also provides a kind of application of urea-modified boron carbon hollow ball in preparation cathode in direct methanol fuel cells prepared according to said method
The invention has the beneficial effects as follows: the present invention adopts urea to prepare urea-modified boron carbon hollow ball as nitrogenous source first, using urea as nitrogenous source, while being doped into nitrogen-atoms, due to the corrosion function of ammonia, add the specific area of boron carbon hollow ball, thus have more avtive spot.In addition, urea-modified boron carbon hollow ball prepared by the present invention, as oxygen reduction catalyst, has with low cost, excellent performance, stable in properties feature, is the high-performance novel catalyst for methanol fuel cell.
Accompanying drawing explanation
Fig. 1 (a) and (b) are scanning electron microscopy (SEM) figure and transmission electron microscope (TEM) figure of urea-modified boron carbon hollow ball before etching, scanning electron microscopy (SEM) figure that (c) and (d) is urea-modified boron carbon hollow ball after HF etching and transmission electron microscope (TEM) figure.
Fig. 2 is x-ray photoelectron power spectrum (XPS) analysis chart of boron, nitrogen in the urea-modified boron carbon hollow ball prepared under different calcining heat.
Fig. 3 is boron carbon hollow ball, nitrogen carbon hollow ball and the cyclic voltammetry figure of urea-modified boron carbon hollow ball in 0.1MKOH solution oxygen and nitrogen atmosphere.
Fig. 4 is linear scan polarization curve (LSV) resolution chart of urea-modified boron carbon hollow ball in 0.1MKOH solution oxygen atmosphere.
Embodiment
The preparation method of urea-modified boron carbon hollow ball of the present invention is:
(1) boron carbon hollow ball is prepared according to prior art, that is: 0.6 ~ 0.8g m-aminophenol, 0.4 ~ 0.2g para hydroxybenzene boric acid are dissolved in 8 ~ 10mL water respectively, add in 4.25mL silicon dioxide core seed solution more successively, after stirring 1 ~ 3min, more slowly drip 1 ~ 1.4mL formalin, the stirring reaction time is 24h, gained solution is transferred to reactor, 100 DEG C of hydro-thermal reaction 24h, products therefrom, in centrifugal, washing, drying, obtains boron carbon hollow ball.
The mass ratio of described m-aminophenol and para hydroxybenzene boronic acid monomer is 3:2 ~ 4:1, and m-aminophenol and formaldehyde mass ratio are 1:1 ~ 1:1.4.
(2) boron carbon hollow ball drying obtained fully mixes with urea and is placed on tube furnace, under nitrogen protection, to carry out high-temperature calcination higher than 600 DEG C.The optimum quality ratio of described urea and boron carbon hollow ball is 5:1 ~ 20:1, and optimum calcinating temperature is 600 ~ 1100 DEG C, and the time is 4h.
(3) by centrifugal after calcined product hf etching, get washing of precipitate, drying, obtain urea-modified boron carbon hollow ball, the optimum condition of this step is: hydrofluoric acid mass fraction 10%, and etch period is 36h, described centrifugal rotational speed is 8000rpm ~ 10000rpm, and the time is 5 ~ 10min; Described washing is that distilled water, ethanol respectively wash 3 times; Described baking temperature is 60 DEG C ~ 70 DEG C, and drying time is 20 ~ 24h.
Below by specific embodiment, the present invention is further described:
The synthesis of embodiment 1 boron carbon hollow ball
Get 0.7g resorcinol respectively, 0.3g para hydroxybenzene boric acid is dissolved in 10mL water, add successively in silica template solution, more slowly drip 1.4mL formalin, at 25 DEG C, 1500rpm rotating speed stirs 24h.Solution is proceeded in 200mL reactor, 100 DEG C of reaction 24h.Solution is taken out, the centrifugal 5min of 8000rpm rotating speed, then wash 3 times with redistilled water, ethanol successively.By dry 24h at the precipitation that obtains again 60 DEG C.
The preliminary preparation of embodiment 2 urea-modified boron carbon hollow ball
Be uniformly mixed in gained boron carbon hollow ball and the water-soluble solution of urea 1:10, moisture evaporation drying is placed in tube furnace, under nitrogen protection, respectively at high temperature pyrolysis 4h at 600 DEG C, 900 DEG C, 1000 DEG C, 1100 DEG C.
The reprocessing of embodiment 3 urea-modified boron carbon hollow ball
Product after heat treatment being immersed in mass fraction is in the hydrofluoric acid solution of 10%, and etching 36h, to remove silica core.The centrifugal 5min of 8000rpm rotating speed again, washs 3 times with redistilled water, ethanol successively.By obtain be deposited in 60 DEG C at dry 24h obtain urea-modified boron carbon hollow ball.
Embodiment 4 urea-modified boron carbon hollow ball electron-microscope scanning
The Electronic Speculum figure of urea-modified boron carbon hollow ball for preparing of the present invention as shown in Figure 1.Fig. 1 a, 1b are respectively ESEM and transmission electron microscope picture, as can be seen from the figure the bead regular appearance of the urea-modified boron carbon hollow ball before etching, uniform particle diameter; Fig. 1 c, 1d are respectively ESEM and the transmission electron microscope picture of the urea-modified boron carbon hollow ball after etching, still maintain good spherical morphology and shell thin and thick is even after etching, there is no appearance of caving in.
Under the different calcining heat of embodiment 5, in urea-modified boron carbon hollow ball, the x-ray photoelectron power spectrum (XPS) of boron, nitrogen is analyzed
As shown in Figure 2, x-ray photoelectron power spectrum (XPS) analysis chart of urea-modified boron carbon hollow ball (BNCS) middle B, N under different calcining heat, wherein N1-N5 is respectively B-N-C, pyridine N, pyrroles N, graphitization N, O-N; B1-B3 is respectively B-C, B-N, B-O.As can be seen from the figure, when temperature is lower, be easy to form B-N key, when the temperature increases, B-N linkage content reduces, and when temperature is increased to 1000 DEG C, in system, B, N are separately and surrounding adjacent C Cheng Jian.
Embodiment 6 performance measurement and comparing
Can find out in boron carbon hollow ball (BNCS) as urea-modified in Fig. 3, boron carbon hollow ball (BHCS) and nitrogen carbon hollow ball (NHCS) the cyclic voltammetry figure in 0.1MKOH solution oxygen atmosphere (solid line) and nitrogen atmosphere (dotted line), the catalytic performance of urea-modified boron carbon hollow ball to redox reactions is best.From linear scan polarization curve (LSV) resolution chart of Fig. 4 urea-modified boron carbon hollow ball in 0.1MKOH solution oxygen atmosphere, along with the rising of calcining heat, in system B, N separately with surrounding adjacent C Cheng Jian, the raising of material hydrogen reduction performance.
Application in embodiment 7 urea-modified boron carbon hollow ball cathode in direct methanol fuel cells
By urea-modified boron carbon hollow ball dispersion in ethanol (1 ~ 5mg/mL).Get 3 ~ 20 μ L to drip on glass carbon, under room temperature in drier after dry 2h, drip the Nafion alcohol dispersion liquid (0.05wt.%) of 1 ~ 10 μ L on its surface, dry 2h in drier under room temperature, obtained cathode in direct methanol fuel cells.
Through detecting, a spike potential for above-mentioned urea-modified boron carbon hollow ball Catalytic Oxygen cathodic reduction is-81mV, and dynamics current density is 6.2mAcm
-2, metastatic electron number is 3.95.The people such as Zheng (Angew.Chem.Int.Ed., 2013,52,3110-3116.) obtain the Graphene of B, N codope with two steps annealing method, a spike potential for its catalytic oxygen reduction is-100mV, and metastatic electron number is 3.81.The people such as Yazdi (ACSAppl.Mater.Inter., 2015,7,7786-7794.) carbon nano-tube of B, N codope is obtained with CVD, a spike potential of its catalytic oxygen reduction and metastatic electron number are all suitable with the material prepared by the present invention, but its dynamics current density is 3.75mAcm
-2, much smaller than the material prepared by the present invention.The people such as Kim (Phys.Chem.Chem.Phys., 2015,17,407-413.) by solution excitation of plasma legal system for B, N carbon dope material altogether, the reduction of its catalytic oxygen to play a spike potential be-90mV, metastatic electron number is for being 3.5.The people such as Tai (RSCAdv., 2014,4,61437-61443.) obtain the Graphene of B, N codope with two-step method, a spike potential for its catalytic oxygen reduction is-170mV, and metastatic electron number is 3.9.The people such as Baik (RSCAdv., 2015,5,24661-24669.) high-temperature calcination obtains B, N and mixes active carbon altogether, and a spike potential for its catalytic oxygen reduction is-130mV, and metastatic electron number is 3.81.In sum, the material prepared by the present invention is compared with same type of material, and react the O_2 cathodic reduction of direct methanol fuel cell, it is more negative that it plays spike potential, and dynamics current density is larger, and metastatic electron number is higher.
More than show and describe general principle of the present invention, principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection range is defined by appending claims and equivalent thereof.
Claims (5)
1. a preparation method for urea-modified boron carbon hollow ball, its step is as follows:
A prepares boron carbon hollow ball according to prior art;
The above-mentioned boron carbon hollow ball prepared fully mixes with urea and is placed on tube furnace, under nitrogen protection, to carry out high-temperature calcination higher than 600 DEG C by b;
C by centrifugal after calcined product hf etching, get washing of precipitate, drying, obtain urea-modified boron carbon hollow ball.
2. the preparation method of a kind of urea-modified boron carbon hollow ball according to claim 1, it is characterized in that: in step a, the preparation method of boron carbon hollow ball is: 0.6 ~ 0.8g m-aminophenol, 0.4 ~ 0.2g para hydroxybenzene boric acid are dissolved in 8 ~ 10mL water respectively, add in 4.25mL silicon dioxide core seed solution more successively, after stirring 1 ~ 3min, slowly drip 1 ~ 1.4mL formalin again, the stirring reaction time is 24h, gained solution is transferred to reactor, 100 DEG C of hydro-thermal reaction 24h, products therefrom is centrifugal, washing, dry, obtain boron carbon hollow ball;
Wherein, the mass ratio of above-mentioned m-aminophenol and para hydroxybenzene boronic acid monomer is 3:2 ~ 4:1, and m-aminophenol and formaldehyde mass ratio are 1:1 ~ 1:1.4.
3. the preparation method of a kind of urea-modified boron carbon hollow ball according to claim 1, is characterized in that: in step b, and the amount of described urea and boron carbon hollow ball is than being 5:1 ~ 20:1, and calcining heat is 600 ~ 1100 DEG C, and calcination time is 4h.
4. the preparation method of a kind of urea-modified boron carbon hollow ball according to claim 1, it is characterized in that: hydrofluoric acid mass fraction 10% in step c, etch period is 36h, and described centrifugal rotational speed is 8000rpm ~ 10000rpm, and the time is 5 ~ 10min; Described washing is that distilled water, ethanol respectively wash 3 times; Described baking temperature is 60 DEG C ~ 70 DEG C, and drying time is 20 ~ 24h.
5. the urea-modified boron carbon hollow ball that according to claim 1 prepared by method is preparing the application in cathode in direct methanol fuel cells.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510490716.9A CN105161728A (en) | 2015-08-11 | 2015-08-11 | Preparation of urea-modified boron-carbon hollow spheres and application of urea-modified boron-carbon hollow spheres in fuel cell |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510490716.9A CN105161728A (en) | 2015-08-11 | 2015-08-11 | Preparation of urea-modified boron-carbon hollow spheres and application of urea-modified boron-carbon hollow spheres in fuel cell |
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| CN109135735B (en) * | 2018-07-27 | 2021-04-20 | 中北大学 | Preparation method of water-soluble BCx quantum dots |
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Application publication date: 20151216 |