CN108993566A - A kind of carbon nano-tube catalyst being used to prepare fuel cell hydrogen and preparation method - Google Patents
A kind of carbon nano-tube catalyst being used to prepare fuel cell hydrogen and preparation method Download PDFInfo
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- CN108993566A CN108993566A CN201810803366.0A CN201810803366A CN108993566A CN 108993566 A CN108993566 A CN 108993566A CN 201810803366 A CN201810803366 A CN 201810803366A CN 108993566 A CN108993566 A CN 108993566A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 80
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 80
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 239000001257 hydrogen Substances 0.000 title claims abstract description 44
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 44
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000000446 fuel Substances 0.000 title claims abstract description 19
- 238000005984 hydrogenation reaction Methods 0.000 title abstract 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 abstract description 39
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 39
- 239000011734 sodium Substances 0.000 claims abstract description 39
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine powder Natural products NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000013019 agitation Methods 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 18
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 10
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 52
- YWDUZLFWHVQCHY-UHFFFAOYSA-N 1,3,5-tribromobenzene Chemical compound BrC1=CC(Br)=CC(Br)=C1 YWDUZLFWHVQCHY-UHFFFAOYSA-N 0.000 claims description 28
- 150000001924 cycloalkanes Chemical group 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 238000006555 catalytic reaction Methods 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 239000002071 nanotube Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical group CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 230000007547 defect Effects 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002344 surface layer Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 239000002048 multi walled nanotube Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- UKKGMDDPINLFIY-UHFFFAOYSA-N [C+4].[O-2].[Ti+4].[O-2].[O-2].[O-2] Chemical compound [C+4].[O-2].[Ti+4].[O-2].[O-2].[O-2] UKKGMDDPINLFIY-UHFFFAOYSA-N 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical group [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 239000013114 Co-MOF-74 Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ANFNKJPBISXCFT-UHFFFAOYSA-N N1=C(N)N=C(N)N=C1N.[N+](=O)([O-])[O-].[Co+2].[N+](=O)([O-])[O-] Chemical compound N1=C(N)N=C(N)N=C1N.[N+](=O)([O-])[O-].[Co+2].[N+](=O)([O-])[O-] ANFNKJPBISXCFT-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a kind of carbon nano-tube catalyst for being used to prepare fuel cell hydrogen and preparation methods.The carbon nano-tube catalyst is made by following steps: a, by metallic sodium and 1, is added dimethylbenzene after the mixing of 3,5- tribromo-benzenes, and magnetic agitation simultaneously reacts and is decomposed to form carbon nanotube；B, high-temperature process after mixing with melamine powder, so that carbon quantum dot is adsorbed on the inside of carbon nanotube, melamine decomposes the C-N key generated and is grafted on the outside of carbon nanotube；C, washing, drying are to get carbon quantum dot, the composite mixed carbon nano-tube catalyst of carbonitride.The method has the advantages that the present invention passes through the nitrogen-atoms of the carbon quantum dot adsorbed inside carbon nanotube and surface layer grafting, effectively increase the defect point inside and outside carbon nanotube, increase specific surface area, active point is more, catalytic activity is good, hydrogen generation efficiency is high, has fabulous application prospect in hydrogen preparation field.
Description
Technical field
The present invention relates to fuel cell fields, and in particular to the preparation of catalyst is used to prepare combustion more particularly, to one kind
Expect the carbon nano-tube catalyst and preparation method of battery hydrogen.
Background technique
The energy is the source that the mankind depend on for existence and development, with the development of the social economy, the existing energy is with more
Carry out faster speed consumption.Hydrogen energy source is the optimal energy, it is different from wind as a kind of important cleaning, green energy resource
The new energies such as energy, tide energy, solar energy, geothermal energy can directly burn.It is not only a kind of source of the physical efficiency containing energy, and it burns
Heat is high, and pollution-free, source is wide, be the traditional energies such as coal, petroleum, natural gas it is incomparable, solve the whole world and face
Energy crisis brings unlimited dawn, especially has extremely excellent prospect, and hydrogen manufacturing skill in the application aspect of fuel cell
Art becomes the key of Hydrogen Energy source domain development.
In hydrogen producing technology, electrolysis water liberation of hydrogen is current most effective hydrogen production process, to reduce overpotential, improving reaction speed
Rate, elctro-catalyst using essential.High-efficient electrolytic water needs to use expensive noble metal catalyst and corrodes to equipment tight
The highly acid electrolyte of weight, this makes high cost, low output and safety issue become main restraining factors.It is electrolysed aquatic products
Another big advantage of hydrogen is that raw material sources are extensive, and various acid-base property electrolyte, industrial wastewater and seawater all can be used as naturally
Hydrogen feedstock, this just needs catalyst all to show high catalytic activity in full pH electrolyte.Therefore, catalyst is in hydrogen manufacturing skill
Very important effect is played in art.
Number of patent application 201711029571.8 discloses a kind of multi-walled carbon nanotube noble metal catalyst and its preparation
Method, the chemical composition CNT/Y/MOFs of material, wherein Y is noble metal nano particles, selected from one of gold, silver, platinum and palladium；
MOFs is Co-MOF-74.The invention additionally provides the preparation method of the multi-walled carbon nanotube noble metal catalyst, resulting
Multi-walled carbon nanotube base precious metal catalytic composite materials have good thermal stability, while the metal organic framework in catalyst
Duct in shell can promote coming into full contact with for reactant and noble metal nano particles, to be conducive to improve urging for catalysis reaction
Change efficiency.The nanocomposite is in vehicle maintenance service, methane reforming reaction, contaminant degradation and photolysis water hydrogen etc.
There is excellent application prospect in chemical reaction.
Number of patent application 201310148706.8 discloses a kind of highly crystalline porous monocrystalline titanium oxide-carbon nanotube composite
The preparation method and applications of material, using ionic liquid as directed agents, water makees solvent, and titanium tetrachloride aqueous solution is titanium source, uses
Microwave-assisted ion thermal synthesis method, cleaning have rapidly synthesized highly crystalline porous monocrystalline titanium oxide-carbon nano tube compound material light
Catalyst, monocrystalline titan oxide particles size are 40 ~ 60nm.The composite material of synthesis will be apparently higher than quotient to the reduction of Cr (VI)
Industry P25, and show good stability.The addition of carbon nanotube is so that this kind of composite material has good electronics empty
Cave separative efficiency and better reaction active site.Such material can also be widely used in photolysis water hydrogen, solar battery, resist
The fields such as bacterium, photocatalysis treatment pollutant.
Number of patent application 201710492721.2 discloses a kind of catalyst for preparing hydrogen and its preparation method and application, and hydrogen manufacturing is urged
Agent includes the active component of carrier and coating on the carrier；Carrier is carbon nanotube, and active component is cerium oxide, manganese oxygen
The composition of compound and nano-titanium dioxide.Catalyst described in the invention is with cerium oxide, Mn oxide and nano-titanium dioxide
Composition is as active component, by the synergistic effect of three, makes catalyst for preparing hydrogen obtained catalytic activity with higher, choosing
Selecting property and stability.
Number of patent application 201711069730.7 discloses a kind of carbon nanotube of N doping, by cobalt nitrate and nitrogenous high score
The mixing of subtree rouge is used as catalyst using cobalt nitrate, and progress high temperature cabonization obtains the carbon nanotube of N doping, a diameter of 10 ~
15 nm, length are 200 ~ 300 nm, and the content of nitrogen is 6 ~ 8 wt%.Preparation method includes rapid: (1) melamine resin
Preparation；(2) cobalt nitrate-melamine resin powder preparation；(3) preparation of the carbon nanotube of N doping.The invention uses
One step carbonization, preparation method are simple；Safety is good, prepares under a nitrogen atmosphere；Used catalyst is cheap and has
There is high activity, has broad application prospects in the preparation field of carbon nanotube.
It can be seen that for the generally existing catalytic activity of catalyst of water electrolysis hydrogen production technology, great number is not lacked in the prior art
It falls into, especially carbon-based material existing defects point is few, specific surface area school, and catalytic activity is lower, it is difficult to the problems such as effectively improving, because
This carbon-based material catalyst for preparing high catalytic activity has highly important practical significance.
Summary of the invention
Effectively to solve above-mentioned technical problem, the invention proposes a kind of carbon nanotubes for being used to prepare fuel cell hydrogen
Catalyst and preparation method, can effectively improve the catalytic activity in water electrolysis hydrogen production, and hydrogen generation efficiency is good.
The specific technical solution of the present invention is as follows:
A kind of preparation method for the carbon nano-tube catalyst being used to prepare fuel cell hydrogen, the carbon nano-tube catalyst be by
Metallic sodium and 1,3,5- tribromo-benzenes occur military hereby reaction and generate symmetric annular alkane and be decomposed into carbon quantum dot, and are adsorbed in two
On the inside of the carbon nanotube that toluene is decomposed to form, melamine decomposes the C-N key generated and is grafted on the outside of carbon nanotube and is made, and has
The preparation step of body are as follows:
A, by metallic sodium and 1,3,5- tribromo-benzenes are mixed in a kettle, and then addition paraxylene, will be anti-as solvent
Kettle is answered to seal, and magnetic agitation, by metallic sodium and 1,3,5- tribromo-benzenes occur force and hereby react, and slough formation pair after halo groups
Claim cyclic alkane structure, while paraxylene is decomposed to form carbon nanotube under the catalysis of metallic sodium；
B, the product of step a is mixed, and high-temperature process with melamine powder, cyclic alkane is made to be decomposed into carbon quantum dot, and
It is grown simultaneously with carbon nanotube, carbon quantum dot is adsorbed on the inside of carbon nanotube, and melamine decomposes the C-N key generated and is grafted on carbon
On the outside of nanotube；
C, carbon quantum dot, the composite mixed carbon nano-tube catalyst of carbonitride is made in washing, drying.
Preferably, in the step a, 15 ~ 20 parts by weight of metallic sodium, 1,3,5- tribromo-benzene, 20 ~ 25 parts by weight, paraxylene
55 ~ 65 parts by weight.
Preferably, in the step a, reaction kettle sealing uses double mechanical seal.
Preferably, in the step a, the revolving speed of magnetic agitation is 150 ~ 300r/min.
Preferably, in the step a, the temperature that force is hereby reacted is 200 ~ 210 DEG C, and the time is 22 ~ 25h.
Preferably, in the step b, 66 ~ 78 parts by weight of product, 22 ~ 34 parts by weight of melamine powder of step a.
Preferably, in the step b, the temperature of high-temperature process is 900 ~ 1100 DEG C, and the time is 5 ~ 7h.
Preferably, in the step c, washing uses one of dehydrated alcohol, propyl alcohol, ether.
Preferably, in the step c, dry temperature is 130 ~ 150 DEG C, and the time is 4 ~ 6h.
The main problem of carbon-based material hydrogen manufacturing at present is that catalytic activity is lower, it is difficult to effectively improve.The invention
By metallic sodium and 1,3,5- tribromo-benzenes occur force and hereby react on ground, form symmetric annular alkane structure after sloughing halo groups, high
In warm reaction process, paraxylene is decomposed to form carbon nanotube under metallic sodium catalysis, and cyclic alkane is decomposed into carbon quantum dot, and two
Person grows simultaneously, and on the inside of carbon nanotube, melamine decomposes the C-N key generated and is grafted on carbon nanometer carbon quantum dot Preferential adsorption
On the outside of pipe, defect point is provided on surface layer, make inside and outside carbon nanotube with more defect point and biggish compares table
Area exposes more active points, to improve catalytic activity.
Above content of the present invention also proposes a kind of carbon nano-tube catalyst for being used to prepare fuel cell hydrogen, by following step
Rapid to be made: a, by metallic sodium and 1 is added dimethylbenzene after the mixing of 3,5- tribromo-benzenes, and magnetic agitation simultaneously reacts and is decomposed to form carbon nanometer
Pipe；B, high-temperature process after mixing with melamine powder, so that carbon quantum dot is adsorbed on the inside of carbon nanotube, melamine is decomposed
The C-N key of generation is grafted on the outside of carbon nanotube；C, washing, drying are to get the composite mixed carbon nano-tube catalyst of carbon quantum dot.
The invention has the benefit that
1. the nitrogen-atoms preparation for proposing the carbon quantum dot adsorbed inside carbon nanotube and surface layer grafting is used to prepare fuel electricity
The method of the carbon nano-tube catalyst of pond hydrogen.
2. the present invention effectively increases carbon by the nitrogen-atoms of the carbon quantum dot adsorbed inside carbon nanotube and surface layer grafting
Defect point inside and outside nanotube, increases specific surface area.
3. the active point of catalyst prepared by the present invention is more, catalytic activity is significantly improved, hydrogen generation efficiency is high, in hydrogen manufacturing
Field has fabulous application prospect.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
A, by metallic sodium and 1,3,5- tribromo-benzenes are mixed in a kettle, and then addition paraxylene, will be anti-as solvent
Kettle is answered to seal, and magnetic agitation, by metallic sodium and 1,3,5- tribromo-benzenes occur force and hereby react, and slough formation pair after halo groups
Claim cyclic alkane structure, while paraxylene is decomposed to form carbon nanotube under the catalysis of metallic sodium；
B, the product of step a is mixed, and high-temperature process with melamine powder, cyclic alkane is made to be decomposed into carbon quantum dot, and
It is grown simultaneously with carbon nanotube, carbon quantum dot is adsorbed on the inside of carbon nanotube, and melamine decomposes the C-N key generated and is grafted on carbon
On the outside of nanotube；
C, carbon quantum dot, the composite mixed carbon nano-tube catalyst of carbonitride is made in washing, drying.
In step a, 20 parts by weight of metallic sodium, 1,3,5- tribromo-benzene, 20 parts by weight, 60 parts by weight of paraxylene.Magnetic agitation
Revolving speed be 300r/min.The temperature that force is hereby reacted is 200 DEG C, time 25h.
In step b, 66 parts by weight of product, 34 parts by weight of melamine powder of step a.The temperature of high-temperature process is 1100
DEG C, time 5h.
In step c, washing uses ether.Dry temperature is 130 DEG C, time 6h.
Embodiment 2
A, by metallic sodium and 1,3,5- tribromo-benzenes are mixed in a kettle, and then addition paraxylene, will be anti-as solvent
Kettle is answered to seal, and magnetic agitation, by metallic sodium and 1,3,5- tribromo-benzenes occur force and hereby react, and slough formation pair after halo groups
Claim cyclic alkane structure, while paraxylene is decomposed to form carbon nanotube under the catalysis of metallic sodium；
B, the product of step a is mixed, and high-temperature process with melamine powder, cyclic alkane is made to be decomposed into carbon quantum dot, and
It is grown simultaneously with carbon nanotube, carbon quantum dot is adsorbed on the inside of carbon nanotube, and melamine decomposes the C-N key generated and is grafted on carbon
On the outside of nanotube；
C, carbon quantum dot, the composite mixed carbon nano-tube catalyst of carbonitride is made in washing, drying.
In step a, 15 parts by weight of metallic sodium, 1,3,5- tribromo-benzene, 20 parts by weight, 65 parts by weight of paraxylene.Magnetic agitation
Revolving speed be 150r/min.The temperature that force is hereby reacted is 210 DEG C, time 23h.
In step b, 78 parts by weight of product, 22 parts by weight of melamine powder of step a.The temperature of high-temperature process is 900
DEG C, time 7h.
In step c, washing uses dehydrated alcohol.Dry temperature is 150 DEG C, time 4h.
Embodiment 3
A, by metallic sodium and 1,3,5- tribromo-benzenes are mixed in a kettle, and then addition paraxylene, will be anti-as solvent
Kettle is answered to seal, and magnetic agitation, by metallic sodium and 1,3,5- tribromo-benzenes occur force and hereby react, and slough formation pair after halo groups
Claim cyclic alkane structure, while paraxylene is decomposed to form carbon nanotube under the catalysis of metallic sodium；
B, the product of step a is mixed, and high-temperature process with melamine powder, cyclic alkane is made to be decomposed into carbon quantum dot, and
It is grown simultaneously with carbon nanotube, carbon quantum dot is adsorbed on the inside of carbon nanotube, and melamine decomposes the C-N key generated and is grafted on carbon
On the outside of nanotube；
C, carbon quantum dot, the composite mixed carbon nano-tube catalyst of carbonitride is made in washing, drying.
In step a, 18 parts by weight of metallic sodium, 1,3,5- tribromo-benzene, 22 parts by weight, 60 parts by weight of paraxylene.Magnetic agitation
Revolving speed be 200r/min.The temperature that force is hereby reacted is 200 DEG C, time 23h.
In step b, 70 parts by weight of product, 30 parts by weight of melamine powder of step a.The temperature of high-temperature process is 1000
DEG C, time 6h.
In step c, washing uses propyl alcohol.Dry temperature is 140 DEG C, time 5h.
Embodiment 4
A, by metallic sodium and 1,3,5- tribromo-benzenes are mixed in a kettle, and then addition paraxylene, will be anti-as solvent
Kettle is answered to seal, and magnetic agitation, by metallic sodium and 1,3,5- tribromo-benzenes occur force and hereby react, and slough formation pair after halo groups
Claim cyclic alkane structure, while paraxylene is decomposed to form carbon nanotube under the catalysis of metallic sodium；
B, the product of step a is mixed, and high-temperature process with melamine powder, cyclic alkane is made to be decomposed into carbon quantum dot, and
It is grown simultaneously with carbon nanotube, carbon quantum dot is adsorbed on the inside of carbon nanotube, and melamine decomposes the C-N key generated and is grafted on carbon
On the outside of nanotube；
C, carbon quantum dot, the composite mixed carbon nano-tube catalyst of carbonitride is made in washing, drying.
In step a, 20 parts by weight of metallic sodium, 1,3,5- tribromo-benzene, 25 parts by weight, 55 parts by weight of paraxylene.Magnetic agitation
Revolving speed be 250r/min.The temperature that force is hereby reacted is 200 DEG C, time 25h.
In step b, 75 parts by weight of product, 25 parts by weight of melamine powder of step a.The temperature of high-temperature process is 900
DEG C, time 5h.
In step c, washing uses ether.Dry temperature is 150 DEG C, time 4h.
Embodiment 5
A, by metallic sodium and 1,3,5- tribromo-benzenes are mixed in a kettle, and then addition paraxylene, will be anti-as solvent
Kettle is answered to seal, and magnetic agitation, by metallic sodium and 1,3,5- tribromo-benzenes occur force and hereby react, and slough formation pair after halo groups
Claim cyclic alkane structure, while paraxylene is decomposed to form carbon nanotube under the catalysis of metallic sodium；
B, the product of step a is mixed, and high-temperature process with melamine powder, cyclic alkane is made to be decomposed into carbon quantum dot, and
It is grown simultaneously with carbon nanotube, carbon quantum dot is adsorbed on the inside of carbon nanotube, and melamine decomposes the C-N key generated and is grafted on carbon
On the outside of nanotube；
C, carbon quantum dot, the composite mixed carbon nano-tube catalyst of carbonitride is made in washing, drying.
In step a, 15 parts by weight of metallic sodium, 1,3,5- tribromo-benzene, 20 parts by weight, 65 parts by weight of paraxylene.Magnetic agitation
Revolving speed be 150r/min.The temperature that force is hereby reacted is 210 DEG C, time 22h.
In step b, 66 parts by weight of product, 34 parts by weight of melamine powder of step a.The temperature of high-temperature process is 1100
DEG C, time 7h.
In step c, washing uses ether.Dry temperature is 150 DEG C, time 4h.
Comparative example 1
A, by metallic sodium and 1,3,5- tribromo-benzenes are mixed in a kettle, and then addition paraxylene, will be anti-as solvent
Kettle is answered to seal, and magnetic agitation, by metallic sodium and 1,3,5- tribromo-benzenes occur force and hereby react, and slough formation pair after halo groups
Claim cyclic alkane structure, while paraxylene is decomposed to form carbon nanotube under the catalysis of metallic sodium；
B, the product of step a is mixed, and high-temperature process with melamine powder, cyclic alkane is made to be decomposed into carbon quantum dot, and
It is grown simultaneously with carbon nanotube, carbon quantum dot is adsorbed on the inside of carbon nanotube, and melamine decomposes the C-N key generated and is grafted on carbon
On the outside of nanotube；
C, carbon quantum dot, the composite mixed carbon nano-tube catalyst of carbonitride is made in washing, drying.
In step a, 15 parts by weight of metallic sodium, 1,3,5- tribromo-benzene, 5 parts by weight, 65 parts by weight of paraxylene.Magnetic agitation
Revolving speed be 150r/min.The temperature that force is hereby reacted is 210 DEG C, time 22h.
In step b, 66 parts by weight of product, 34 parts by weight of melamine powder of step a.The temperature of high-temperature process is 1100
DEG C, time 7h.
In step c, washing uses ether.Dry temperature is 150 DEG C, time 4h.
Comparative example 1 reduces the dosage of 1,3,5- tribromo-benzene, so that carbon quantum dot is reduced, composite mixed carbon nanotube is made
For catalyst.Catalytic activity is substantially reduced.
Carbon nano-tube catalyst made from above-described embodiment 1 ~ 5 and comparative example 1 tests its specific surface area and produces hydrogen volume,
Method or the condition for testing characterization are as follows:
Specific surface area: taking 1g carbon nano-tube catalyst produced by the present invention, measures specific surface using BET specific surface area tester
Product.
It produces hydrogen volume: carrying out Photocatalyzed Hydrogen Production test in the heatproof glass container of a 600mL, stone is set inside container
500W collimation high-pressure sodium lamp is placed in quartzy jacketed pipe as light source is reacted by English jacketed pipe, and logical cooling water filters out red in collet
Outer light simultaneously keeps temperature of reactor constant.When test, 0.2g catalyst produced by the present invention is added in 600mL water, magnetic force stirs
Mix, reaction temperature is 50 DEG C or so, react the gas of output and collected using draining water gathering of gas law, respectively measurement 20min, 40min and
The volume for generating gas is measured when 60min, using Hewlett-Packard 6890A gas chromatograph ingredient, it is known that the gas of generation is pure hydrogen.
The results are shown in Table 1.
Table 1:
Claims (10)
1. a kind of preparation method for the carbon nano-tube catalyst for being used to prepare fuel cell hydrogen, it is characterised in that: the carbon is received
Mitron catalyst is hereby to be reacted to generate symmetric annular alkane and be decomposed into carbon quantum with 1,3,5- tribromo-benzene generation force by metallic sodium
Point, and be adsorbed on the inside of the carbon nanotube that paraxylene is decomposed to form, melamine decomposes the C-N key generated and is grafted on carbon nanometer
It is made, specific preparation step on the outside of pipe are as follows:
A, by metallic sodium and 1,3,5- tribromo-benzenes are mixed in a kettle, and then addition paraxylene, will be anti-as solvent
Kettle is answered to seal, and magnetic agitation, by metallic sodium and 1,3,5- tribromo-benzenes occur force and hereby react, and slough formation pair after halo groups
Claim cyclic alkane structure, while paraxylene is decomposed to form carbon nanotube under the catalysis of metallic sodium；
B, the product of step a is mixed, and high-temperature process with melamine powder, cyclic alkane is made to be decomposed into carbon quantum dot, and
It is grown simultaneously with carbon nanotube, carbon quantum dot is adsorbed on the inside of carbon nanotube, and melamine decomposes the C-N key generated and is grafted on carbon
On the outside of nanotube；
C, carbon quantum dot, the composite mixed carbon nano-tube catalyst of carbonitride is made in washing, drying.
2. a kind of preparation method for the carbon nano-tube catalyst for being used to prepare fuel cell hydrogen according to claim 1,
It is characterized in that: in the step a, 15 ~ 20 parts by weight of metallic sodium, 1,3,5- tribromo-benzene, 20 ~ 25 parts by weight, paraxylene 55 ~ 65
Parts by weight.
3. a kind of preparation method for the carbon nano-tube catalyst for being used to prepare fuel cell hydrogen according to claim 1,
Be characterized in that: in the step a, reaction kettle sealing uses double mechanical seal.
4. a kind of preparation method for the carbon nano-tube catalyst for being used to prepare fuel cell hydrogen according to claim 1,
Be characterized in that: in the step a, the revolving speed of magnetic agitation is 150 ~ 300r/min.
5. a kind of preparation method for the carbon nano-tube catalyst for being used to prepare fuel cell hydrogen according to claim 1,
Be characterized in that: in the step a, the temperature that force is hereby reacted is 200 ~ 210 DEG C, and the time is 22 ~ 25h.
6. a kind of preparation method for the carbon nano-tube catalyst for being used to prepare fuel cell hydrogen according to claim 1,
It is characterized in that: in the step b, 66 ~ 78 parts by weight of product, 22 ~ 34 parts by weight of melamine powder of step a.
7. a kind of preparation method for the carbon nano-tube catalyst for being used to prepare fuel cell hydrogen according to claim 1,
Be characterized in that: in the step b, the temperature of high-temperature process is 900 ~ 1100 DEG C, and the time is 5 ~ 7h.
8. a kind of preparation method for the carbon nano-tube catalyst for being used to prepare fuel cell hydrogen according to claim 1,
Be characterized in that: in the step c, washing uses one of dehydrated alcohol, propyl alcohol, ether.
9. a kind of preparation method for the carbon nano-tube catalyst for being used to prepare fuel cell hydrogen according to claim 1,
Be characterized in that: in the step c, dry temperature is 130 ~ 150 DEG C, and the time is 4 ~ 6h.
10. a kind of carbon nano-tube catalyst for being used to prepare fuel cell hydrogen, it is characterized in that by any one of claim 1 ~ 9 institute
The method of stating is prepared.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111302476A (en) * | 2020-02-27 | 2020-06-19 | 南京大学 | Preparation and application of magnetic material capable of activating persulfate and allowing MOF (metal-organic framework) in-situ growth of CNT (carbon nano tube) |
| CN114262913A (en) * | 2021-11-26 | 2022-04-01 | 常州大学 | Preparation method of catalyst for producing hydrogen by electrolyzing water with high current density |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111302476A (en) * | 2020-02-27 | 2020-06-19 | 南京大学 | Preparation and application of magnetic material capable of activating persulfate and allowing MOF (metal-organic framework) in-situ growth of CNT (carbon nano tube) |
| CN111302476B (en) * | 2020-02-27 | 2021-12-17 | 南京大学 | Preparation and application of magnetic material capable of activating persulfate and allowing MOF (metal-organic framework) in-situ growth of CNT (carbon nano tube) |
| CN114262913A (en) * | 2021-11-26 | 2022-04-01 | 常州大学 | Preparation method of catalyst for producing hydrogen by electrolyzing water with high current density |
| CN114262913B (en) * | 2021-11-26 | 2023-08-22 | 常州大学 | Preparation method of catalyst for preparing hydrogen by high-current density water electrolysis |
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