CN108097253B - A kind of carbon nanotube loaded metallic cobalt nanoparticle catalyst and its preparation method and application - Google Patents
A kind of carbon nanotube loaded metallic cobalt nanoparticle catalyst and its preparation method and application Download PDFInfo
- Publication number
- CN108097253B CN108097253B CN201711099891.0A CN201711099891A CN108097253B CN 108097253 B CN108097253 B CN 108097253B CN 201711099891 A CN201711099891 A CN 201711099891A CN 108097253 B CN108097253 B CN 108097253B
- Authority
- CN
- China
- Prior art keywords
- carbon nanotube
- cobalt
- nanoparticle catalyst
- solution
- nanotube loaded
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000010941 cobalt Substances 0.000 title claims abstract description 70
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 70
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 67
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 64
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 18
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000011232 storage material Substances 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000003851 azoles Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 18
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 4
- 230000005518 electrochemistry Effects 0.000 abstract description 3
- 238000005119 centrifugation Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 11
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 11
- 229910012375 magnesium hydride Inorganic materials 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 238000009396 hybridization Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- BKXAWQXZFFNQHY-UHFFFAOYSA-N C(C)O.[N+](=O)([O-])[O-].[Co+2].[N+](=O)([O-])[O-] Chemical compound C(C)O.[N+](=O)([O-])[O-].[Co+2].[N+](=O)([O-])[O-] BKXAWQXZFFNQHY-UHFFFAOYSA-N 0.000 description 2
- SLCITEBLLYNBTQ-UHFFFAOYSA-N CO.CC=1NC=CN1 Chemical compound CO.CC=1NC=CN1 SLCITEBLLYNBTQ-UHFFFAOYSA-N 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- GANMEEJISNNTGT-UHFFFAOYSA-N ethanol;2-methyl-1h-imidazole Chemical compound CCO.CC1=NC=CN1 GANMEEJISNNTGT-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- -1 Hydrogen Chemical class 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- NVLDSCWHEUSPCV-UHFFFAOYSA-N [Co++].CO.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [Co++].CO.[O-][N+]([O-])=O.[O-][N+]([O-])=O NVLDSCWHEUSPCV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000001241 arc-discharge method Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- QQZGYZFGNGKDOE-UHFFFAOYSA-N cobalt;methanol Chemical compound [Co].OC QQZGYZFGNGKDOE-UHFFFAOYSA-N 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
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000004050 hot filament vapor deposition Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 238000001182 laser chemical vapour deposition Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B01J35/399—
-
- B01J35/40—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0026—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof of one single metal or a rare earth metal; Treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0078—Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
-
- 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
- Y02E60/32—Hydrogen storage
Abstract
The invention discloses a kind of preparation methods of carbon nanotube loaded metallic cobalt nanoparticle catalyst, it include: that (1) instills divalent cobalt solution in 2-methylimidazole solution, it reacts 4~6 hours under stiring, violet precipitate is collected by centrifugation after reaction, obtains violet solid after washed, dry；(2) violet solid that step (1) obtains is carbonized in protection gas, obtained black powder is the carbon nanotube loaded metallic cobalt nanoparticle catalyst.The invention also discloses carbon nanotube loaded metallic cobalt nanoparticle catalyst obtained by the above method and its preparing the application in composite hydrogen storage material.The metal cobalt nanometer particle that the method for the present invention obtains can equably, be carried on carbon nano tube surface securely, and preparation method of the present invention is simple, and yield is high.Meanwhile a large amount of preparations of this carbon nanotube loaded metallic cobalt nanoparticle catalyst may be implemented using the present invention, and be widely used in electrochemistry and catalytic field.
Description
Technical field
The present invention relates to field of catalyst preparation, and in particular to a kind of carbon nanotube loaded metallic cobalt nanoparticle catalyst
And its preparation method and application.
Background technique
It is well known that the structure of material determines its property, the unique tubulose one-dimentional structure of carbon nanotube (CNT) is made it have
Superior physicochemical characteristics.Composite hybridization structure based on carbon nanotube has a variety of excellent performances, therefore in many necks
Domain is applied widely, and such as forming composite hybridization structure using carbon nanotube loaded various metal catalyst particles can be improved
The dispersibility of catalyst granules and make it have higher catalytic activity.Various metals particle such as Pd, Au, Co and Fe etc. have only
Special photoelectricity magnetic characteristic and catalytic effect modifies these upper particles in carbon nano tube surface and by the spy of its characteristic and carbon nanotube
Property combine the composite hybridization structure of acquisition, there is important application value in electrochemistry and catalytic field.
The method of preparation carbon nanotube has much at present, and main method can be classified as three classes: arc discharge method, laser ablation
Method and chemical vapour deposition technique (CVD).Wherein catalytic chemical vapor deposition technique prepares the method for CNT due to technique stream
The advantages that journey is simple, controllability is strong and be widely adopted.But its conversion yield is relatively low, generally below 40%.
The technique of conventional preparation carbon nanotube composite hybridization structure includes the pretreatment carbon nanotube and matrix of carbon nanotube
Or the separation and purification of the blending hybrid structure of decorative material and etc..Influence factor is more during this, Yao Shixian hydridization
The controllable preparation of structure is more difficult.Simultaneously as the stronger hydrophobicity of carbon nanotube, so that most of metallic particles can not be straight
The surface for loading to carbon nanotube is connect, so usually carrying out strong acid oxidation processes to it in advance, introduces hydroxyl, carboxyl etc. on surface
Functional group.But the surface texture of carbon nanotube can be destroyed after strong acid treatment, the corrosion resistance of carbon nanotube is reduced, and then reduce
The service life of catalyst.
Summary of the invention
Object of the present invention is to be directed to cumbersome carbon nanotube preparation process, loaded metal particle bad dispersibility, provide
It is a kind of it is easy, the synthesis for realizing carbon nanotube and the preparation in carbon nano tube surface carried metal cobalt nano-particle can be synchronized
Method.The present invention is achieved in the following ways:
A kind of preparation method of carbon nanotube loaded metallic cobalt nanoparticle catalyst, includes the following steps:
(1) divalent cobalt and 2-methylimidazole are dissolved in a certain amount of solvent respectively, obtain divalent cobalt solution and 2- first
Base imidazole solution instills divalent cobalt solution in 2-methylimidazole solution, under stiring reaction 4~6 hours, after reaction
Violet precipitate is collected by centrifugation, obtains violet solid after washed, dry；
(2) violet solid that step (1) obtains is carbonized in protection gas, obtained black powder is described
Carbon nanotube loaded metallic cobalt nanoparticle catalyst.
By adjusting the proportion of divalent cobalt and 2-methylimidazole, presoma is synthesized at room temperature, using high temperature cabonization
Effect forms carbon nano tube structure, and simultaneously receive cobalt nano-particle uniform load in carbon using the cobalt in cobalt salt as catalyst
Nanotube surface passes through the metal cobalt loaded nanoparticle catalyst of one-step method carbon nano-tube in situ, the method for the present invention process letter
It is single, it is easy to control.
In step (1), the temperature of reaction is 25~35 DEG C.
The solvent is methanol, dehydrated alcohol or deionized water.
The divalent cobalt is sulfate, chloride, nitrate, acetate or the perchlorate of cobalt.
The concentration of the divalent cobalt solution is 0.5~0.7mol/L, the concentration of the 2-methylimidazole solution is 1.0~
1.4mol/L。
Divalent cobalt and the molar ratio of 2-methylimidazole are 1:2~4, in the proportional region, the presoma that is collapsed
Frame, and the formation for having enough cobalt elements to carry out catalyzing carbon nanotube obtain high carbon nanotube conversion ratio.
In step (1), mixing speed is 500~800 revs/min, and mixing speed appropriate can make presoma forming core equal
It is even, and then obtain the uniform carbon nanotube of diameter dimension.
In step (1), the rate of addition of divalent cobalt solution is 5~15ml/min.
In step (1), the revolving speed of centrifugally operated is 8000~12000 revs/min.
In step (1), the drying is vacuum drying, and drying temperature is 60~80 DEG C, and drying time is 20~24 hours.
In step (2), it is carbonized in tube furnace, carburizing temperature is 600~700 DEG C, and carbonization time is 5~7 hours,
Heating rate is 1~3 DEG C/min；Protection gas used is nitrogen or argon gas.
The present invention also provides carbon nanotube loaded metallic cobalt nanoparticle catalysts prepared by the above method, should
In carbon nanotube loaded metallic cobalt nanoparticle catalyst, metal cobalt nano-particle high-dispersion load in carbon nano tube surface,
Wherein, the caliber size of carbon nanotube is 20~30nm, and the partial size of metallic cobalt is 15~20nm.
It is multiple in preparation that it is a further object of the present invention to provide the carbon nanotube loaded metallic cobalt nanoparticle catalysts
The application closed in hydrogen storage material improves metallic cobalt since metal cobalt nano-particle high-dispersion load is in carbon nano tube surface
The properties effect of nano particle, the carbon nanotube loaded metallic cobalt nanoparticle catalyst have extensive in catalytic field
Using.
It is an advantage of the current invention that synthesizing presoma at room temperature, and one-step synthesis carbon nanometer is reacted by high temperature cabonization
Manage metal cobalt loaded nanoparticle catalyst.The metal nanoparticle that the method obtains can equably, be carried on carbon securely
Nanotube surface, and preparation method of the present invention is simple, and yield is high.Meanwhile this carbon nanotube may be implemented using the present invention
A large amount of preparations of metal cobalt loaded nanoparticle catalyst, and it is widely used in electrochemistry and catalytic field.
Detailed description of the invention
Fig. 1 is the SEM figure of carbon nanotube loaded metallic cobalt nanoparticle catalyst prepared by embodiment 1；
Fig. 2 is the TEM figure of carbon nanotube loaded metallic cobalt nanoparticle catalyst prepared by embodiment 1；
Fig. 3 is the XRD diagram of carbon nanotube loaded metallic cobalt nanoparticle catalyst prepared by embodiment 1；
Fig. 4 is the SEM figure of carbon nanotube loaded metallic cobalt nanoparticle catalyst prepared by embodiment 4；
Fig. 5 is the SEM figure of carbon plate carried metal Co catalysts prepared by embodiment 5；
Fig. 6 is the TEM figure of carbon plate carried metal Co catalysts prepared by embodiment 5；
Fig. 7 is the carbon nanotube loaded metallic cobalt nanoparticle catalyst of the preparation of embodiment 1 to MgH2Catalysis isothermal inhale
Hydrogen performance comparison figure；
Fig. 8 is the carbon nanotube loaded metallic cobalt nanoparticle catalyst of the preparation of embodiment 1 to MgH2Catalysis alternating temperature put
Hydrogen performance comparison figure.
Specific embodiment
The invention will be further described With reference to embodiment.
Embodiment 1
(1) at 25 DEG C of environment temperature, 3.823g cobalt nitrate is dissolved in 20mL deionized water, cobalt nitrate aqueous solution is obtained, it will
4.315g 2-methylimidazole is dissolved in 40mL deionized water, obtains 2-methylimidazole aqueous solution, will with the drop rate of 10ml/min
Cobalt nitrate aqueous solution is added dropwise in 2-methylimidazole aqueous solution, with 500r/min at the uniform velocity mechanical stirring, reacts 4 hours, obtains
Purple liquid；Purple solution after completion of the reaction is subjected to 10000r/min centrifugally operated, and is washed with deionized three times, is received
Collect violet precipitate, is dried in vacuo 24 hours at 80 DEG C, obtains purple powder.
(2) purple powder that 1g is prepared, is put into porcelain boat, moves into tube furnace, argon gas protection gas is passed through, 600
DEG C carry out high temperature cabonization, heating rate be 2 DEG C/min, soaking time be 5 hours.The black powder that carbonization obtains is collected, as
The carbon nanotube loaded metallic cobalt nanoparticle catalyst being prepared.
The SEM of carbon nanotube loaded metallic cobalt nanoparticle catalyst manufactured in the present embodiment schemes as shown in Figure 1, TEM schemes
As shown in Fig. 2, XRD diagram is as shown in figure 3, in Fig. 3, Co@CNT is carbon nanotube loaded metallic cobalt nanometer manufactured in the present embodiment
Grain catalyst, detected diffraction maximum and Co PDF#15-0806 standard card are corresponding very well.
Embodiment 2
(1) at 25 DEG C of environment temperature, 3.823g cobalt nitrate is dissolved in 20mL dehydrated alcohol, cobalt nitrate ethanol solution is obtained,
4.315g 2-methylimidazole is dissolved in 40mL dehydrated alcohol, 2-methylimidazole ethanol solution is obtained, with the dropwise addition speed of 10ml/min
Cobalt nitrate ethanol solution is added dropwise in 2-methylimidazole ethanol solution rate, and with 500r/min at the uniform velocity mechanical stirring, reaction 5 is small
When, obtain purple liquid；Purple solution after completion of the reaction is subjected to 10000r/min centrifugally operated, and is washed with dehydrated alcohol
Three times, violet precipitate is collected, is dried in vacuo 24 hours at 60 DEG C, obtains purple powder.
(2) purple powder that 1g is prepared, is put into porcelain boat, moves into tube furnace, argon gas protection gas is passed through, 600
DEG C carry out high temperature cabonization, heating rate be 3 DEG C/min, soaking time be 6 hours.The black powder that carbonization obtains is collected, as
The carbon nanotube loaded metallic cobalt nanoparticle catalyst being prepared.
Embodiment 3
(1) at 30 DEG C of environment temperature, 3.823g cobalt nitrate is dissolved in 20mL methanol, obtains cobalt nitrate methanol solution, it will
4.315g 2-methylimidazole is dissolved in 40mL methanol, obtains 2-methylimidazole methanol solution, with the drop rate of 10ml/min by nitre
Sour cobalt methanol solution is added dropwise in 2-methylimidazole methanol solution, with 500r/min at the uniform velocity mechanical stirring, reacts 6 hours, obtains
To purple liquid；Purple solution after completion of the reaction is subjected to 10000r/min centrifugally operated, and is washed three times with methanol, is collected
Violet precipitate is dried in vacuo 24 hours at 60 DEG C, obtains purple powder.
(2) purple powder that 1g is prepared, is put into porcelain boat, moves into tube furnace, nitrogen protection gas is passed through, 700
DEG C carry out high temperature cabonization, heating rate be 2 DEG C/min, soaking time be 5 hours.The black powder that carbonization obtains is collected, as
The carbon nanotube loaded metallic cobalt nanoparticle catalyst being prepared.
Embodiment 4
(1) at 25 DEG C of environment temperature, 2.911g cobalt nitrate is dissolved in 10mL deionized water, cobalt nitrate aqueous solution is obtained, it will
1.642g 2-methylimidazole is dissolved in 15mL deionized water, obtains 2-methylimidazole aqueous solution, will with the drop rate of 10ml/min
Cobalt nitrate aqueous solution is added dropwise in 2-methylimidazole aqueous solution, with 600r/min at the uniform velocity mechanical stirring, reacts 6 hours, obtains
Purple liquid；Purple solution after completion of the reaction is subjected to 12000r/min centrifugally operated, and is washed with deionized three times, is received
Collect violet precipitate, is dried in vacuo 24 hours at 80 DEG C, obtains purple powder.
(2) purple powder that 1g is prepared, is put into porcelain boat, moves into tube furnace, is passed through nitrogen protection gas, In
600 DEG C of progress high temperature cabonizations, heating rate are 2 DEG C/min, and soaking time is 7 hours.The black powder that carbonization obtains is collected, i.e.,
For the carbon nanotube loaded metallic cobalt nanoparticle catalyst being prepared.
The SEM of carbon nanotube loaded metallic cobalt nanoparticle catalyst manufactured in the present embodiment schemes as shown in figure 3, from figure
It can be seen that changing the ratio of divalent cobalt and 2-methylimidazole, the diameter of carbon nanotube changes, and has fraction miscellaneous
The conversion ratio of matter phase, carbon nanotube decreases.
Embodiment 5
(1) at 25 DEG C of environment temperature, 0.956g cobalt nitrate is dissolved in 5mL deionized water, cobalt nitrate aqueous solution is obtained, it will
8.630g 2-methylimidazole is dissolved in 80mL deionized water, obtains 2-methylimidazole aqueous solution, will with the drop rate of 10ml/min
Cobalt nitrate aqueous solution is added dropwise in 2-methylimidazole aqueous solution, with 500r/min at the uniform velocity mechanical stirring, reacts 4 hours, obtains
Purple liquid；Purple solution after completion of the reaction is subjected to 10000r/min centrifugally operated, and is washed with deionized three times, is received
Collect violet precipitate, is dried in vacuo 24 hours at 80 DEG C, obtains purple powder.
(2) purple powder that 1g is prepared, is put into porcelain boat, moves into tube furnace, argon gas protection gas is passed through, 600
DEG C carry out high temperature cabonization, heating rate be 2 DEG C/min, soaking time be 5 hours.The black powder that carbonization obtains is collected, as
The metal cobalt loaded nanoparticle catalyst of the carbon plate being prepared.
The SEM figure of catalyst manufactured in the present embodiment is as shown in Figure 5, it is possible to find when the ratio of divalent cobalt and 2-methylimidazole
Example can not form carbon nano tube structure beyond after the scope of the invention；TEM figure is as shown in fig. 6, as seen from the figure, metallic cobalt loads
In on carbon plate, and not formed carbon nano tube structure, and metal cobalt granule is larger, diameter is 30~40nm.
Embodiment 6
The carbon nanotube loaded metallic cobalt nanoparticle catalyst of 0.05g prepared by embodiment 1 is adulterated using ball grinding technique
To 0.95g MgH2In metal hydride (400 revs/min of drum's speed of rotation, Ball-milling Time 2 hours, ratio of grinding media to material 40:1), test
The carbon nanotube loaded metallic cobalt nanoparticle catalyst is to MgH2The catalytic effect of hydrogen storage property
Hydrogen release tester is inhaled using PCT, and MgH is catalyzed to carbon nanotube loaded metal cobalt nano-particle2Hydrogen storage property into
Test is gone.Hydrogen release test method is under vacuum conditions, to be raised to 500 DEG C with the heating rate of 5 DEG C/min, pass through recorder
The change value of pressure of device is calculated hydrogen release mass ratio.Inhaling hydrogen test method is, at 250 DEG C, pressure of the sample in 3MPa
Lower progress isothermal inhales hydrogen, is calculated by the changing value of register instrument pressure and inhales hydrogen mass ratio.
The result shows that the carbon nanotube loaded metallic cobalt nanoparticle catalyst is to MgH2Hydrogen discharging performance have it is very excellent
Different catalytic effect.Fig. 7 is carbon nanotube loaded metallic cobalt nanoparticle catalyst to MgH2Catalysis isothermal hydrogen sucking function pair
Than figure, the MgH undoped with catalyst2250 DEG C inhale hydrogen 300 seconds after hydrogen-sucking amount be no more than 5.0wt% (mass percent, under
Together), it is doped with the MgH of carbon nanotube loaded metallic cobalt nanoparticle catalyst (Co@CNT)2At 250 DEG C in suction hydrogen 30 seconds
Hydrogen-sucking amount can be more than 6.0wt%, and hydrogen-absorption speed improves 10 times or more.Fig. 8 is carbon nanotube loaded metal cobalt nano-particle
Catalyst is to MgH2Catalysis alternating temperature hydrogen discharging performance comparison diagram, undoped with catalyst MgH2It needs just to start at 350 DEG C significant
Hydrogen release, hydrogen release cut-off temperature are 430 DEG C；And it is doped with the MgH of Co@CNT catalyst2It can start significant hydrogen release at 170 DEG C,
Its hydrogen release cut-off temperature is effectively reduced to 350 DEG C.
Claims (5)
1. a kind of carbon nanotube loaded metallic cobalt nanoparticle catalyst exists preparing the application in composite hydrogen storage material, feature
In the carbon nanotube loaded metallic cobalt nanoparticle catalyst is made by following steps:
(1) divalent cobalt and 2-methylimidazole are dissolved in a certain amount of solvent respectively, obtain divalent cobalt solution and 2- methyl miaow
Azoles solution instills divalent cobalt solution in 2-methylimidazole solution, reacts 4~6 hours, is centrifuged under stiring after reaction
Violet precipitate is collected, obtains violet solid after washed, dry；
(2) violet solid that step (1) obtains is carbonized in protection gas, obtained black powder is that the carbon is received
The metal cobalt loaded nanoparticle catalyst of mitron；
In step (1), the molar ratio of divalent cobalt and 2-methylimidazole is 1:2~4.
2. application according to claim 1, which is characterized in that the divalent cobalt is sulfate, chloride, the nitre of cobalt
Hydrochlorate, acetate or perchlorate.
3. application according to claim 1, which is characterized in that the concentration of the divalent cobalt solution is 0.5~0.7mol/
L, the concentration of the 2-methylimidazole solution are 1.0~1.4mol/L.
4. application according to claim 1, which is characterized in that in step (1), mixing speed is 500~800 revs/min.
5. application according to claim 1, which is characterized in that in step (2), it is carbonized in tube furnace, carbonization temperature
Degree is 600~700 DEG C, and carbonization time is 5~7 hours, and heating rate is 1~3 DEG C/min；Protection gas used is nitrogen or argon
Gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711099891.0A CN108097253B (en) | 2017-11-09 | 2017-11-09 | A kind of carbon nanotube loaded metallic cobalt nanoparticle catalyst and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711099891.0A CN108097253B (en) | 2017-11-09 | 2017-11-09 | A kind of carbon nanotube loaded metallic cobalt nanoparticle catalyst and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108097253A CN108097253A (en) | 2018-06-01 |
| CN108097253B true CN108097253B (en) | 2019-11-19 |
Family
ID=62207654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711099891.0A Active CN108097253B (en) | 2017-11-09 | 2017-11-09 | A kind of carbon nanotube loaded metallic cobalt nanoparticle catalyst and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108097253B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112409983B (en) * | 2020-12-15 | 2023-09-08 | 合肥工业大学 | Electromagnetic wave absorber based on 2-methylimidazole cobalt derivative cobalt and carbon nanotube composite and preparation method thereof |
| CN112645309B (en) * | 2021-01-14 | 2023-02-24 | 齐鲁工业大学 | Fluorinated bamboo-like carbon nanotube and preparation method and application thereof |
| CN115108532B (en) * | 2022-08-26 | 2022-11-15 | 苏州清德氢能源科技有限公司 | Magnesium-based hydrogen storage material and preparation method thereof |
-
2017
- 2017-11-09 CN CN201711099891.0A patent/CN108097253B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108097253A (en) | 2018-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109304201B (en) | Carbon-coated transition metal nanocomposite and preparation method and application thereof | |
| CN111620311B (en) | Porous carbon-loaded monoatomic metal nitrogen coordination composite material and preparation method thereof | |
| Li et al. | Porous PdRh nanobowls: facile synthesis and activity for alkaline ethanol oxidation | |
| CN108579783B (en) | Preparation method of nitrogen-doped porous carbon loaded metal monoatomic material | |
| CN108097253B (en) | A kind of carbon nanotube loaded metallic cobalt nanoparticle catalyst and its preparation method and application | |
| Kalidindi et al. | Nanostructured Cu and Cu@ Cu 2 O core shell catalysts for hydrogen generation from ammonia–borane | |
| Horváth et al. | Methane dry reforming with CO2 on CeZr-oxide supported Ni, NiRh and NiCo catalysts prepared by sol–gel technique: Relationship between activity and coke formation | |
| CN107744822B (en) | Metal phosphide-porous carbon framework composite material and preparation method and application thereof | |
| CN112044462B (en) | Graphene-loaded transition metal nitride nanocomposite and preparation method and application thereof | |
| CN109126844B (en) | Molybdenum carbide nanosheet and preparation method and application thereof | |
| CN110639549A (en) | Universal method for preparing high-stability noble metal monatomic catalyst | |
| CN106607018B (en) | A kind of catalyst for dehydrogenation of low-carbon paraffin and preparation method and application | |
| CN109908945A (en) | A kind of methane portion oxidation synthesis gas PtO@S-1 hierarchical porous structure molecular sieve and its preparation method and application | |
| CN106607019B (en) | Propane dehydrogenation catalyst and preparation method | |
| CN113209964A (en) | Supported palladium-based catalyst and preparation method and application thereof | |
| CN104797338A (en) | Catalyst comprising iron and carbon nanotubes | |
| Ni et al. | Target-oriented confinement of Ru-Co nanoparticles inside N-doped carbon spheres via a benzoic acid guided process for high-efficient low-temperature ammonia synthesis | |
| JP5585275B2 (en) | Carbon nanotube manufacturing method | |
| WO2011080275A1 (en) | Method for preparation of bimetallic compositions of cobalt and palladium on an intert material support and compositions obtainable by the same | |
| Tang et al. | Decorating multi-walled carbon nanotubes with nickel nanoparticles for selective hydrogenation of citral | |
| CN111554944A (en) | Application of hollow mesoporous carbon spheres | |
| CN108262043B (en) | Preparation method of Fischer-Tropsch synthesis catalyst and prepared Fischer-Tropsch synthesis catalyst | |
| CN108262044B (en) | Preparation method of Fischer-Tropsch synthesis catalyst and prepared Fischer-Tropsch synthesis catalyst | |
| CN106607017B (en) | Catalyst for dehydrogenation of low-carbon paraffin and preparation and application | |
| CN115090293A (en) | Core-shell cerium dioxide nanorod supported nickel catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |