CN107159214A - A kind of porous active carbon material load cobalt nanometer particle material and its preparation method and application - Google Patents
A kind of porous active carbon material load cobalt nanometer particle material and its preparation method and application Download PDFInfo
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- CN107159214A CN107159214A CN201710480109.3A CN201710480109A CN107159214A CN 107159214 A CN107159214 A CN 107159214A CN 201710480109 A CN201710480109 A CN 201710480109A CN 107159214 A CN107159214 A CN 107159214A
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- cobalt
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 87
- 239000010941 cobalt Substances 0.000 title claims abstract description 72
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 72
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000002245 particle Substances 0.000 title claims abstract description 65
- 239000000463 material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 52
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 52
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 20
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 230000007062 hydrolysis Effects 0.000 claims abstract description 17
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 11
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000007599 discharging Methods 0.000 claims abstract description 10
- -1 nitrogen-containing compound Chemical class 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 8
- 239000008103 glucose Substances 0.000 claims abstract description 8
- 238000009826 distribution Methods 0.000 claims abstract description 7
- 230000004087 circulation Effects 0.000 claims abstract description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 238000006722 reduction reaction Methods 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 52
- 229910052799 carbon Inorganic materials 0.000 claims description 48
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 229910000085 borane Inorganic materials 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 150000003349 semicarbazides Chemical class 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- 150000007529 inorganic bases Chemical group 0.000 claims description 2
- ZENDWEPAVHORFD-UHFFFAOYSA-N pyrimidine;urea Chemical compound NC(N)=O.C1=CN=CN=C1 ZENDWEPAVHORFD-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims 1
- 230000001154 acute effect Effects 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 230000006378 damage Effects 0.000 claims 1
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- 229910000104 sodium hydride Inorganic materials 0.000 claims 1
- 239000012312 sodium hydride Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000000446 fuel Substances 0.000 abstract description 2
- 235000013495 cobalt Nutrition 0.000 description 57
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 229910001316 Ag alloy Inorganic materials 0.000 description 8
- SQWDWSANCUIJGW-UHFFFAOYSA-N cobalt silver Chemical compound [Co].[Ag] SQWDWSANCUIJGW-UHFFFAOYSA-N 0.000 description 8
- 239000002121 nanofiber Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000003795 desorption Methods 0.000 description 5
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910003203 NH3BH3 Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SYSKEFYWNYDUCK-BTVCFUMJSA-N N1=CN=CC=C1.O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO Chemical compound N1=CN=CC=C1.O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO SYSKEFYWNYDUCK-BTVCFUMJSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003797 solvolysis reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000009283 thermal hydrolysis Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- 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
-
- B01J35/393—
-
- B01J35/618—
-
- B01J35/643—
-
- 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
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/068—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents the hydrogen being generated from the water as a result of a cyclus of reactions, not covered by groups C01B3/063 or C01B3/105
-
- 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 porous active carbon material load cobalt nanometer particle material, by glucose and nitrogen-containing compound, loose structure carbon material is prepared into by hydro-thermal method and subsequent treatment, then obtained by impregnating chemical reduction method load cobalt particle to carbon material, the scope of its specific surface area is 3026 ~ 3277 m2 g‑1, micro content is more than 95.18%, and pore-size distribution is homogeneous, is mainly distributed on 1.24 ~ 1.95 nm.Its preparation method includes 3 steps：1）Prepare nitrogenous precursor；2）Prepare loose structure carbon material；3）Load cobalt nanometer particle.When the present invention puts the application of hydrogen catalyst as catalysis ammonia borane hydrolysis, 10 min complete to put hydrogen, and hydrogen discharging rate reaches 865.2 mL min‑1 g‑1；It can be recycled, undergo after four circulations, putting the hydrogen time is maintained at 10 ~ 45min, and hydrogen discharging rate is maintained at 208.2 865.2 mL min‑1 g‑1.Material preparation method of the present invention is simple, production cost is low, it is recyclable reuse, it is practical, had broad application prospects in fields such as hydrogen manufacturing, fuel cells.
Description
Technical field
The present invention relates to carbon material and the technical field of catalysis ammonia borane hydrolysis hydrogen manufacturing, and in particular to carbon material preparation side
Method, and carbon load the preparation and application of cobalt nanometer particle.
Background technology
With the economic continuous growth developed rapidly with population, the demand of the energy is in expansion increasingly.Although fossil
Fuel still occupies the significantly ratio of energy resource structure, but fossil fuel is non-renewable resources, and brings certain pollution to environment,
Resulting serious problem of energy crisis is increasingly highlighted.The key factor for solving problems is that exploitation is new renewable low
Carbon green energy resource and its high-efficiency cleaning storage transformation technology.Hydrogen Energy as a kind of rich reserves, energy density it is high, easy to use,
Widely used secondary energy sources, receive the extensive concern of domestic and international researcher.Hydrogen Energy is a kind of preferable secondary energy sources.
Ammonia borine（NH3BH3, AB）With 19.6 %（Wt, mass fraction）Hydrogen content and receive significant attention.American energy in 2008
Portion is summarized in annual energy unanimously to be thought in meeting, and worldwide energy resource consumption continues to increase, at the same time, worldwide production
The energy crisis brought is increasingly serious.By taking the U.S. as an example, most of energy resource consumption is that in the form of electric power, the second largest energy disappears
Consumption field is traffic, and up to 27.8%.The energy usage type of field of traffic includes oil, natural gas and bio-fuel, oil
95% is accounted for as the energy of consumption.From after the crude oil production peak of 1970, crude oil production glides year by year.U.S. domestic
Energy output yield can not meet the state of demand for energy and continue many decades.Hydrogen Energy is a kind of preferably secondary energy
Source.Ammonia borine（NH3BH3, AB）With 19.6 wt%（Mass fraction）Hydrogen content and by domestic and international extensive concern.
Ammonia borine has high stability and environment friendly, is used as a kind of potential hydrogen storage material.The dehydrogenation of ammonia borine
Mode has 3 kinds, respectively solvolysis, thermal decomposition and hydrolysis.
Activated carbon is current topmost commercial electrode material, and it has substantial amounts of pore structure, big specific surface area is special
The advantages of point, strong adsorption capacity, stable physical and chemical performance and wide inexpensive material and be widely used in ultracapacitor, lithium
The frontier science and technology fields such as ion battery, gas absorption are with separating, water body purification.The synthetic method of current porous carbon materials is much led
It is classified as two classes：Template and activation method.The aperture of the carbon material prepared by conventional template method is single, and micro content is low and deposits
Complex operation, preparation time length and be difficult to ensure carbon material purity the shortcomings of.Therefore, activation method is prepared as researchers
One of study hotspot of loose structure and high-specific surface area carbon material.
The characteristics of with porous carbon big specific surface area, loads cobalt nanometer particle, cobalt nanometer particle can be allowed dispersed and not
Reunite, what cobalt nanometer particle was stablized is supported on the surface of carbon, so as to efficiently be catalyzed ammonia borane hydrolysis hydrogen manufacturing, and makes
It can be reused, had a extensive future by the method for filtering for the catalyst gone out, it is practical.
Wang et al. loads copper-cobalt alloy on porous carbon by first preparing porous carbon materials, then and prepares catalyst, but
Be prepared porous carbon materials micro content it is smaller, specific surface area is relatively low, reuse catalyst after effect substantially weaken.
Therefore, seek that a kind of preparation method is simple, specific surface area is big, pore structure enriches practical carbon material as current research
Focus.
The content of the invention
It is an object of the invention to provide a kind of porous active carbon material load cobalt nanometer particle material, by preparing porous carbon
Material, obtains big specific surface area material and pore-size distribution, allows cobalt nanometer particle can be uniformly dispersed on carbon material and do not roll into a ball
It is poly-, so that efficient catalytic ammonia borane hydrolysis hydrogen manufacturing is realized, and with good circulation performance, while solving current ammonia borane hydrolysis
Hydrogen discharging rate is low, catalyst agglomeration, the problems such as catalyst is unstable.
In order to realize foregoing invention purpose, the technical solution adopted by the present invention is carbon source, semicarbazides or urea using glucose
Pyrimidine is nitrogen source, uses alkali inorganic substance KOH etc. for activator, and stable three-dimensional porous carbon materials are synthesized using chemical activation method
Material.Nitrogen not only can successfully be entrained in carbon material, may be used also as the nitrogen source of high nitrogen content by semicarbazides or urea pyrimidine
As pore creating material, to occur pyrolytic reaction with carbon matrix precursor in carbonisation, so that increase the specific surface area of material as far as possible,
So as to load substantial amounts of cobalt nanometer particle, and then efficient catalytic ammonia borane hydrolysis hydrogen manufacturing.
Realizing the concrete technical scheme of the object of the invention is：
A kind of porous active carbon material load cobalt nanometer particle material, by, as carbon source, being added a certain amount of nitrogenous by glucose
Compound, then prepares porous carbon materials, soaking, drying, calcining, immersion, washing, filtering, drying, grinding by hydro-thermal method
Loose structure carbon material is obtained, then cobalt particle is loaded to carbon material by impregnating chemical reduction method, obtains porous active carbon material
Expect Supported Co nanometer particle material；The scope of its specific surface area is 3026 ~ 3277 m2 g-1, micro content is more than 95.18%, hole
Footpath distribution is homogeneous, is mainly distributed on 1.24 ~ 1.95 nm.
A kind of preparation method of porous active carbon material load cobalt nanometer particle material comprises the following steps：
Step 1）Nitrogenous precursor is prepared, is 1.0 by the mass ratio of glucose and nitrogen-containing compound:（0.5~4.0）, by glucose
Stirring and dissolving in deionized water is added to nitrogen-containing compound, is then placed in reactor, under the conditions of reaction temperature is 180 DEG C
Reaction, product is filtered, wash, dry after reaction, obtains nitrogenous precursor, and described nitrogen-containing compound is that semicarbazides and urea are phonetic
One or two kinds of mixing of pyridine；
Step 2）Loose structure carbon material is prepared, by step 1）Nitrogenous precursor and alkali inorganic substance mass ratio be 1.0:
（1.0~4.0）Mixing, immersion in deionized water, after drying, is put into tube furnace, under the conditions of temperature is 600 ~ 900 DEG C, calcining
2 ~ 8 hours, carbon material is obtained, the carbon material after calcining is taken out after cooling and is ground, after grinding, 1 mol/L hydrochloric acid is put into
Soaked in solution, by washing, filtering, drying, grinding, obtain loose structure carbon material, the alkali inorganic substance is inorganic base
Or alkaline, inorganic salts；
Step 3）Cobalt nanometer particle is loaded, is according to the mass ratio of cobalt element and carbon（5~9）:1, take cobalt chloride hexahydrate and
Above-mentioned steps 2）After obtained loose structure carbon material, the cobalt chloride solution that cobalt chloride is made into 0.1 mol/L, add porous
Structure carbon material, the ratio between the amount for meeting certain material with cobalt chloride and sodium borohydride is 1:2 relation, is 0.05 by concentration
Mol/L sodium borohydride solution is added drop-wise in cobalt chloride solution under the conditions of magnetic agitation, it is ensured that solution homogeneous reaction is abundant,
Prevent reaction from acutely destroying very much material surface structure, until after bubble-free generation, with water and ethanol cyclic washing, decompression suction filtration
Afterwards, 5 ~ 10 h are dried in vacuo at 80 DEG C, obtain porous active carbon material load cobalt nanometer particle material.
Porous active carbon material load cobalt nanometer particle material puts the application of hydrogen catalyst as catalysis ammonia borane hydrolysis,
The even cobalt nanometer particle for being dispersed in carbon surface can efficiently be catalyzed ammonia borane hydrolysis and put hydrogen at room temperature, and 10 min complete to put hydrogen,
Hydrogen discharging rate reaches 865.2 mL min-1 g-1。
Porous active carbon material load cobalt nanometer particle material puts the application of hydrogen catalyst as catalysis ammonia borane hydrolysis, many
Hole active carbon material Supported Co nanometer particle material can be recycled by filtering, washing, the method dried, and undergone four times and followed
After ring, putting the hydrogen time is maintained at 10 ~ 45 min, and hydrogen discharging rate is maintained at 208.2-865.2 mL min-1 g-1。
The carbon material supported front and rear Electronic Speculum that is scanned of porous active prepared to above-described embodiment is detected：
The carbon material supported preceding ESEM testing result of porous active shows that porous active carbon material aperture disperses more uniform；
Porous active carbon after porous active is carbon material supported loads cobalt nanometer particle ESEM result and shown, porous carbon surface
Many particles are loaded, these are evengranular to be dispersed in around hole, pattern is good, and homogeneity is good, and is supported on porous
Cobalt nanometer particle on carbon is not reunited.
Low temperature nitrogen isothermal adsorption table is carried out to porous active carbon material load cobalt nanometer particle prepared by above-described embodiment
Levy, as a result show, gas absorption amount has a rapid growth to pressure span in low phase, and this is attributed to micropore filling, and it has
Higher ratio surface.Its specific surface area is in the range of 3026 ~ 3277 m2 g-1, aperture is mainly distributed on 1.24 ~ 1.95 nm, micro-
Hole content is more than 95.18%, the porous carbon materials even aperture distribution that further instruction is prepared, and specific surface area is big, and micropore is rich
Rich the features such as
XRD detections are carried out to porous active carbon material load cobalt nanometer particle prepared by above-described embodiment, as a result shown unsupported
Porous active carbon material 2 θ be 29.8 ° and 42.1 ° occur two obvious Bao Feng, the peak of carbon, porous work can be attributed to
Property carbon load cobalt nanometer particle, 2 θ=43.5 ° and 50.3 ° appearance two cobalts wide and weak peak, illustrate load cobalt be amorphous
State, because cobalt is amorphous state, and cobalt is attached on carbon, so obvious weaken occurs in the peak of carbon.
FTIR spectrum detection is carried out to porous active carbon material load cobalt nanometer particle prepared by above-described embodiment,
As a result show, 3410 cm-1For the unsaturated stretching vibration of carbon, 1450 cm-1With 1400 cm-1The peak of position is that C=C double bonds are stretched
, there is peak intensity decrease, equally demonstrates XRD accuracy in contracting vibration after reaction.
Raman spectrum detection is carried out to porous active carbon material load cobalt nanometer particle prepared by above-described embodiment, as a result shown
Show, be 1340 and 1598 cm in wave number-1There is being low intensive D the G bands peak with peak and high intensity, the strength ratio of G bands and D bands
About 1.02, illustrate that the carbon material prepared has unformed shape and carbonization structure, degree of graphitization is preferable.
Nano-fibre supported cobalt silver alloy catalysis ammonia borane hydrolysis reaction method prepared by above-described embodiment, takes ammonia borine 50
Mg, adds the porous carbon load mg of cobalt nanometer particle 11.12 made, adds magnetic stirrer, then will fill the container of solution
In the water-bath for being placed in 25 DEG C, container is connected with water-filled gauge line；Hydrogen, the water essence of discharge are surveyed with draining weight method
Close balance measurement, first examines the air-tightness three times of pipeline, 10 mL deionized waters is then added into container, then allows magnetic stirring
Son is stirred always, it is seen that balance numeral terminates reaction not in increase.
Test result shows that porous active carbon Supported Co nano-particle catalyst completes in 10 min and puts hydrogen, hydrogen desorption capacity
105 mL are reached, close to the mL of theoretical value 118.It is many and same quality catalyst cobalt particle catalyst about completes to put hydrogen in 55 min
The mL min of the activated carbon loaded cobalt nanometer particle catalyst hydrogen discharging rate r in hole=865.2-1 g-1.Catalyst is efficiently catalyzed ammonia boron
Hydrogen is released in alkane hydrolysis.
Nano-fibre supported cobalt silver alloy catalysis ammonia borane hydrolysis reaction repeat performance prepared by above-described embodiment is surveyed
Examination：Nano-fibre supported cobalt silver alloy after having reacted takes 50 mg ammonia borines by distilling water washing, filtering, drying, plus
Enter the nano-fibre supported cobalt silver alloy of drying, then carry out reperformance test four times.Test result shows, after four circulations,
The hydrogen time is put for 45 min, hydrogen desorption capacity is 93.7 mL, keeps the 97% of circulation for the first time, cycle performance is good.
Therefore, porous carbon of the present invention loads cobalt nanometer particle for prior art, with advantages below：
First, the present invention is raw materials used commercially available, with low cost, is advantageously implemented large-scale standardized production；
2nd, it is that nitrogen source is decomposed in the condition of high temperature using semicarbazides in the present invention, advantageously forms more micropores, and can be
Different types of nitrogen-atoms is mixed on carbon wall, so as to form substantial amounts of micropore and big specific surface area on the surface of carbon.
3rd, its specific surface area of the carbon material of preparation is up to 3026 m2 g-1, aperture is mainly distributed on 1.24 and 1.95 nm,
Micro content is 95.18%.
4th, the carbon load cobalt-based nano-particle catalyst that prepared by this method, cobalt nanometer particle can be uniformly dispersed in carbon surrounding,
Cobalt nanometer particle, which can be stabilized on carbon material, does not reunite.
5th, as the application of properties material, the catalyst of synthesis can at room temperature can efficient catalytic ammonia borane hydrolysis
Put hydrogen, the mL min of hydrogen discharging rate r=865.2-1 g-1, hydrogen desorption capacity is close to theoretical value.
6th, material of the present invention can realize that recovery is reused.
Therefore, the present invention has broad application prospects in fields such as hydrogen manufacturing material, fuel cells.
Brief description of the drawings：
Fig. 1 is the scanning electron microscope (SEM) photograph of porous active carbon material；
Fig. 2 is the scanning electron microscope (SEM) photograph that porous active carbon loads cobalt nanometer particle；
Fig. 3 is the low temperature nitrogen adsorption isothermal curve of porous active carbon material；
Fig. 4 is the pore size distribution curve of porous active carbon material；
Fig. 5 is porous active carbon Supported Co nano-particle catalyst XRD analysis figure；
Fig. 6 is that porous active carbon loads cobalt nanometer particle FTIR spectrum figure；
Fig. 7 is that porous active carbon loads cobalt nanometer particle Raman spectrogram；
Fig. 8 is that hydrogen figure is released in porous active carbon load cobalt nanometer particle hydrolysis；
Fig. 9 is that porous active carbon loads cobalt nanometer particle cycle performance test chart.
Embodiment
The present invention is described in further detail by embodiment with reference to Figure of description to present invention, but is not pair
The limitation of the present invention.
Embodiment
The preparation method of porous active carbon material load cobalt nanometer particle material is as follows：
Step 1）Nitrogenous precursor is prepared, by 4 g glucose and 2 g semicarbazides, 60 mL deionized water stirring and dissolving is added
In deionized water after stirring and dissolving, 180 DEG C of reactions are then placed in reactor, product is filtered after reaction, washed, dries and obtains
Presoma；
Step 2）Loose structure carbon material is prepared, by step 1）Presoma and potassium hydroxide according to 1:2 mass ratio mixing, leaching
Bubble in deionized water, after drying, is put into tube furnace, under nitrogen protection, 2 h is calcined under 700 DEG C of temperature conditionss, carbon is obtained
Material, takes out the carbon material after calcining and is ground after cooling, after grinding, be put into the hydrochloric acid solution that concentration is 1 mol/L and soak
Bubble, by washing, filtering, drying, grinding, obtains loose structure carbon material；
Step 3）Cobalt nanometer particle is loaded, is 9 according to the mass ratio of cobalt element and carbon:1 ratio, takes the six of 1.265 g
Hydrated cobalt chloride and 35 mg above-mentioned steps 2）Obtained loose structure carbon material, cobalt chloride is made into 0.1 mol/L cobalt chloride
After solution, loose structure carbon material is added, it is under conditions of magnetic agitation, concentration is molten for 0.05 mol/L sodium borohydride
Drop is added in cobalt chloride solution, until after bubble-free generation, respectively being washed three times, being filtered under diminished pressure, Ran Hou with water and ethanol
Under the conditions of 80 DEG C, the h of vacuum drying 10 obtains porous active carbon material load cobalt nanometer particle material.
The carbon material supported front and rear Electronic Speculum that is scanned of porous active prepared to above-described embodiment is detected：
The carbon material supported preceding ESEM testing result of porous active is as shown in figure 1, ESEM result is shown, porous active carbon
Material aperture disperses more uniform；
Porous active carbon load cobalt nanometer particle ESEM result after porous active is carbon material supported is as shown in Fig. 2 scanning
Electronic Speculum result shows, many particles of porous supported on carbon surface, and these are evengranular to be dispersed in around hole, and pattern is good,
Homogeneity is good, and is supported on the cobalt nanometer particle on porous carbon and does not reunite.
Low temperature nitrogen isothermal adsorption table is carried out to porous active carbon material load cobalt nanometer particle prepared by above-described embodiment
Levy, as a result as shown in Figures 3 and 4, gas absorption amount has a rapid growth to pressure span in low phase, and this is attributed to micropore and filled out
Fill, it has higher specific surface area（3026 m2 g-1）, aperture is mainly distributed on 1.24 and 1.95 nm, and micro content is
95.18%, the porous carbon materials even aperture distribution that further instruction is prepared, specific surface area is big, the features such as micropore quantity is more
To above-described embodiment prepare porous active carbon material load cobalt nanometer particle carry out XRD detections, as a result as shown in figure 5,
Unsupported porous active carbon material is 29.8 ° and 42.1 ° appearance, two obvious Bao Feng in 2 θ, can be attributed to the peak of carbon,
Porous active carbon loads cobalt nanometer particle, at the wide and weak peak of two cobalts in 2 θ=43.5 ° and 50.3 ° of appearance, illustrates the cobalt of load
For amorphous state, because cobalt is amorphous state, and cobalt is attached on carbon, so obvious weaken occurs in the peak of carbon.
FTIR spectrum detection is carried out to porous active carbon material load cobalt nanometer particle prepared by above-described embodiment,
As a result as shown in fig. 6,3410 cm-1For the unsaturated stretching vibration of carbon, 1450 cm-1With 1400 cm-1The peak of position is C=C
Occur peak intensity decrease after double bond stretching vibration, reaction, equally demonstrate XRD accuracy.
Raman spectrum detection, such as Fig. 7 are carried out to porous active carbon material load cobalt nanometer particle prepared by above-described embodiment
It is shown, it is 1340 and 1598 cm in wave number-1There is being low intensive D the G bands peak with peak and high intensity, the intensity of G bands and D bands
Than being about 1.02, illustrate that the carbon material prepared has unformed shape and carbonization structure, degree of graphitization is preferable.
Nano-fibre supported cobalt silver alloy catalysis ammonia borane hydrolysis reaction method prepared by above-described embodiment, takes ammonia borine 50
Mg, adds the porous carbon load mg of cobalt nanometer particle 11.12 made, adds magnetic stirrer, then will fill the container of solution
In the water-bath for being placed in 25 DEG C, container is connected with water-filled gauge line；Hydrogen, the water essence of discharge are surveyed with draining weight method
Close balance measurement, first examines the air-tightness three times of pipeline, 10 mL deionized waters is then added into container, then allows magnetic stirring
Son is stirred always, it is seen that balance numeral terminates reaction not in increase.
Test result, as shown in figure 8, porous active carbon Supported Co nano-particle catalyst is completed in 10 min puts hydrogen,
Hydrogen desorption capacity reaches 105 mL, close to the mL of theoretical value 118.And same quality catalyst cobalt particle catalyst is about completed in 55 min
Put hydrogen, the mL min of porous active carbon Supported Co nano-particle catalyst hydrogen discharging rate r=865.2-1 g-1.Catalyst is efficiently urged
Change ammonia borane hydrolysis and release hydrogen.
Nano-fibre supported cobalt silver alloy catalysis ammonia borane hydrolysis reaction repeat performance prepared by above-described embodiment is surveyed
Examination：Nano-fibre supported cobalt silver alloy after having reacted takes 50 mg ammonia borines by distilling water washing, filtering, drying, plus
Enter the nano-fibre supported cobalt silver alloy of drying, then carry out reperformance test five times.Test result, is illustrated in figure 9 catalysis
Four design sketch are reused in agent, after being circulated through four times, put the hydrogen time for 45 min, and hydrogen desorption capacity is 93.7 mL, is kept for the first time
The 97% of circulation, cycle performance is good.
Claims (10)
1. a kind of porous active carbon material load cobalt nanometer particle material, it is characterised in that：By glucose as carbon source, one is added
Quantitative nitrogen-containing compound, then prepares porous carbon materials, soaking, drying, calcining, immersion, washing, mistake by hydro-thermal method
Filter, drying, grinding obtain loose structure carbon material, then load cobalt particle to carbon material by impregnating chemical reduction method, obtain
Porous active carbon material load cobalt nanometer particle material.
2. porous active carbon material load cobalt nanometer particle material according to claim 1, it is characterised in that：It compares table
The scope of area is 3026 ~ 3277 m2 g-1, micro content is more than 95.18%, and pore-size distribution is homogeneous, it is mainly distributed on 1.24 ~
1.95 nm。
3. the preparation method of porous active carbon material load cobalt nanometer particle material according to claim 1, it is characterised in that
Comprise the following steps：
Step 1）Nitrogenous precursor is prepared, by certain mass ratio, glucose is added in deionized water with nitrogen-containing compound and stirred
Dissolving is mixed, is then placed in reactor, is reacted at a certain temperature, product is filtered after reaction, wash, dried, obtains nitrogenous
Presoma；
Step 2）Loose structure carbon material is prepared, by step 1）Nitrogenous precursor and alkali inorganic substance it is mixed by certain mass ratio
Close, immersion in deionized water, after drying, is put into tube furnace, calcined under certain condition, obtain carbon material, taken out after cooling
Carbon material after calcining is ground, after grinding, is put into 1 mol/L hydrochloric acid solution and is soaked, by washing, filtering, dry,
Grinding, obtains loose structure carbon material；
Step 3）Load cobalt nanometer particle, certain mass ratio is met according to cobalt element and carbon, take cobalt chloride hexahydrate and
Above-mentioned steps 2）After obtained loose structure carbon material, the cobalt chloride solution that cobalt chloride is made into 0.1 mol/L, add porous
Structure carbon material, the ratio between the amount that certain material is met with cobalt chloride and sodium borohydride relation, by the boron that concentration is 0.05 mol/L
Sodium hydride solution under certain condition, is added drop-wise in cobalt chloride solution, after after bubble-free generation, washing, filtering, drying
To porous active carbon material load cobalt nanometer particle material.
4. preparation method according to claim 3, it is characterised in that：The step 1）Glucose and nitrogen-containing compound
Mass ratio is 1.0:（0.5~4.0）, reaction temperature is 180 DEG C.
5. preparation method according to claim 3, it is characterised in that：The step 1）Nitrogen-containing compound for semicarbazides and
One or two kinds of mixing of urea pyrimidine.
6. preparation method according to claim 3, it is characterised in that：The step 2）Nitrogenous precursor and basic mineral
The mass ratio of thing is 1.0:（1.0~4.0）, the alkali inorganic substance is inorganic base or alkaline, inorganic salts.
7. preparation method according to claim 3, it is characterised in that：The step 2）Calcining heat be 600 ~ 900 DEG C,
Calcination time is 2 ~ 8 hours.
8. preparation method according to claim 3, it is characterised in that：The step 3）Cobalt element and carbon matter
Measuring ratio is（5~9）:1, the concentration of the sodium borohydride solution of dropwise addition is 0.05 mol/L, the amount of the material of cobalt chloride and sodium borohydride
The ratio between be 1:2, dropwise addition condition be magnetic agitation under the conditions of be added dropwise, it is ensured that solution homogeneous reaction fully, prevent react it is too acute
Strong destruction material surface structure, washing methods is to use water and ethanol cyclic washing, and the method for filtering is decompression suction filtration, dry bar
Part is 80 DEG C of 5 ~ 10 h of vacuum drying.
9. porous active carbon material load cobalt nanometer particle material is put as catalysis ammonia borane hydrolysis according to claim 1
The application of hydrogen catalyst, it is characterised in that：Ammonia can be efficiently catalyzed at room temperature by being dispersed in the cobalt nanometer particle of carbon surface
Borane hydrolysis puts hydrogen, and 10 min complete to put hydrogen, and hydrogen discharging rate reaches 865.2 mL min-1 g-1。
10. porous active carbon material load cobalt nanometer particle material is put as catalysis ammonia borane hydrolysis according to claim 9
The application of hydrogen catalyst, it is characterised in that：Porous active carbon material load cobalt nanometer particle material can by filtering, washing,
Dry method is recycled, and is undergone after four circulations, is put the hydrogen time and is maintained at 10 ~ 45 min, hydrogen discharging rate is maintained at
208.2-865.2 mL min-1 g-1。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500377A (en) * | 2011-11-01 | 2012-06-20 | 南开大学 | Preparation method for binary transition metal catalyst for catalyzing hydrolysis of ammonia borane |
| CN103816906A (en) * | 2014-02-19 | 2014-05-28 | 南开大学 | Ni3B load carbon composite catalyst for hydrogen production by ammonia borane hydrolysis |
| CN105498823A (en) * | 2016-02-26 | 2016-04-20 | 南开大学 | Preparation method and application of nitrogen-doped porous carbon-loaded cobalt catalyst |
| CN106334566A (en) * | 2016-07-29 | 2017-01-18 | 湖北大学 | Core-shell structured supported carbon nanotube catalyst and preparation method thereof |
| CN106865540A (en) * | 2017-03-24 | 2017-06-20 | 桂林电子科技大学 | A kind of N doping loose structure carbon material and its preparation method and application |
-
2017
- 2017-06-22 CN CN201710480109.3A patent/CN107159214A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500377A (en) * | 2011-11-01 | 2012-06-20 | 南开大学 | Preparation method for binary transition metal catalyst for catalyzing hydrolysis of ammonia borane |
| CN103816906A (en) * | 2014-02-19 | 2014-05-28 | 南开大学 | Ni3B load carbon composite catalyst for hydrogen production by ammonia borane hydrolysis |
| CN105498823A (en) * | 2016-02-26 | 2016-04-20 | 南开大学 | Preparation method and application of nitrogen-doped porous carbon-loaded cobalt catalyst |
| CN106334566A (en) * | 2016-07-29 | 2017-01-18 | 湖北大学 | Core-shell structured supported carbon nanotube catalyst and preparation method thereof |
| CN106865540A (en) * | 2017-03-24 | 2017-06-20 | 桂林电子科技大学 | A kind of N doping loose structure carbon material and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| 何杰等: "《工业催化》", 31 July 2014, 中国矿业大学出版社 * |
| 王海霞: "多孔碳负载钴基纳米颗粒制备及催化氨硼烷水解制氢研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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