CN110116003A - Preparing hydrogen by sodium borohydride hydrolysis complex class coral pattern catalyst - Google Patents
Preparing hydrogen by sodium borohydride hydrolysis complex class coral pattern catalyst Download PDFInfo
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- CN110116003A CN110116003A CN201910395396.7A CN201910395396A CN110116003A CN 110116003 A CN110116003 A CN 110116003A CN 201910395396 A CN201910395396 A CN 201910395396A CN 110116003 A CN110116003 A CN 110116003A
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- Prior art keywords
- coo
- sodium borohydride
- preparing hydrogen
- catalyst
- borohydride hydrolysis
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- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000001257 hydrogen Substances 0.000 title claims abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 36
- 235000014653 Carica parviflora Nutrition 0.000 title claims abstract description 24
- 241000243321 Cnidaria Species 0.000 title claims abstract description 24
- 229910000033 sodium borohydride Inorganic materials 0.000 title claims abstract description 24
- 239000012279 sodium borohydride Substances 0.000 title claims abstract description 24
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 20
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052796 boron Inorganic materials 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000002105 nanoparticle Substances 0.000 claims description 11
- 150000001868 cobalt Chemical class 0.000 claims description 10
- 238000000197 pyrolysis Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 239000012452 mother liquor Substances 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract description 11
- 239000010941 cobalt Substances 0.000 abstract description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 11
- 229910000428 cobalt oxide Inorganic materials 0.000 abstract description 6
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 230000009257 reactivity Effects 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 2
- 241000894007 species Species 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000011943 nanocatalyst Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- IUNLYRFGCQIVIB-UHFFFAOYSA-N [Na].[B].C1=CC=CC=C1 Chemical compound [Na].[B].C1=CC=CC=C1 IUNLYRFGCQIVIB-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910021649 silver-doped titanium dioxide Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
-
- B01J35/50—
-
- 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
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C01B3/065—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 from a hydride
-
- 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 present invention relates to technical field of hydrogen preparation.A kind of preparation method of the composite catalyst of the class coral pattern of preparing hydrogen by sodium borohydride hydrolysis gas, is made Co (OH) using hydro-thermal method2, by Co (OH)2The pyrogenically prepared CoO-Co as coral pattern3O4Composite catalyst.The present invention not only successfully synthesizes the CoO-Co of class coral pattern3O4Catalyst, but also carbon and boron element are introduced, this may promote the interaction of cobalt oxidation species and carrier.It is catalyzed preparing hydrogen by sodium borohydride hydrolysis using highly crystalline compound cobalt/cobalt oxide, the simple cobalt oxide of reactivity ratio, cobaltosic oxide will be got well.
Description
Technical field
The present invention relates to one kind to be used for preparing hydrogen by sodium borohydride hydrolysis CoO-Co3O4Complex class coral pattern catalyst, belongs to hydrogen
Gas preparation technical field.
Background technique
A large amount of burn of disposable fossil fuel causes global energy crisis and shortage of resources, and therefore and caused by
The problems such as environmental pollution and climate change, the final outlet of human development will be become by developing novel, reproducible green energy resource.Hydrogen
New energy of the energy as high effect cleaning, not only storage capacity is more, abundance, but also has very high energy density, becomes company
Connect the important bridge of fossil fuel and renewable energy.However, the technical problem in the storage and preparation of hydrogen hinders its city
Fieldization application.A series of development and utilization of hydrogen storage materials gradually causes the concern of scholar.Sodium borohydride is due to hydrogen storage content
High, the features such as stability is good, hydrolysate is pollution-free, becomes promising chemical hydrogen storage material.Its reaction is as follows:
The efficiency of its hydrolytic hydrogen production all relies on the selection of catalyst.Current catalyst used in the reaction is broadly divided into two classes:
One kind is non-load type metal catalyst, such as Pt, Ru, CoB, but since noble metal is at high cost, base metal is easy to difficulty of reuniting
To carry out industrialized production；Another kind of is load type metal catalyst, such as: Chinese patent CN 102950009 discloses a kind of use
Chemically plating is for CoB/Ag-TiO2And the CoB/Ag-TiO that Mo, W are modified2Catalyst, the catalyst hydrolyze sodium borohydride
Producing hydrogen reaction has high catalytic activity, and shows good reuse ability, also very high in the stability of air, non-
Often it is suitble to the practical requirement for producing hydrogen.Chinese patent CN107159227 discloses a kind of preparation method of load type cobalt-base catalyst.
The catalyst is carried on foam nickel surface by single pulse electrodpositing method by cobalt, tungsten and boron and is prepared.The preparation of the catalyst
Method is simple and convenient, at low cost, hydrogen generation efficiency is high, distribution is fine and close, performance is stable, can be mass produced, and can be nothing
Man-machine, Biomimetic Fish and other portable fuel battery power supplys and outdoor hydrogen balloon provide chemistry live hydrogen producing technology.Chinese patent
CN107413360 disclose it is a kind of prepare carbon cloth load C oMoP with galvanoplastic, which has high catalytic activity.
These two types of catalyst are all made of the cobalt of metallic state as active component, and the oxide of cobalt is rarely employed as active component.Benefit
Use metal oxide as active component, the strong reducing property that both can use sodium borohydride is reduced into cobalt, can also be in certain journey
Cobalt nano-particle is avoided to reunite during the reaction on degree.The metal simple-substance or compound of report different from the past are as system
The effective active component of hydrogen, this patent propose a kind of catalyst of compound effective catalysis sodium borohydride hydrogen manufacturing of metal oxide.
Summary of the invention
The object of the present invention is to provide a kind of CoO-Co for preparing hydrogen by sodium borohydride hydrolysis3O4Complex class coral pattern is urged
Agent, using the class coral structures of metal oxide and high-specific surface area, so that catalytic activity is improved,
The technical scheme adopted by the invention is that: a kind of CoO-Co of the class coral pattern of preparing hydrogen by sodium borohydride hydrolysis gas3O4It is multiple
Catalyst is closed, Co (OH) is made using hydro-thermal method2, by Co (OH)2The pyrogenically prepared CoO-Co as coral pattern3O4Composite catalyzing
Agent.
As a kind of preferred embodiment: Co (OH) is made in hydro-thermal method2Nanometer grain preparation method includes the following steps:
(1) 1 ~ 10g soluble metal cobalt salt is weighed, is dissolved in 30ml methanol, cobalt salt solution is made；
(2) it weighs 1 ~ 10g tetraphenylboron sodium to be dissolved in 30ml methanol, mother liquor is made；
(3) under sonic oscillation, pour into cobalt salt solution into mother liquor, shaken at room temperature 1-2 hours, be put into hydrothermal synthesis kettle in
100-200 DEG C of reaction 3-5h；
(4) it is cooled to room temperature, gained precipitating is collected by centrifugation, and respectively washed for several times with methanol, ethyl alcohol；
(5) precipitating that will be obtained is dried to obtain Co (OH) in vacuum drying oven at 50 ~ 100 DEG C2Nanoparticle.
As a kind of preferred embodiment: soluble metal cobalt salt is cobalt nitrate, a kind of in cobalt chloride；Alkaline precipitating agent is four benzene
Boron sodium.
As a kind of preferred embodiment: Co (OH)2The CoO- Co of the pyrogenically prepared class coral pattern of nano particle3O4Composite catalyzing
Agent, preparation method are to weigh 1 ~ 2 g Co (OH) is made using hydro-thermal method2Nanoparticle is placed in helium injection gas in tube furnace and is pyrolyzed,
Its pyrolysis temperature is 600-800 DEG C, time 1-3h, and heating rate is 1-5 DEG C/min, obtains the CoO- of class coral pattern
Co3O4Composite catalyst.
As a kind of preferred embodiment: being carried out in the atmosphere of helium.
As a kind of preferred embodiment: carbon and boron element adulterate simultaneously, i.e., tetraphenylboron sodium provides carbon source and boron source.
As a kind of preferred embodiment: pyrolysis temperature is 600 DEG C, pyrolysis time 3h.
As a kind of preferred embodiment: being pyrolyzed in air.
The beneficial effects of the present invention are: (1) is synthetically prepared the CoO- of class coral pattern using hydro-thermal method and a step pyrolysismethod
Co3O4Catalyst, process is simple, is easy to control.(2) preparation method not only successfully synthesizes the CoO- of class coral pattern
Co3O4Catalyst, but also carbon and boron element are introduced, this may promote the interaction of cobalt oxidation species and carrier.(3) sharp
Preparing hydrogen by sodium borohydride hydrolysis, the simple cobalt oxide of reactivity ratio, four oxidations three are catalyzed with highly crystalline compound cobalt/cobalt oxide
Cobalt will be got well.
Detailed description of the invention
Fig. 1 is Co (OH) before being pyrolyzed in the embodiment of the present invention 12The transmission electron microscope picture of nanoparticle；
Fig. 2 is Co (OH) before being pyrolyzed in the embodiment of the present invention 12The XRD diagram of nanoparticle；
Fig. 3 is the compound CoO- Co after being pyrolyzed in the embodiment of the present invention 13O4The transmission electron microscope picture of catalyst；
Fig. 4 is the compound CoO-Co after being pyrolyzed in the embodiment of the present invention 13O4The XRD diagram of catalyst；
The XRD diagram of CoO catalyst after being pyrolyzed in Fig. 5 embodiment of the present invention 2；
Co after being pyrolyzed in Fig. 6 embodiment of the present invention 33O4The XRD diagram of catalyst.
Specific embodiment
Embodiment 1
Catalyst preparation: 1.092g Co (NO is weighed3)26H2O, which is added in 30ml methanol, sufficiently to be dissolved, and it is molten to obtain cobalt salt
Liquid；It weighs 0.856g tetraphenylboron sodium to be dissolved in 30ml methanol, obtains mother liquor；Cobalt salt solution is poured into mother liquor under under sonic oscillation
In, it vibrates 20 minutes at room temperature.Reaction solution is transferred in 100ml polytetrafluoroethylene (PTFE) hydrothermal synthesis kettle, 120 DEG C, 4 are kept
Hour.It is cooled to room temperature, sediment is collected by centrifugation, is respectively washed for several times through methanol, ethyl alcohol, 60 DEG C of dryings 24 are small in vacuum drying oven
When obtain Co (OH)2Nanoparticle.0.5gCo (OH) is taken later2Nanoparticle is gone in tube furnace under the conditions of 600 DEG C of helium injection gas
Roasting 2 hours, obtains compound CoO-Co3O4Nanocatalyst.
Compound CoO-Co of the transmission electron microscope picture of metal nanoparticle referring to Fig. 1, after pyrolysis before being pyrolyzed3O4Catalyst referring to
Fig. 2.
Catalytic performance test: weighing 10mg catalyst and set in a round bottom flask, and flask is immersed in temperature controlled water-bath,
Water-bath is placed on magnetic stirring apparatus.Then, by 800mgNaOH and 100mgNaBH4It is dissolved in aqueous solution (10ml).It mixes molten
After liquid is injected into round-bottomed flask by syringe, reaction starts.The volume of hydrogen is calculated using traditional drainage.According to
Lower formula calculates the generating rate (rB) of hydrogen:
rB=V(ml) ·t-1(min)·mcat -1(g)
Catalyst used in recycling every time will be washed with deionized water for several times, and drying uses.
The result of embodiment 1 is as shown in table 1,2.
The compound CoO-Co of table 13O4The result of nanocatalyst catalysis preparing hydrogen by sodium borohydride hydrolysis
The compound CoO-Co of table 23O4The circulation result of nanocatalyst catalysis preparing hydrogen by sodium borohydride hydrolysis
Embodiment 2
Catalyst preparation is referring to embodiment 1, and pyrolysis time 3h, remaining condition is identical, and appraisal result is shown in Table 3.
The result of 3 CoO catalyst preparing hydrogen by sodium borohydride hydrolysis of table
Embodiment 3
Catalyst preparation reference implementation example 1, when pyrolysis obstructed helium, remaining condition is identical.Examination condition is examined referring to embodiment 1
It comments and the results are shown in Table 4.
4 Co of table3O4The result of catalyst preparing hydrogen by sodium borohydride hydrolysis
By comparison as can be seen that being catalyzed preparing hydrogen by sodium borohydride hydrolysis, reactivity using highly crystalline compound cobalt/cobalt oxide
It is got well than simple cobalt oxide, cobaltosic oxide.
Claims (7)
1. a kind of CoO-Co of the class coral pattern of preparing hydrogen by sodium borohydride hydrolysis gas3O4Composite catalyst, it is characterised in that: use
Co (OH) is made in hydro-thermal method2, by Co (OH)2The CoO-Co of pyrogenically prepared class coral pattern3O4Composite catalyst.
2. a kind of CoO-Co of the class coral pattern of preparing hydrogen by sodium borohydride hydrolysis gas as described in claim 13O4Composite catalyzing
Agent, it is characterised in that: Co (OH) is made in hydro-thermal method2Nanometer grain preparation method includes the following steps:
(1) 1 ~ 10g soluble metal cobalt salt is weighed, is dissolved in 30ml methanol, cobalt salt solution is made；
(2) it weighs 1 ~ 10g tetraphenylboron sodium to be dissolved in 30ml methanol, mother liquor is made；
(3) under sonic oscillation, cobalt salt solution is poured into mother liquor；It shaken at room temperature 1-2 hours, is put into hydrothermal synthesis kettle；
100-200 DEG C, react 3-5h；
(4) it is cooled to room temperature, gained precipitating is collected by centrifugation, and respectively washed for several times with methanol, ethyl alcohol；
(5) precipitating that will be obtained is dried to obtain Co (OH) in vacuum drying oven at 50 ~ 100 DEG C2Nanoparticle.
3. a kind of CoO-Co of the class coral pattern of preparing hydrogen by sodium borohydride hydrolysis gas as claimed in claim 1 or 23O4It is compound to urge
Agent, it is characterised in that: soluble metal cobalt salt is cobalt nitrate, a kind of in cobalt chloride；Alkaline precipitating agent is tetraphenylboron sodium.
4. a kind of CoO-Co of the class coral pattern of preparing hydrogen by sodium borohydride hydrolysis gas as described in claim 13O4Composite catalyzing
Agent, it is characterised in that: Co (OH)2The CoO-Co of the pyrogenically prepared class coral pattern of nano particle3O4Composite catalyst, preparation side
Method is to weigh 1 ~ 2 g Co (OH) is made using hydro-thermal method2Nanoparticle is placed in helium injection gas in tube furnace and is pyrolyzed, and pyrolysis temperature is
600-800 DEG C, time 1-3h, heating rate is 1-5 DEG C/min, obtains the CoO-Co of class coral pattern3O4Composite catalyst.
5. a kind of CoO-Co of the class coral pattern of preparing hydrogen by sodium borohydride hydrolysis gas as claimed in claim 43O4Composite catalyzing
Agent, it is characterised in that: carbon and boron element adulterate simultaneously, i.e., tetraphenylboron sodium provides carbon source and boron source enters CoO-Co3O4It is compound
Catalyst.
6. a kind of CoO-Co of the class coral pattern of preparing hydrogen by sodium borohydride hydrolysis gas as claimed in claim 43O4Composite catalyzing
Agent, it is characterised in that: pyrolysis temperature is 600 DEG C, pyrolysis time 3h.
7. a kind of CoO-Co of the class coral pattern of preparing hydrogen by sodium borohydride hydrolysis gas as claimed in claim 43O4Composite catalyzing
Agent, it is characterised in that: be pyrolyzed in air.
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