CN110116003B - Sodium borohydride hydrolysis hydrogen production composite coral-like morphology catalyst - Google Patents
Sodium borohydride hydrolysis hydrogen production composite coral-like morphology catalyst Download PDFInfo
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- CN110116003B CN110116003B CN201910395396.7A CN201910395396A CN110116003B CN 110116003 B CN110116003 B CN 110116003B CN 201910395396 A CN201910395396 A CN 201910395396A CN 110116003 B CN110116003 B CN 110116003B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000001257 hydrogen Substances 0.000 title claims abstract description 31
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 239000012279 sodium borohydride Substances 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 230000007062 hydrolysis Effects 0.000 title claims description 10
- 238000006460 hydrolysis reaction Methods 0.000 title claims description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 title abstract description 14
- 238000000197 pyrolysis Methods 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 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 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052796 boron Inorganic materials 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 6
- 238000013329 compounding Methods 0.000 claims abstract description 5
- 235000014653 Carica parviflora Nutrition 0.000 claims abstract description 3
- 241000243321 Cnidaria Species 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 150000001868 cobalt Chemical class 0.000 claims description 12
- 239000002105 nanoparticle Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- -1 sodium tetraphenylborate Chemical compound 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012266 salt solution 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
- 239000010413 mother solution Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000005406 washing 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 compound [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
- 230000010355 oscillation Effects 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000012716 precipitator Substances 0.000 claims 1
- 229910000428 cobalt oxide Inorganic materials 0.000 abstract description 9
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 2
- 241000894007 species Species 0.000 abstract description 2
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 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
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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
- B01J23/002—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
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- 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
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- 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 relates to the technical field of hydrogen preparation. A preparation method of a coral-like morphology composite catalyst for preparing hydrogen by hydrolyzing sodium borohydride adopts a hydrothermal method to prepare Co (OH)2Of Co (OH)2The CoO-Co with the appearance like coral is prepared by pyrolysis3O4And (3) compounding a catalyst. The invention not only successfully synthesizes the CoO-Co with the appearance similar to coral3O4The catalyst, but also the introduction of carbon and boron elements, may promote the interaction of cobalt oxide species with the support. The hydrogen is prepared by catalyzing sodium borohydride to hydrolyze by using the high-crystalline composite cobalt oxide, and the reaction activity of the catalyst is better than that of pure cobalt oxide and cobaltosic oxide.
Description
Technical Field
The invention relates to CoO-Co for preparing hydrogen by hydrolyzing sodium borohydride3O4A composite coral-like morphology catalyst belongs to the technical field of hydrogen preparation.
Background
The massive combustion of disposable fossil fuel causes global energy crisis and resource shortage, and the problems of environmental pollution and climate change caused by the global energy crisis and resource shortage, and the development of renewable green energy sources becomes the final way for human development. Hydrogen energy is used as a new high-efficiency and clean energy source, not only has a large storage capacity and a rich source, but also has very high energy density, and becomes an important bridge for connecting fossil fuel and renewable energy. However, technical problems in the storage and production of hydrogen gas have prevented its marketability. The development and utilization of a range of hydrogen storage materials is of increasing interest to scholars. Sodium borohydride is a promising chemical hydrogen storage material due to its high hydrogen storage content, good stability, no pollution of the hydrolysis product, and the like. It reacts as follows:
the efficiency of the hydrolysis hydrogen production depends on the selection of the catalyst. The catalysts currently used in this reaction are mainly classified into two types: a non-supported metal catalyst, such as Pt, Ru, CoB and the like, but because of high cost of noble metal, non-noble metal is easy to agglomerate and difficult to industrially produce; another class is supported metal catalysts, such as: chinese patent CN 102950009 discloses a method for preparing CoB/Ag-TiO by chemical plating2And Mo and W modified CoB/Ag-TiO2The catalyst has high catalytic activity for the hydrogen production reaction by sodium borohydride hydrolysis, shows good reuse capacity, has very high stability in air, and is very suitable for the requirement of actual hydrogen production. Chinese patent CN107159227 discloses a preparation method of a supported cobalt-based catalyst. The catalyst is prepared by loading cobalt, tungsten and boron on the surface of foamed nickel by a single pulse electrodeposition method. The preparation method of the catalyst is simple and convenient, has low cost, high hydrogen production efficiency, compact distribution and stable performance, can be used for large-scale production, and can provide a chemical field hydrogen production technology for unmanned aerial vehicles, bionic fish and other portable fuel cell power supplies and outdoor hydrogen balloons. Chinese patent CN107413360 discloses a method for preparing carbon fiber cloth load by electroplatingCoMoP, which has high catalytic activity. Both of these catalysts use cobalt in a metallic state as an active component, and cobalt oxide is rarely used as an active component. The metal oxide is used as an active component, so that the cobalt can be reduced by utilizing the strong reducibility of sodium borohydride, and the cobalt nanoparticles can be prevented from being agglomerated in the reaction process to a certain extent. Unlike the previous reports that a simple metal substance or a compound is used as an effective active component for hydrogen production, the patent provides a catalyst for effectively catalyzing sodium borohydride to produce hydrogen by compounding metal oxides.
Disclosure of Invention
The invention aims to provide CoO-Co for preparing hydrogen by hydrolyzing sodium borohydride3O4The composite coral-like morphology catalyst utilizes metal oxide and coral-like structure with high specific surface area, thereby improving catalytic activity,
the technical scheme adopted by the invention is as follows: coral-like CoO-Co for preparing hydrogen by hydrolyzing sodium borohydride3O4The composite catalyst is prepared into Co (OH) by a hydrothermal method2Of Co (OH)2The CoO-Co with the appearance like coral is prepared by pyrolysis3O4And (3) compounding a catalyst.
As a preferred mode: hydrothermal preparation of Co (OH)2The preparation method of the nano-particles comprises the following steps:
(1) weighing 1-10 g of soluble metal cobalt salt, and dissolving the soluble metal cobalt salt in 30ml of methanol to prepare a cobalt salt solution;
(2) weighing 1-10 g of sodium tetraphenylborate, and dissolving in 30ml of methanol to prepare a mother solution;
(3) under ultrasonic oscillation, cobalt salt solution is poured into the mother solution, the mother solution is oscillated for 1 to 2 hours at room temperature and then is put into a hydrothermal synthesis kettle to react for 3 to 5 hours at the temperature of 100 plus materials and 200 ℃;
(4) cooling to room temperature, centrifuging, collecting the obtained precipitate, and washing with methanol and ethanol for several times;
(5) drying the obtained precipitate in a vacuum oven at 50-100 ℃ to obtain Co (OH)2Nanoparticles.
As a preferred mode: the soluble metal cobalt salt is one of cobalt nitrate and cobalt chloride; the alkaline precipitant is sodium tetraphenylborate.
As a preferred mode: co (OH)2The nanometer particles are pyrolyzed to prepare the CoO-Co with the appearance similar to coral3O4The preparation method of the composite catalyst comprises the steps of weighing 1-2 g of Co (OH) prepared by adopting a hydrothermal method2The nano particles are put in a tube furnace and pyrolyzed by introducing helium, wherein the pyrolysis temperature is 600-800 ℃, the time is 1-3h, and the heating rate is 1-5 ℃/min, so that the CoO-Co with the coral-like morphology is obtained3O4And (3) compounding a catalyst.
As a preferred mode: in an atmosphere of helium.
As a preferred mode: the carbon element and the boron element are doped simultaneously, namely sodium tetraphenylborate provides a carbon source and a boron source.
As a preferred mode: the pyrolysis temperature is 600 ℃, and the pyrolysis time is 3 h.
As a preferred mode: pyrolysis in air.
The beneficial effects of the invention are: (1) adopts a hydrothermal method and a one-step pyrolysis method to synthesize and prepare the coral-like shape CoO-Co3O4The catalyst has simple process and easy control. (2) The preparation method not only successfully synthesizes the CoO-Co with the coral-like morphology3O4The catalyst, but also the introduction of carbon and boron elements, may promote the interaction of cobalt oxide species with the support. (3) The hydrogen is prepared by catalyzing sodium borohydride to hydrolyze by using the high-crystalline composite cobalt oxide, and the reaction activity of the catalyst is better than that of pure cobalt oxide and cobaltosic oxide.
Drawings
FIG. 1 shows Co (OH) before pyrolysis in example 1 of the present invention2Transmission electron microscopy images of the nanoparticles;
FIG. 2 shows Co (OH) before pyrolysis in example 1 of the present invention2XRD pattern of the nanoparticles;
FIG. 3 shows the pyrolyzed CoO-Co complex in example 1 of the present invention3O4Transmission electron micrographs of the catalyst;
FIG. 4 shows the pyrolyzed composite CoO-Co in example 1 of the present invention3O4XRD pattern of the catalyst;
FIG. 5 XRD pattern of the CoO catalyst after pyrolysis in example 2 of the invention;
FIG. 6 pyrolyzed Co in example 3 of the invention3O4XRD pattern of the catalyst.
Detailed Description
Example 1
Preparing a catalyst: weighing 1.092g Co (NO)3)2Adding 6H2O into 30ml of methanol for full dissolution to obtain a cobalt salt solution; weighing 0.856g of sodium tetraphenylborate, and dissolving in 30ml of methanol to obtain mother liquor; the cobalt salt solution was poured into the mother liquor under ultrasonic shaking and shaken at room temperature for 20 minutes. The reaction solution was transferred to a 100ml polytetrafluoroethylene hydrothermal synthesis kettle and maintained at 120 ℃ for 4 hours. Cooling to room temperature, centrifuging to collect precipitate, washing with methanol and ethanol for several times, and drying at 60 deg.C for 24 hr in vacuum oven to obtain Co (OH)2Nanoparticles. Then 0.5g of Co (OH) is taken2The nano particles are transferred into a tube furnace to be roasted for 2 hours under the condition of introducing helium at 600 ℃ to obtain the composite CoO-Co3O4And (3) a nano catalyst.
Transmission Electron microscopy of Metal nanoparticles before pyrolysis referring to FIG. 1, composite CoO-Co after pyrolysis3O4The catalyst is shown in figure 2.
Evaluation of catalytic Performance: 10mg of catalyst was weighed into a round bottom flask, which was immersed in a temperature controlled water bath on a magnetic stirrer. Then, 800mgNaOH and 100mgNaBH were added4Dissolved in an aqueous solution (10 ml). The reaction started after the mixed solution was injected into the round-bottom flask by syringe. The volume of hydrogen was calculated using a conventional water displacement method. The hydrogen generation rate (rB) was calculated according to the following formula:
rB=V(ml) ·t-1(min)·mcat -1(g)
the catalyst used in each circulation is washed by deionized water for several times and dried for use.
The results of example 1 are shown in tables 1 and 2.
TABLE 1 composite CoO-Co3O4Results of hydrogen production by sodium borohydride hydrolysis catalyzed by nano catalyst
TABLE 2 composite CoO-Co3O4Circulation result of hydrogen production by hydrolyzing sodium borohydride under catalysis of nano catalyst
Example 2
The catalyst was prepared according to example 1, the pyrolysis time was 3 hours, and the other conditions were the same, and the evaluation results are shown in Table 3.
TABLE 3 CoO catalyst results for hydrogen production by hydrolysis of sodium borohydride
Example 3
Catalyst preparation reference example 1, pyrolysis without helium, the rest of the conditions. The evaluation conditions were as described in example 1, and the evaluation results are shown in Table 4.
TABLE 4 Co3O4The result of hydrogen production by hydrolysis of sodium borohydride under catalysis of catalyst
The comparison shows that the reaction activity of the hydrogen prepared by catalyzing the hydrolysis of sodium borohydride by using the high-crystalline composite cobalt oxide is better than that of pure cobalt oxide and cobaltosic oxide.
Claims (2)
1. Coral-like CoO-Co for preparing hydrogen by hydrolyzing sodium borohydride3O4A composite catalyst characterized by: hydrothermal preparation of Co (OH)2Prepared from Co (OH)2The CoO-Co with the appearance similar to that of coral is prepared by pyrolysis3O4A composite catalyst;
hydrothermal method to obtain Co (OH)2The preparation method of the nano-particles comprises the following steps:
(1) weighing 1-10 g of soluble metal cobalt salt, and dissolving the soluble metal cobalt salt in 30mL of methanol to prepare a cobalt salt solution;
(2) weighing 1-10 g of sodium tetraphenylborate, and dissolving in 30mL of methanol to prepare a mother solution;
(3) under ultrasonic oscillation, cobalt salt solution is poured into the mother solution; oscillating for 1-2 hours at room temperature, and putting the mixture into a hydro-thermal synthesis kettle;
reacting for 3-5h at 100-200 ℃;
(4) cooling to room temperature, centrifuging, collecting the obtained precipitate, and washing with methanol and ethanol for several times;
(5) drying the obtained precipitate in a vacuum oven at 50-100 ℃ to obtain Co (OH)2Nanoparticles;
the soluble metal cobalt salt is one of cobalt nitrate and cobalt chloride; the alkaline precipitator is sodium tetraphenylborate; the carbon element and the boron element are simultaneously doped, namely sodium tetraphenylborate provides a carbon source and a boron source to enter CoO-Co3O4A composite catalyst;
Co(OH)2the nanometer particles are pyrolyzed to prepare the CoO-Co with the appearance similar to coral3O4The preparation method of the composite catalyst comprises the following steps: weighing 1-2 g, and preparing Co (OH) by a hydrothermal method2Placing the nano particles in a tubular furnace, introducing helium for pyrolysis at the pyrolysis temperature of 600-800 ℃, the time of 2h and the heating rate of 1-5 ℃/min to obtain the CoO-Co with the appearance similar to coral3O4And (3) compounding a catalyst.
2. The coral-like shaped CoO-Co of claim 1 for hydrogen production by hydrolysis of sodium borohydride3O4A composite catalyst characterized by: the pyrolysis temperature was 600 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1067091A2 (en) * | 1999-07-05 | 2001-01-10 | Seijirau Suda | Hydrogen-generating agent and method for generation of hydrogen using the same |
| CN101193703A (en) * | 2005-06-29 | 2008-06-04 | 三星工程株式会社 | Metal oxide catalyst for hydrogen generation and method of producing the same |
| CN103691480A (en) * | 2014-01-15 | 2014-04-02 | 辽宁石油化工大学 | Preparation technology of catalyst used for preparing hydrogen by hydrolyzing sodium borohydride |
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