CN109205681A - A kind of three-dimensional hierarchical structure metal oxide and preparation method thereof - Google Patents
A kind of three-dimensional hierarchical structure metal oxide and preparation method thereof Download PDFInfo
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- CN109205681A CN109205681A CN201811059549.2A CN201811059549A CN109205681A CN 109205681 A CN109205681 A CN 109205681A CN 201811059549 A CN201811059549 A CN 201811059549A CN 109205681 A CN109205681 A CN 109205681A
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- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 33
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002086 nanomaterial Substances 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 12
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000012545 processing Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 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
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 1
- 238000010306 acid treatment Methods 0.000 abstract description 11
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000018044 dehydration Effects 0.000 abstract description 2
- 238000006297 dehydration reaction Methods 0.000 abstract description 2
- 238000013459 approach Methods 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
- 239000012535 impurity Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 23
- 239000003054 catalyst Substances 0.000 description 15
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229960003284 iron Drugs 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- Y02E60/13—Energy storage using capacitors
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
It is 6~12h of impregnation at 100 DEG C by metal hydroxide precursors ultrasonic disperse in the concentrated sulfuric acid the present invention provides a kind of three-dimensional hierarchical structure metal oxide and preparation method thereof；Then the sample after processing is placed in tube furnace, 500 DEG C of calcining 2h, obtain metal oxide nano-material in air.The present invention utilizes dense H2SO4Strong oxidizing property and dehydration property, in dipping process oxidation remove undesired impurities simultaneously be dehydrated so that inside substance formed enriches staggered pore structure, so that the metal oxide with bigger serface be prepared.Compared with untreated metal hydroxides, the metal hydroxides through dense sulfuric acid treatment is having bigger specific surface area, richer pore structure after calcining, and the preparation for three-dimensional hierarchical structure metal oxide nano-material provides new approaches.
Description
Technical field
The present invention relates to field of material technology more particularly to a kind of three-dimensional hierarchical structure metal oxide and its preparation sides
Method.
Background technique
Metal oxide has many peculiar properties, has a wide range of applications, is in material supply section in recent decades
Study frontier.Metal oxide under nanoscale, physics and chemical property all can great changes will take place.Many institute's weeks
Know, the physics of nano material, chemical property are not only related with its size dimension, also with its surface texture, exposed crystal face, dimension etc.
It is closely related, so can control any one of these parameters can effectively regulate and control their property.In order to make this
The metal oxide nano-materials with good characteristic are used widely a bit, rationally design simple, economic, effective, environment friend
Good preparation method has a very important significance to realize the control to nano material size, pattern, structure.So far,
The technical method for preparing metal oxide nano-material has very much, such as calcining, thermal decomposition, ion exchange, dehydration etc..
Metal oxide nano-material is because its size is small, large specific surface area, activated centre are more, and unique crystal structure
With special surface characteristic (high surface and surface energy), system reaction efficiency is improved as catalyst.Therefore, construct nanometer
Material catalyst and its application in catalytic field are widely paid close attention to.In addition, the mankind are studying new and effective energy
Conversion and storage element in, put into many energy, at present most study mainly include sodium-ion battery, lithium ion battery,
Zinc-air battery, supercapacitor etc..Electrode material is the core composition of battery or capacitor, storage mode, the capacitor of charge
Performance, cycle life are determined by the property of electrode material.Wherein metal oxide is a kind of important electrode material.Metal oxidation
Object has the advantages that a variety of oxidation state, programmable special construction, high theoretical specific capacitance, hypotoxicity and low cost and is recognized
To be one of most potential electrode material.
Summary of the invention
The purpose of the invention is to provide a kind of preparation of novel three-dimensional hierarchical structure metal oxide nano-material
Method.
It is a further aim of the invention providing a kind of with three-dimensional hierarchical structure metal oxide nano-material preparation
Electrode catalyst of fuel cell, capacitor electrode material and heavy-metal adsorption material.
A kind of preparation method of three-dimensional hierarchical structure metal oxide, comprising the following steps:
(1) metal salt and sodium hydroxide are added to the water with certain molar ratio, stirring is uniformly mixed it, in room temperature
4~16h of lower reaction；After the reaction was completed, it filters, it is dry, obtain metal hydroxide precursors；
(2) metal hydroxides is placed in the concentrated sulfuric acid, 6~12h is impregnated at 100 DEG C, then by the sample after processing
Product are placed in tube furnace, are calcined in air, and metal oxide nano-material is obtained.
Further, the preparation method of three-dimensional hierarchical structure metal oxide as described above, the metal salt include: chlorination
Iron, nickel acetate, cobalt acetate or cobalt nitrate.
Further, the preparation method of three-dimensional hierarchical structure metal oxide as described above, metal hydroxide in step (1)
The drying condition of object precursor are as follows: 60 DEG C of vacuum drying are for 24 hours.
Further, the preparation method of three-dimensional hierarchical structure metal oxide as described above, metal salt and sodium hydroxide
Molar ratio is 1:3.
Further, the preparation method of three-dimensional hierarchical structure metal oxide as described above, the middle condition calcined of step (2)
For 500 DEG C of calcining 2h.
The three-dimensional hierarchical structure metal oxide that any the method as above is prepared.
The utility model has the advantages that
1, the oxide of formation is calcined again using dense sulfuric acid treatment hydroxide than oxygen that dinectly bruning hydroxide obtains
Compound has more holes and bigger specific surface area.
2, dense sulfuric acid treatment hydroxide is conducive to construct the oxide of three-dimensional hierarchical structure.
3, the recyclable recycling of the concentrated sulfuric acid in experiment, and experimental technique is simple, is lost small.
Detailed description of the invention
Fig. 1 is obtained Fe after dense sulfuric acid treatment2O3SEM figure；
Fig. 2 is dinectly bruning Fe (OH)3The Fe of formation2O3With dense sulfuric acid treatment Fe (OH)3The Fe obtained afterwards2O3XRD diagram；
Fig. 3 is 20%wtPt/C and Fe2O3The Linear Circulation volt-ampere test chart of-Pt/C in 0.1M KOH solution；
Fig. 4 is 20%wtPt/C and Fe2O3The cyclic voltammetry figure of-Pt/C in 0.1M KOH solution.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, the technical solution below in the present invention carries out clear
Chu is fully described by, it is clear that described embodiments are some of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
The present invention develops a kind of novel synthetic method, introduces dense sulfuric acid treatment hydroxide precursor.Pass through the concentrated sulfuric acid
It is affected when handling metal hydroxides to its pattern and structure, to realize three-dimensional hierarchical structure metal oxide nano
The preparation of material.The present invention calcines to obtain the metal oxygen of three-dimensional hierarchical structure using dense sulfuric acid treatment metal hydroxide precursors again
Compound.The oxide has more pore structure, enhances catalytic activity while increasing specific surface area.Electrocatalytic oxidation also
Former, capacitor and heavy metal adsorption etc. have preferable application prospect.
The preparation method of three-dimensional hierarchical structure metal oxide nano-material of the invention, comprises the following steps that:
(1) metal salt and sodium hydroxide are added to the water with certain molar ratio, stirring is uniformly mixed it, in room temperature
4~16h of lower reaction；After the reaction was completed, it filters, it is dry, obtain metal hydroxide precursors；
(2) metal hydroxide precursors are placed in the concentrated sulfuric acid, 6~12h is impregnated at 100 DEG C, after then handling
Sample be placed in tube furnace, 500 DEG C of calcining 2h, obtain metal oxide nano-material in air.
Material of the invention is with dense sulfuric acid treatment Fe (OH)3Precursor, then handle to obtain three-dimensional classification knot with high-temperature calcination
The Fe of structure2O3.Fig. 1 is three-dimensional hierarchical structure Fe2O3Scanning electron microscope (SEM) figure of nano material.From figure 1 it appears that material
In three-dimensional netted distribution.
Fig. 2 is three-dimensional hierarchical structure Fe prepared by the present invention2O3The XRD diagram of nano material.From figure 2 it can be seen that directly
It calcines Fe (OH)3The Fe of formation2O3XRD appearance is more sharp, and peak width is narrower, illustrates that the material of dinectly bruning agglomerates into bulk, and
The sample that dense sulfuric acid treatment is crossed, XRD appearance is opposite to weaken, and peak width is wider, this also shows that form three-dimensional hierarchical structure mutual with Fig. 1
It should demonstrate,prove.
Three-dimensional hierarchical structure Fe of the present invention2O3The preparation method of nanostructured materials catalyst is by FeCl3With NaOH with 1:3's
Molar ratio is added to the water, and stirring is uniformly mixed it, reacts 4h at room temperature；After the reaction was completed, it filters, it is dry, obtain Fe
(OH)3Precursor；Iron hydroxide is placed in the concentrated sulfuric acid, impregnates 12h at 100 DEG C, the sample after processing is placed in tube furnace
In the middle, 500 DEG C of calcining 2h in air, obtain Fe2O3。
The three-dimensional hierarchical structure Fe of above-mentioned preparation2O3The performance test of nanostructured materials catalyst: by Fe2O3With 20%wtPt/
The catalyst that C is mixed to get has carried out the test of Linear Circulation volt-ampere in 0.1M KOH solution, and with individual 20%
WtPt/C is compared.Fig. 3 is 20%wtPt/C and Fe2O3The cyclic voltammetry figure of-Pt/C in 0.1M KOH solution.
Fe as seen from Figure 32O3For-Pt/C catalyst in linear cyclic voltammetry, hydrogen reduction take-off potential compares 20%wtPt/C
It is opposite to be advanced by.Illustrate that the iron oxide material for the three-dimensional hierarchical structure that the present invention is formed has certain contribution to catalytic oxidation-reduction.
Three-dimensional hierarchical structure Fe2O3Nanostructured materials catalyst tests hydrogen reduction catalytic durability: by Fe2O3With 20%
The catalyst that wtPt/C is mixed to get has carried out cyclic voltammetry in 0.1M KOH solution, and with individual 20%
WtPt/C is compared.Fig. 4 is 20%wtPt/C and Fe2O3The cyclic voltammetry figure of-Pt/C in 0.1M KOH solution.
Fe as seen from Figure 42O3- Pt/C in cyclic voltammetry, the dehydrogenation zone areas of 1000 circles reduce it is seldom, and 20%
The dehydrogenation zone area that wtPt/C catalyst 1000 encloses has very big reduction, illustrates the oxidation for the three-dimensional hierarchical structure that the present invention is formed
Iron material is conducive to the raising of 20%wtPt/C stability.
In conclusion metal oxide catalyst stability of the present invention is good, active high, long service life.In hydrogen reduction
Good catalytic activity is shown in journey, can be used for fuel-cell catalyst.
Embodiment 1
(1) three-dimensional hierarchical structure Fe2O3The preparation of nano material
In 100ml round-bottomed flask, 1mmol FeCl is added3With the H of 30ml2O is stirred evenly；0.12g hydroxide is added
Sodium continues to stir, in room temperature reaction 4h: after the reaction was completed, filtering, washing, 70 DEG C of dry 10h obtain Fe (OH)3Precursor.
By Fe (OH)3It is placed in the concentrated sulfuric acid, 12h is impregnated at 100 DEG C, the sample after dense sulfuric acid treatment is then placed in pipe
In formula furnace, 500 DEG C of calcining 2h, finally obtain the Fe of three-dimensional hierarchical structure in air2O3。
(2) preparation of 20%wtPt/C catalyst is mixed
By 60mg 20%wtPt/C and 15mgFe2O3Ball milling is uniformly mixed it, so that in the catalyst, Fe2O3With
The mass ratio of 20%wtPt/C is 1:4.
Fe2O3- Pt/C catalyst take-off potential ratio 20%wtPt/C in hydrogen reduction performance test is advanced by.In addition, three-dimensional
The iron oxide of hierarchical structure also has certain effect to heavy metal adsorption.
Embodiment 2
(1) preparation of three-dimensional hierarchical structure NiO nano material
By 2mmol Ni (CH3COO it) 2 is added in 60mL water, stirring forms green transparent solution and go to being completely dissolved
In 100mL reaction kettle, 200 DEG C of reaction 6h are centrifugated, and washing, 70 DEG C of dry 10h obtain Ni (OH)2Precursor.
By Ni (OH)2Precursor is placed in the concentrated sulfuric acid, and 12h is impregnated at 100 DEG C, then sets the sample after dense sulfuric acid treatment
In tube furnace, 500 DEG C of calcining 2h, finally obtain three-dimensional netted NiO in air.
(2) preparation of capacitor electrode material
By 8mg NiO, 1mg acetylene black, sample preparation after 1 microlitre of PTFE mixing, then sample is pressed in nickel foam, electricity is made
Pole.
It is tested in 6M KOH, the specific capacitance of NiO electrode reaches 315F/g under the current density of 2A/g.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (6)
1. a kind of preparation method of three-dimensional hierarchical structure metal oxide, which comprises the following steps:
(1) metal salt and sodium hydroxide are added to the water with certain molar ratio, stirring is uniformly mixed it, at room temperature instead
Answer 4~16h；After the reaction was completed, it filters, it is dry, obtain metal hydroxide precursors；
(2) metal hydroxides is placed in the concentrated sulfuric acid, 6~12h is impregnated at 100 DEG C, then sets the sample after processing
It in tube furnace, is calcined in air, obtains metal oxide nano-material.
2. the preparation method of three-dimensional hierarchical structure metal oxide as described in claim 1, it is characterised in that: the metal salt packet
It includes: iron chloride, nickel acetate, cobalt acetate or cobalt nitrate.
3. the preparation method of three-dimensional hierarchical structure metal oxide as described in claim 1, it is characterised in that: golden in step (1)
Belong to the drying condition of hydroxide precursor are as follows: 60 DEG C of vacuum drying are for 24 hours.
4. the preparation method of three-dimensional hierarchical structure metal oxide as described in claim 1, it is characterised in that: metal salt and hydrogen-oxygen
The molar ratio for changing sodium is 1:3.
5. the preparation method of three-dimensional hierarchical structure metal oxide as described in claim 1, it is characterised in that: step is forged in (2)
The condition of burning is 500 DEG C of calcining 2h.
6. a kind of three-dimensional hierarchical structure metal oxide being prepared using any the method for claim 1-5.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101264942A (en) * | 2008-04-22 | 2008-09-17 | 吉林市金泰化工有限公司 | Method and device for producing high-grade nickel oxide |
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