CN106976905A - The sub- titanium oxide and its controllable method for preparing of core shell structure - Google Patents
The sub- titanium oxide and its controllable method for preparing of core shell structure Download PDFInfo
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- CN106976905A CN106976905A CN201710131497.4A CN201710131497A CN106976905A CN 106976905 A CN106976905 A CN 106976905A CN 201710131497 A CN201710131497 A CN 201710131497A CN 106976905 A CN106976905 A CN 106976905A
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- titanium oxide
- shell structure
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- active metal
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 239000011258 core-shell material Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title abstract description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 138
- 239000002245 particle Substances 0.000 claims abstract description 13
- 239000004408 titanium dioxide Substances 0.000 claims description 52
- 239000002184 metal Substances 0.000 claims description 51
- 239000003708 ampul Substances 0.000 claims description 47
- 239000010453 quartz Substances 0.000 claims description 47
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 47
- 229910052751 metal Inorganic materials 0.000 claims description 43
- 239000010936 titanium Substances 0.000 claims description 33
- 238000002360 preparation method Methods 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 16
- 238000009413 insulation Methods 0.000 claims description 15
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims description 13
- 150000004706 metal oxides Chemical class 0.000 claims description 13
- 230000009467 reduction Effects 0.000 claims description 13
- 238000005530 etching Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 7
- 229910009848 Ti4O7 Inorganic materials 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 6
- 229910009973 Ti2O3 Inorganic materials 0.000 claims description 5
- 229910009815 Ti3O5 Inorganic materials 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- GQUJEMVIKWQAEH-UHFFFAOYSA-N titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 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 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 13
- 238000005253 cladding Methods 0.000 abstract description 9
- 230000005611 electricity Effects 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000004020 conductor Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 description 33
- 239000000843 powder Substances 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 238000000967 suction filtration Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000003647 oxidation Effects 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 15
- 238000001816 cooling Methods 0.000 description 13
- 238000006722 reduction reaction Methods 0.000 description 13
- 230000001603 reducing effect Effects 0.000 description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 9
- 239000011812 mixed powder Substances 0.000 description 9
- 239000004570 mortar (masonry) Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000006479 redox reaction Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000001239 high-resolution electron microscopy Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000004832 voltammetry Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910010420 TinO2n-1 Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/043—Titanium sub-oxides
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
-
- 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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- 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
- C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
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- 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
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- C01—INORGANIC CHEMISTRY
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- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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Abstract
The present invention relates to the sub- titanium oxide and its controllable method for preparing of core shell structure, the sub- titanium oxide has core shell structure, and its Surface coating has sub- titanium oxide amorphous layer.Central Asia titanium oxide of the present invention has the core shell structure of the sub- titanium oxide amorphous layer cladding in unique surface, it not only has the unique electricity, the optical property that have uniqueness of sub- titanium oxide, excellent heat endurance and the electrical conductivity of superelevation, also there is the good performances such as particle diameter is small, specific surface area is high, microscopic structural units are controllable, it can be used for catalyst and catalyst carrier, high-effective conductive material and prepare efficient rechargeable battery etc..
Description
Technical field
The invention belongs to materials science field, and in particular to a kind of sub- oxidation of surface amorphous layers coated core-shell structure
Titanium and its method for controllable preparation.
Background technology
Sub- titanium oxide is a series of general designation (Ti that non-stoichiometry aoxidize titaniumnO2n-1), with high conductivity (electrical conductivity
1500S/cm, far above graphite material), high chemical stability (strong alkali-acid resistance) and electrochemical stability are (stable in the aqueous solution
Voltage window is more than 3.0V) many advantages, such as.In catalyst/catalyst carrier, the field such as fuel cell, flow battery has good
Good application prospect.
Nineteen fifty-nine, Magn é li have carried out the research of crystal structure to this kind of material first, therefore sub- titanium oxide is also known as Magn é
Li phase oxidation titaniums.Sub- titanium oxide has the crystal structure based on rutile titanium dioxide, can regard a shared TiO as2Eight
The network structure of face body, the network shares all edges (side altogether) on a surface.In TinO2n-1In, each n-th layer has individual oxygen
Atom lacks to form shear surface.On shear surface, octahedral two-dimentional chain becomes face and shared.Its unique crystal structure assigns it
There is high conductivity and high chemical stability simultaneously.
Sub- titanium oxide can be by heating TiO under an inert atmosphere2Obtained with Titanium reaction, can also be by under high temperature
Use reducing agent such as hydrogen reducing TiO2Obtain, such as more than 1200 DEG C at a high temperature of use hydrogen reducing TiO2Prepare sub- titanium oxide.
But these preparation methods are directed to pyroreaction (being higher than 1000 DEG C), there are costly equipment investment, power consumption height, process conditions multiple
Miscellaneous the shortcomings of, it is difficult to realize industrialization, limit the application of both approaches.Pyroreaction causes reaction violent, uncontrollable, difficult
To realize the structure regulating of sub- titanium oxide.
In addition, in preparation process, sub- titanium oxide is highly prone to reaction condition, and (reactant composition, reducing agent are in the feed
Decentralization, particle size, temperature curve be processing time etc.) influence, it is difficult to synthesize pure phase.Therefore, sub- titanium oxide is restricted
One subject matter of application is exactly the sub- titanium oxide pure phase of preparation of low cost.
Present hydrogen reduces TiO2Obtained sub- titanium oxide only has weaker electro catalytic activity in itself, is typically due to its excellent
Different stability and high conductivity as catalyst carrier.Whether it is possible to realize the preparation of sub- titanium oxide under cryogenic
And its surface texture regulation and control, make it have excellent electrocatalysis characteristicIt is still not controllable on low cost under cryogenic conditions at present
Prepare document report and the patent application of the core shell structure regulation and control of sub- titanium oxide pure phase method and its surface amorphous layers cladding.
The content of the invention
In view of the above-mentioned problems, it is an object of the invention to provide a kind of Asia of the core shell structure coated with surface amorphous layers
Titanium oxide and its can the sub- titanium oxide pure phase of inexpensive controllable preparation under cryogenic preparation method.
On the one hand, the invention provides a kind of sub- titanium oxide with core shell structure, the sub- titanium oxide has nucleocapsid knot
Structure, its Surface coating has sub- titanium oxide amorphous layer.
Central Asia titanium oxide of the present invention has the core shell structure of the sub- titanium oxide amorphous layer cladding in unique surface, and it not only has
Sub- the titanium oxide unique electricity, optical property, excellent heat endurance and the electrical conductivity of superelevation that have uniqueness, also with particle diameter
The good performance such as small, specific surface area is high, microscopic structural units are controllable, can be used for catalyst and catalyst carrier, efficiently leads
Electric material and prepare efficient rechargeable battery etc..In addition, Central Asia titania surface of the present invention has one layer of sub- titanium oxide amorphous layer,
The presence of amorphous layer can be obviously improved the electrocatalysis characteristic of sub- titanium oxide.
It is preferred that the particle diameter of the sub- titanium oxide is 5nm~5 μm, the thickness of sub- titanium oxide amorphous layer is 1~3nm, preferably
For 1~2nm, amorphous layer thickness is too thin, then electrocatalysis characteristic lifting is not notable, and amorphous layer blocked up (being more than 2nm) then causes material
Electric conductivity is reduced, and also reduces electrocatalysis characteristic.
It is preferred that the chemical formula of the sub- titanium oxide is TiO, Ti2O3、Ti3O5、Ti4O7Or the sub- oxygen of other oxygen-containing vacancies
Change titanium.
On the other hand, present invention also offers a kind of system of the above-mentioned sub- titanium oxide for stating surface amorphous layers coated core-shell structure
Preparation Method, using titanium dioxide as presoma, is placed in vacuum-tight quartz ampoule by reducing agent of active metal after uniform mixing,
Prior to being incubated for the first stipulated time at 100~500 DEG C of the first temperature, provided then at insulation second at 550~800 DEG C of second temperature
Time, reduce titanium dioxide to obtain sub- titanium oxide using active metal.
The present invention is placed in vacuum tightness after being well mixed using titanium dioxide as the active metal of presoma and different meterings ratio
Quartz ampoule in be heated to being heated to second temperature insulation after the first temperature stipulated time as defined in the time, utilize active gold
Category reduction titanium dioxide is so as to obtain sub- titanium oxide.In the present invention, under negative pressure (vacuum), using active metal is heated, make gold
Category and titanium dioxide reaction, reduce titanium dioxide, so as to obtain sub- titanium oxide.The present invention uses two heat treatment holding temperatures：
First temperature is incubated the stipulated time under lower temperature (100~500 DEG C) and realizes being sufficiently mixed for active metal and titanium dioxide
Uniformly, it can make it that reaction is more uniform, it is ensured that the sub- titanium oxide pure phase of generation；Second temperature is at higher temperature (550~800 DEG C)
The lower insulation stipulated time, which will provide enough thermodynamical reaction, can cause reduction reaction to carry out completely, it is final realize sub- titanium oxide can
Control is standby.Wherein, because the ordered arrangement of atom is destroyed in active metal during titanium dioxide is reduced, so as to form amorphous
Layer.The method of the invention can be handled directly titanium dioxide powder on a large scale, obtain the sub- oxidation of high catalytic activity
Titanium valve body.
It is preferred that controlling the mol ratio of the active metal and titanium dioxide in (1.6~0.2)：It is variable to adjust in 1
State O/Ti ratios in sub- titanium oxide.
It is preferred that the active metal is at least one of lithium, magnesium, calcium, potassium, strontium, barium, Na, Al, Zn, Fe, Sn, Pb,
Preferably at least one of lithium, magnesium, calcium, potassium, strontium, barium.The present invention mainly considers metal reaction activity, selected active
Metal reaction activity is all higher than tradition H.
It is preferred that prior to being incubated 2~48 hours at 100~500 DEG C of the first temperature, at 550~800 DEG C of second temperature
Insulation 2~48 hours.
It is preferred that be first warming up to the first temperature with 1~5 DEG C/min of speed, then with 1~5 DEG C/min of speed from the
One temperature is warming up to second temperature.
It is preferred that first temperature is 400~500 DEG C.
It is preferred that the second temperature is 550~700 DEG C.
It is preferred that the vacuum of the quartz ampoule is less than 30Pa, preferably smaller than 1Pa.
It is preferred that the sub- titanium oxide prepared is put into etching liquid, unreacted active metal and generation are removed
Active metal oxide.
Also, it is preferred that the etching liquid is that hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, hydrogen peroxide, sodium hydroxide are water-soluble
At least one of liquid and potassium hydroxide aqueous solution.
Compared with conventional high-temperature hydrogen reduction method, low for equipment requirements, short preparation period of the invention can be in relative low temperature
Under the conditions of (550 DEG C) obtain the titanium dioxide powder of controllable crystalline phase, controllable crystal, high catalytic performance.The present invention is using active gold
Category reduction titanium dioxide prepares the sub- titania meterial with unique surface amorphous layers coated core-shell structure, not only with sub- oxygen
Change the unique electricity of titanium, optical property, excellent heat endurance and the electrical conductivity of superelevation, also with particle diameter is small, specific surface area is high,
The good performance of the controllable grade of microscopic structural units, can be used for catalyst and catalyst carrier, and high-effective conductive material and preparation are high
Imitate rechargeable battery etc..
Brief description of the drawings
Fig. 1 shows the XRD photos of the sub- titanium oxide of the method synthesis of the present invention, and wherein a is that TiO prepared by embodiment 2 is pure
Phase, b is Ti prepared by embodiment 12O3Pure phase；C is Ti prepared by embodiment 33O5Pure phase, d is Ti prepared by embodiment 44O7It is pure
Phase；
Fig. 2 shows the transmission electron microscope picture of sub- titanium oxide prepared by embodiments of the invention 1, can be clearly observable from picture
The cladding of surface amorphous layers, shows its unique core shell structure；
Fig. 3 a show the high resolution electron microscopy picture of sub- titanium oxide prepared by embodiments of the invention 1；
Fig. 3 b show the corresponding lattice diffraction of the high resolution electron microscopy picture (Fig. 3 a) of the sub- titanium oxide of the method synthesis of the present invention
Spot；
Fig. 4 shows that the sub- titanium dioxide powder of the method synthesis of the present invention is surveyed as the performance of the catalyst of electrocatalytic oxidation reduction reaction
Attempt, a is different sub- titanium oxide (wherein Ti under the same scan speed that linear voltammetry is measured2O3Prepared by embodiment 1)
Electrocatalytic oxidation reducing property, b is Ti prepared by embodiment 44O7Electrocatalytic oxidation reproducibility under rotating disk electrode (r.d.e) different rotating speeds
Energy；
Fig. 5 shows that the sub- titanium dioxide powder and common high-temperature hydrogen reduction of the preparation of the embodiment of the present invention 4 prepare sub- oxidation
Titanium powder as electrocatalytic oxidation reduction reaction catalyst performance comparison diagram.
Embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
The present invention provides a kind of sub- titanium oxide with surface amorphous layers coated core-shell structure and its can be under cryogenic
The preparation method of the sub- titanium oxide pure phase of inexpensive controllable preparation.Titanium dioxide is reduced using active metal, in relative low temperature condition
The controllable preparation of the sub- titanium oxide of (550 DEG C) realizations.The sub- titanium oxide prepared under this cryogenic conditions has unique surface amorphous
The core shell structure of layer cladding, with excellent electrocatalytic oxidation reducing property.
In the present invention, as long as titanium dioxide can be transformed into Rutile Type, titanium dioxide by suitable method
The microscopic pattern of (rutile titanium dioxide) includes but is not limited to the different morphologies such as ball, rod, band, pipe and irregular polygon.
In the present invention, the particle diameter of titanium dioxide can be 5nm~5um, preferably 5nm~50nm.By regulating and controlling titanium dioxide powder
The diameter of body, can regulate and control the diameter of the sub- titanium oxide of gained, and then can influence electrocatalytic oxidation reducing property.In the present invention, two
The preferred nano particle of titanium oxide powder.Therefore, the sub- titanium oxide finally given is nano particle.
Titanium dioxide can also be prepared voluntarily purchased from commercialization.In an example, nanometer ultrafine titania
Preparation method include：Titanium tetrachloride is hydrolyzed in frozen water, received by controlling reaction condition to regulate and control titanium dioxide
The particle diameter of rice grain, specific control method can use techniques known.
The active metal of titanium dioxide and different meterings ratio is well mixed.Described active metal amount can be according to waiting to make
Standby sub- titanium oxide is suitably selected.The mol ratio of the active metal and titanium dioxide may generally be (1.6~0.22)：1.Can
O/Ti ratios in the sub- titanium oxide are adjusted by controlling the mol ratio of active metal and titanium dioxide.When the active metal and
The mol ratio of titanium dioxide is (0.42-0.65):When 1, gained Asia titanium oxide chemical formula is Ti2O3.When the active metal and two
The mol ratio of titanium oxide is (0.9-1.6):When 1, gained Asia titanium oxide chemical formula is TiO.When the active metal and titanium dioxide
The mol ratio of titanium is (0.31-0.35):When 1, gained Asia titanium oxide chemical formula is Ti3O5.When the active metal and titanium dioxide
Mol ratio be (0.23-0.28):When 1, gained Asia titanium oxide chemical formula is Ti4O7.In the present invention, active metal is included but not
It is limited at least one of lithium, magnesium, calcium, potassium, strontium, barium, Na, Al, Zn, Fe, Sn, Pb etc..
Preparation of the stoichiometry of active metal and titanium dioxide to sub- titanium oxide pure phase has a major impact.Stoichiometry mistake
The high or too low preparation for being unfavorable for sub- titanium oxide pure phase, can cause the mixed phase for generating sub- titanium oxide.
Powder after will be well mixed is placed in vacuum-tight quartz ampoule.As an example, powder is added into one end
The quartz ampoule of opening, then vacuumizes tube sealing.In the present invention, the control of vacuum (negative pressure) in quartz ampoule is excellent less than 30Pa
Choosing is less than 1Pa.
Vacuum can have a major impact to the preparation of sub- titanium oxide pure phase.Vacuum is inadequate, remaining air in quartz ampoule
In oxygen will participate in reacting, the reaction that is deviates anticipated chemical metering ratio, can cause the mixed phase for generating sub- titanium oxide.
After being placed in vacuum-tight quartz ampoule, prior to being incubated at 100~500 DEG C of the first temperature (the first heat treatment temperature)
First stipulated time, it was incubated for the second stipulated time at 550~800 DEG C of second temperature (the second heat treatment temperature), makes active
Metal reduction titanium dioxide is so as to obtain sub- titanium oxide.As an example, after vacuum sealing tube, sample is heat-treated, made
Active metal reduces titanium dioxide, and Asia titanium oxide is made.The heat treatment is preferably to be carried out in two steps, i.e., advanced to exercise to obtain powder
More mixed uniformly first heat treatment, then carry out the second heat treatment of active metal reduction titanium dioxide.First heat treatment temperature
Degree can be 100~500 DEG C, preferably 400~500 DEG C.The heat treatment time (the first stipulated time) of first heat treatment temperature can be 2
~48 hours, preferably 4~8 hours.Second heat treatment temperature can be 550~800 DEG C, preferably 550~700 DEG C.Second heat treatment
The heat treatment time (the second stipulated time) of temperature can be 2~48 hours, preferably 4~8 hours.Wherein first with 1~5 DEG C/min
Speed be warming up to the first temperature.Second temperature is warming up to from the first temperature with 1~5 DEG C/min of speed again.
Cooling obtains sample after heat treatment, and cooling includes but is not limited to quenching, air cooling, furnace cooling.
Etching method can be used by removing the metal oxide of the metal not reacted completely and reaction generation, after will cooling down
Material is put into etching liquid, removes metal and metal oxide.The etching liquid include but is not limited to hydrochloric acid, sulfuric acid, nitric acid,
At least one of phosphoric acid, hydrofluoric acid, hydrogen peroxide, sodium hydrate aqueous solution and potassium hydroxide aqueous solution.The temperature of etching and when
Between can according to the metal reasonable selection used so that metal and reaction produce metal oxide remove completely.Show at one
In example, etching temperature is room temperature, and etch period can be 0.5~48 hour.The sub- titanium oxide property of generation is sufficiently stable, acid and alkali-resistance
Corrosion.Therefore it will not be etched in above-mentioned etching process Central Asia titanium oxide.
The present invention only needs to common tube sealing equipment and extensive system inexpensive under sub- titanium oxide cryogenic conditions can be achieved
It is standby.
Sub- titanium oxide prepared in accordance with the present invention has the core shell structure of unique Surface coating amorphous layer.The sub- oxidation
Titanium has core shell structure, and its Surface coating has sub- titanium oxide amorphous layer.The particle diameter of the sub- titanium oxide can be 5nm~5 μm.Wherein
The thickness of sub- titanium oxide amorphous layer can be 1~3nm.
Generally speaking, the present invention is placed in after being well mixed using titanium dioxide as the active metal of presoma and different meterings ratio
It is heated to being heated to the second temperature insulation defined time after the first temperature stipulated time in vacuum-tight quartz ampoule, makes
Active metal reduction titanium dioxide is so as to obtain sub- titanium oxide.The present invention can also be warm by the amount and heat treatment that adjust active metal
Degree, realizes controllable reduction, prepares TiO, Ti2O3、Ti3O5、Ti4O7And the sub- titanium oxide of other anoxics.The present invention is mainly
The amount of active metal is adjusted to realize controllable reduction, but if second temperature is too low, then kinetics is too slow, reaction can not
Carry out completely.As for the first temperature primarily to reaction is more uniform.The sub- Titanium dioxide nanoparticle of gained has unique
The core shell structure of surface amorphous layers cladding.Sub- titanium oxide prepared by the present invention not only has the unique electricity for having uniqueness of sub- titanium oxide
, optical property, excellent heat endurance and the electrical conductivity of superelevation, also with particle diameter is small, specific surface area is high, microscopic structural units
The good performance of controllable grade, can be used for catalyst and catalyst carrier, high-effective conductive material and prepare efficient rechargeable battery
Deng.
Sub- titanium oxide prepared by the present invention has excellent electrocatalytic oxidation reducing property after tested.Therefore the present invention is prepared
The sub- titanium oxide of core shell structure that there are surface amorphous layers to coat had broad application prospects in energy storage and catalytic field.
In the example of the present invention, the flow of the sub- titanium oxide of the core shell structure coated with surface amorphous layers is prepared
It is as follows：
(1) using titanium dioxide as presoma, using active metal as reducing agent, wherein, respectively with different molar percent metals：
TiO2Weigh the ground and mixed in mortar uniform；
(2) well mixed powder is added in the quartz ampoule of one end open, connects vavuum pump, vacuum is less than 30Pa, and
Quartz ampoule openend is melted using oxyhydrogen flame rifle afterwards and sealed；
(3) vacuum-tight quartz ampoule is placed in Muffle furnace, 1 DEG C/min heating rate is raised to the first temperature from 30 DEG C, protected
The warm stipulated time, and second temperature is raised to from the first temperature with 1 DEG C/min heating rate, it is cold with stove after the insulation stipulated time
But；
(4) vacuum tightness quartz ampoule is opened, gained black powder and water are mixed and stirred 0.5~48 hour, part is removed incomplete
The metal of reaction；
(5) it will be mixed 0.5~48 hour in the watery hydrochloric acid that 1M is added after the solution suction filtration after stirring, plus deionized water washing
Suction filtration is to filtrate in neutrality, and the sub- titanium oxide for obtaining surface amorphous layers coated core-shell structure is taken out in 60 DEG C of drying of low temperature, different
Stoichiometric proportion correspond respectively to different sub- titanium oxide pure phases；
(6) gained sample is assembled into electrode.
Referring to Fig. 1, it shows the XRD photos for the sub- titanium oxide that the method for the present invention is prepared；Therefrom visible different bars
The sub- titanium oxide prepared under part corresponds to TiO phases, Ti respectively2O3Phase, Ti3O5Phase, Ti4O7Phase, embodies the controllable of this method
Standby property；
Referring to Fig. 2, it shows the transmission electron microscope picture of the sub- titanium oxide of the method synthesis of the present invention, can clearly seen from picture
The cladding of surface amorphous layers is observed, shows its unique core shell structure, sub- titan oxide particles size is 50nm or so；
Referring to Fig. 3 a and Fig. 3 b, its show the sub- titanium oxide of the method synthesis of the present invention high resolution electron microscopy picture (Fig. 3 a) and its
Corresponding lattice diffraction spot (Fig. 3 b), the really sub- titanium oxide pure phase therefrom proved and the nucleocapsid coated with surface amorphous layers
Structure.
Referring to Fig. 4, it shows sub- titanium dioxide powder the urging as electrocatalytic oxidation reduction reaction of the method synthesis of the present invention
A figures are the electro-catalysis of different sub- titanium oxide under the same scan speed that linear voltammetry is measured in the performance test figure of agent, Fig. 4
B figures are Ti in hydrogen reduction performance, Fig. 44O7Electrocatalytic oxidation reducing property under rotating disk electrode (r.d.e) different rotating speeds, it can be determined that
Obtained Ti4O7Show most excellent electrocatalytic oxidation reducing property；
Referring to Fig. 5, it shows that the sub- titanium dioxide powder and common high-temperature hydrogen reduction of the method synthesis of the present invention are prepared
Sub- titanium dioxide powder as electrocatalytic oxidation reduction reaction catalyst performance comparison diagram, it can be determined that the present invention obtain have table
The sub- titanium oxide of the core shell structure of face amorphous layer cladding shows small overpotential, and big saturation current shows its excellent electricity
Catalytic oxidation-reduction performance.
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright the above is made belong to protection scope of the present invention.Following examples are specific
Technological parameter etc. is also only that an example in OK range, i.e. those skilled in the art can be done properly by this paper explanation
In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.If without specified otherwise, institute in embodiments of the invention
It is rutile titanium dioxide to be related to titanium dioxide (presoma).
Embodiment 1
(1) using titanium dioxide as presoma, using magnesium metal as reducing agent, wherein, with molar percent magnesium metal：TiO2=
55% weighing ground and mixed in mortar is uniform；
(2) well mixed powder is added in the quartz ampoule of one end open, connects vavuum pump, vacuum is less than 1Pa, then
Quartz ampoule openend is melted using oxyhydrogen flame rifle and sealed；
(3) vacuum-tight quartz ampoule is placed in Muffle furnace, 1 DEG C/min heating rate is raised to 450 DEG C, insulation 6 from 30 DEG C
Hour, and 550 DEG C are raised to from 450 DEG C with 1 DEG C/min heating rate, furnace cooling after being incubated 6 hours；
(4) vacuum tightness quartz ampoule is opened, gained black powder and water are mixed and stirred 6 hours, removes what part was not reacted completely
Metal；
(5) it will be mixed 6 hours in the watery hydrochloric acid that 1M is added after the solution suction filtration after stirring, plus deionized water washing suction filtration is extremely
Filtrate takes out the Ti for obtaining surface amorphous layers coated core-shell structure in neutrality, 60 DEG C of drying of low temperature2O3。
Embodiment 2
(1) using titanium dioxide as presoma, using magnesium metal as reducing agent, wherein, with molar percent magnesium metal：TiO2=
105% weighing ground and mixed in mortar is uniform；
(2) well mixed powder is added in the quartz ampoule of one end open, connects vavuum pump, vacuum is less than 1Pa, then
Quartz ampoule openend is melted using oxyhydrogen flame rifle and sealed；
(3) vacuum-tight quartz ampoule is placed in Muffle furnace, 1 DEG C/min heating rate is raised to 450 DEG C, insulation 6 from 30 DEG C
Hour, and 550 DEG C are raised to from 450 DEG C with 1 DEG C/min heating rate, furnace cooling after being incubated 6 hours；
(4) vacuum tightness quartz ampoule is opened, gained black powder and water are mixed and stirred 6 hours, removes what part was not reacted completely
Metal；
(5) it will be mixed 6 hours in the watery hydrochloric acid that 1M is added after the solution suction filtration after stirring, plus deionized water washing suction filtration is extremely
Filtrate takes out the TiO for obtaining surface amorphous layers coated core-shell structure in neutrality, 60 DEG C of drying of low temperature.
Embodiment 3
(1) using titanium dioxide as presoma, using magnesium metal as reducing agent, wherein, with molar percent magnesium metal：TiO2=
34% weighing ground and mixed in mortar is uniform；
(2) well mixed powder is added in the quartz ampoule of one end open, connects vavuum pump, vacuum is less than 1Pa, then
Quartz ampoule openend is melted using oxyhydrogen flame rifle and sealed；
(3) vacuum-tight quartz ampoule is placed in Muffle furnace, 1 DEG C/min heating rate is raised to 450 DEG C, insulation 6 from 30 DEG C
Hour, and 550 DEG C are raised to from 450 DEG C with 1 DEG C/min heating rate, furnace cooling after being incubated 6 hours；
(4) vacuum tightness quartz ampoule is opened, gained black powder and water are mixed and stirred 6 hours, removes what part was not reacted completely
Metal；
(5) it will be mixed 6 hours in the watery hydrochloric acid that 1M is added after the solution suction filtration after stirring, plus deionized water washing suction filtration is extremely
Filtrate takes out the Ti for obtaining surface amorphous layers coated core-shell structure in neutrality, 60 DEG C of drying of low temperature3O5。
Embodiment 4
(1) using titanium dioxide as presoma, using magnesium metal as reducing agent, wherein, with molar percent magnesium metal：TiO2=
26% weighing ground and mixed in mortar is uniform；
(2) well mixed powder is added in the quartz ampoule of one end open, connects vavuum pump, vacuum is less than 1Pa, then
Quartz ampoule openend is melted using oxyhydrogen flame rifle and sealed；
(3) vacuum-tight quartz ampoule is placed in Muffle furnace, 1 DEG C/min heating rate is raised to 450 DEG C, insulation 6 from 30 DEG C
Hour, and 550 DEG C are raised to from 450 DEG C with 1 DEG C/min heating rate, furnace cooling after being incubated 6 hours；
(4) vacuum tightness quartz ampoule is opened, gained black powder and water are mixed and stirred 6 hours, removes what part was not reacted completely
Metal；
(5) it will be mixed 6 hours in the watery hydrochloric acid that 1M is added after the solution suction filtration after stirring, plus deionized water washing suction filtration is extremely
Filtrate takes out the Ti for obtaining surface amorphous layers coated core-shell structure in neutrality, 60 DEG C of drying of low temperature4O7。
Embodiment 5
(1) using titanium dioxide as presoma, using magnesium metal as reducing agent, wherein, with molar percent magnesium metal：TiO2=
55% weighing ground and mixed in mortar is uniform；
(2) well mixed powder is added in the quartz ampoule of one end open, connects vavuum pump, vacuum is less than 1Pa, then
Quartz ampoule openend is melted using oxyhydrogen flame rifle and sealed；
(3) vacuum-tight quartz ampoule is placed in Muffle furnace, 1 DEG C/min heating rate is raised to 500 DEG C, insulation 6 from 30 DEG C
Hour, and 600 DEG C are raised to from 500 DEG C with 1 DEG C/min heating rate, furnace cooling after being incubated 6 hours；
(4) vacuum tightness quartz ampoule is opened, gained black powder and water are mixed and stirred 6 hours, removes what part was not reacted completely
Metal；
(5) it will be mixed 6 hours in the watery hydrochloric acid that 1M is added after the solution suction filtration after stirring, plus deionized water washing suction filtration is extremely
Filtrate takes out the Ti for obtaining surface amorphous layers coated core-shell structure in neutrality, 60 DEG C of drying of low temperature2O3。
Embodiment 6
(1) using titanium dioxide as presoma, using magnesium metal as reducing agent, wherein, with molar percent magnesium metal：TiO2=
55% weighing ground and mixed in mortar is uniform；
(2) well mixed powder is added in the quartz ampoule of one end open, connects vavuum pump, vacuum is less than 1Pa, then
Quartz ampoule openend is melted using oxyhydrogen flame rifle and sealed；
(3) vacuum-tight quartz ampoule is placed in Muffle furnace, 1 DEG C/min heating rate is raised to 450 DEG C, insulation 6 from 30 DEG C
Hour, and 700 DEG C are raised to from 450 DEG C with 1 DEG C/min heating rate, furnace cooling after being incubated 6 hours；
(4) vacuum tightness quartz ampoule is opened, gained black powder and water are mixed and stirred 6 hours, removes what part was not reacted completely
Metal；
(5) it will be mixed 6 hours in the watery hydrochloric acid that 1M is added after the solution suction filtration after stirring, plus deionized water washing suction filtration is extremely
Filtrate takes out the Ti for obtaining surface amorphous layers coated core-shell structure in neutrality, 60 DEG C of drying of low temperature2O3。
Embodiment 7
(1) using titanium dioxide as presoma, using calcium metal as reducing agent, wherein, with molar percent calcium metal：TiO2=
55% weighing ground and mixed in mortar is uniform；
(2) well mixed powder is added in the quartz ampoule of one end open, connects vavuum pump, vacuum is less than 1Pa, then
Quartz ampoule openend is melted using oxyhydrogen flame rifle and sealed；
(3) vacuum-tight quartz ampoule is placed in Muffle furnace, 1 DEG C/min heating rate is raised to 450 DEG C, insulation 6 from 30 DEG C
Hour, and 550 DEG C are raised to from 450 DEG C with 1 DEG C/min heating rate, furnace cooling after being incubated 6 hours；
(4) vacuum tightness quartz ampoule is opened, gained black powder and water are mixed and stirred 6 hours, removes what part was not reacted completely
Metal；
(5) it will be mixed 6 hours in the watery hydrochloric acid that 1M is added after the solution suction filtration after stirring, plus deionized water washing suction filtration is extremely
Filtrate takes out the Ti for obtaining surface amorphous layers coated core-shell structure in neutrality, 60 DEG C of drying of low temperature2O3。
Embodiment 8
(1) using titanium dioxide as presoma, using Preparation of Metallic Strontium as reducing agent, wherein, with molar percent Preparation of Metallic Strontium：TiO2=
55% weighing ground and mixed in mortar is uniform；
(2) well mixed powder is added in the quartz ampoule of one end open, connects vavuum pump, vacuum is less than 1Pa, then
Quartz ampoule openend is melted using oxyhydrogen flame rifle and sealed；
(3) vacuum-tight quartz ampoule is placed in Muffle furnace, 1 DEG C/min heating rate is raised to 450 DEG C, insulation 6 from 30 DEG C
Hour, and 550 DEG C are raised to from 450 DEG C with 1 DEG C/min heating rate, furnace cooling after being incubated 6 hours；
(4) vacuum tightness quartz ampoule is opened, gained black powder and water are mixed and stirred 6 hours, removes what part was not reacted completely
Metal；
(5) it will be mixed 6 hours in the watery hydrochloric acid that 1M is added after the solution suction filtration after stirring, plus deionized water washing suction filtration is extremely
Filtrate takes out the Ti for obtaining surface amorphous layers coated core-shell structure in neutrality, 60 DEG C of drying of low temperature2O3。
The Ti with surface amorphous layers coated core-shell structure prepared through the embodiment of the present invention 12O3XRD piece such as
It is Ti in Fig. 1 shown in b2O3Involved Ti in pure phase, Fig. 42O3It is also that the present embodiment prepares gained Ti2O3Pure phase.
The Ti with surface amorphous layers coated core-shell structure that method through the present invention is prepared2O3Transmission electron microscope picture
Piece shows its unique core shell structure, particle as shown in Fig. 2 can be clearly observable the cladding of surface amorphous layers from picture
Size is 50nm or so, and the thickness of sub- titanium oxide amorphous layer is 1.5nm.
The Ti with surface amorphous layers coated core-shell structure that method through the present invention is prepared2O3High resolution electron microscopy
Picture and its diffraction spot are as shown in Figure 3 a and Figure 3 b shows, it was demonstrated that be strictly sub- titanium oxide pure phase and coated with surface amorphous layers
Core shell structure.
The Ti with surface amorphous layers coated core-shell structure that method through the present invention is prepared2O3For electrocatalytic oxidation
Reducing property test pictures are as shown in Figure 4, it can be determined that it shows excellent electrocatalytic oxidation reducing property.
Referring to Fig. 5, it shows prepared by the sub- titanium dioxide powder and common high-temperature hydrogen reduction of the preparation of the embodiment of the present invention 4
Obtain sub- titanium dioxide powder (commercially available：Jiangsu Morgan new high-tech material Science and Technology Ltd., electrode material Ti4O7Powder) make
For the catalyst performance comparison diagram of electrocatalytic oxidation reduction reaction, it can be determined that what the present invention was obtained has what surface amorphous layers were coated
The sub- titanium oxide of core shell structure shows small overpotential, and big saturation current shows its excellent electrocatalytic oxidation reducing property.
Industrial applicability
This method is low for equipment requirements, short preparation period, the sub- oxygen with surface amorphous layers coated core-shell structure prepared
Changing titanium not only has the unique electricity, optical property, excellent heat endurance and the electrical conductivity of superelevation that have uniqueness of sub- titanium oxide,
Also there is the good performances such as particle diameter is small, specific surface area is high, microscopic structural units are controllable.What the present invention was prepared has surface
The sub- titanium oxide of amorphous layer coated core-shell structure has broad application prospects in catalysis energy storage field.
Claims (10)
1. a kind of sub- titanium oxide with core shell structure, it is characterised in that the sub- titanium oxide has core shell structure, its surface bag
It is covered with sub- titanium oxide amorphous layer.
2. sub- titanium oxide according to claim 1, it is characterised in that the particle diameter of the sub- titanium oxide is 5nm~5 μm, sub-
The thickness of titanium oxide amorphous layer is 1~3nm.
3. sub- titanium oxide according to claim 1 or 2, it is characterised in that the chemical formula of the sub- titanium oxide be TiO,
Ti2O3、Ti3O5、Ti4O7Or the sub- titanium oxide of other oxygen-containing vacancies.
4. the preparation method of a kind of sub- titanium oxide as any one of claim 1-3, it is characterised in that with titanium dioxide
For presoma, be placed in by reducing agent of active metal after uniform mixing in vacuum-tight quartz ampoule, prior to the first temperature 100~
It was incubated for the first stipulated time at 500 DEG C, was incubated for the second stipulated time at 550~800 DEG C of second temperature, utilizes active metal
Reduction titanium dioxide is so as to obtain the sub- titanium oxide.
5. preparation method according to claim 4, it is characterised in that mole of the control active metal and titanium dioxide
Than（1.6~0.2）：It is variable to adjust O/Ti ratios in the sub- titanium oxide in 1.
6. the preparation method according to claim 4 or 5, it is characterised in that the active metal be sodium, aluminium, zinc, iron, tin,
At least one of lead, lithium, magnesium, calcium, potassium, strontium, barium.
7. the preparation method according to any one of claim 4-6, it is characterised in that prior to 100~500 DEG C of the first temperature
Lower insulation 2~48 hours, 2~48 hours are incubated at 550~800 DEG C of second temperature.
8. the preparation method according to any one of claim 4-7, it is characterised in that the vacuum of the quartz ampoule is less than
30Pa, preferably smaller than 1Pa.
9. the preparation method according to any one of claim 4-8, it is characterised in that put the sub- titanium oxide prepared
Enter in etching liquid, remove the active metal oxide of unreacted active metal and generation.
10. preparation method according to claim 9, it is characterised in that the etching liquid is hydrochloric acid, sulfuric acid, nitric acid, phosphorus
At least one of acid, hydrofluoric acid, hydrogen peroxide, sodium hydrate aqueous solution and potassium hydroxide aqueous solution.
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