CN106976905B - The sub- titanium oxide and its controllable method for preparing of nucleocapsid - Google Patents
The sub- titanium oxide and its controllable method for preparing of nucleocapsid Download PDFInfo
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 238000000034 method Methods 0.000 title abstract description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 154
- 239000004408 titanium dioxide Substances 0.000 claims description 53
- 239000002184 metal Substances 0.000 claims description 51
- 239000003708 ampul Substances 0.000 claims description 48
- 239000010453 quartz Substances 0.000 claims description 48
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 48
- 229910052751 metal Inorganic materials 0.000 claims description 43
- 239000010936 titanium Substances 0.000 claims description 31
- 238000002360 preparation method Methods 0.000 claims description 28
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- 238000004321 preservation 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
- 238000005530 etching Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 229910009848 Ti4O7 Inorganic materials 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 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
- 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
- 229910009815 Ti3O5 Inorganic materials 0.000 claims description 5
- 239000011133 lead Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 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
- 229910009973 Ti2O3 Inorganic materials 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
- 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
- 238000002156 mixing Methods 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
- GQUJEMVIKWQAEH-UHFFFAOYSA-N titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 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 15
- 238000005253 cladding Methods 0.000 abstract description 15
- 230000005611 electricity Effects 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 5
- 239000004020 conductor Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 description 34
- 239000000843 powder Substances 0.000 description 25
- 239000011258 core-shell material Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 230000003647 oxidation Effects 0.000 description 16
- 238000007254 oxidation reaction Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000001603 reducing effect Effects 0.000 description 13
- 238000001816 cooling Methods 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 11
- 230000009467 reduction Effects 0.000 description 10
- 235000013339 cereals Nutrition 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
- 238000001914 filtration Methods 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
- 238000005303 weighing Methods 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 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
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000001239 high-resolution electron microscopy Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 230000001276 controlling effect Effects 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
- 239000002245 particle 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
- 230000008859 change Effects 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
- 238000012360 testing method Methods 0.000 description 2
- 238000004832 voltammetry Methods 0.000 description 2
- 241001614291 Anoplistes Species 0.000 description 1
- 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
- 238000006555 catalytic reaction Methods 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
- 239000006185 dispersion Substances 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000001788 irregular Effects 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
- 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
- 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
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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
- C01P2002/72—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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- 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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- 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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- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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Abstract
The present invention relates to the sub- titanium oxide and its controllable method for preparing of nucleocapsid, the Asia titanium oxide has nucleocapsid, and surface is coated with sub- titanium oxide amorphous layer.Central Asia titanium oxide of the present invention has the nucleocapsid of unique surface Asia titanium oxide amorphous layer cladding, it not only has that sub- titanium oxide is unique unique electricity, optical property, the conductivity of excellent thermal stability and superelevation, also there is the good performances such as grain size 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 fields, and in particular to a kind of sub- oxidation of surface amorphous layers coated core-shell structure
Titanium and its method of controllable preparation.
Background technology
Sub- titanium oxide is a series of general designation (Ti of non-stoichiometry oxidation titaniumsnO2n-1), there is high conductivity (conductivity
1500S/cm is far above graphite material), high chemical stability (strong alkali-acid resistance) and electrochemical stability (are stablized in aqueous solution
Voltage window is 3.0V or more) many advantages, such as.In catalyst/catalyst carrier, the fields such as fuel cell, flow battery have good
Good application prospect.
Nineteen fifty-nine, Magn é li have carried out the research of crystal structure to this substance 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 share all edges (side altogether) on a surface.In TinO2n-1In, each n-th layer has a oxygen
Atom lacks to form shear surface.On shear surface, octahedral two dimension chain becomes face and shares.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 atmosphere2It is obtained by the reaction with Titanium, it can also be by under high temperature
Use reducing agent such as hydrogen reducing TiO2It obtains, hydrogen reducing TiO is such as used at a high temperature of 1200 DEG C or more2Prepare sub- titanium oxide.
But these preparation methods are directed to pyroreaction (be higher than 1000 DEG C), and that there are equipment investments is costly, energy consumption is high, process conditions are multiple
The shortcomings of miscellaneous, it is difficult to realize industrialization, limit the application of both methods.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
Dispersion degree, particle size, temperature curve, that is, processing time etc.) influence, it is difficult to synthesize pure phase.Therefore, sub- titanium oxide is restricted
One main problem of application is exactly the preparation Asia titanium oxide pure phase of low cost.
Present hydrogen restores TiO2Obtained sub- titanium oxide itself only has weaker electro catalytic activity, and it is excellent to be typically due to its
Carrier of the different stability and high conductivity as catalyst.Whether it is possible that realizing 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 about low cost under cryogenic conditions at present
Prepare document report and the patent application of the nucleocapsid regulation and control of sub- titanium oxide pure phase method and its surface amorphous layers cladding.
Invention content
In view of the above-mentioned problems, the purpose of the present invention is to provide a kind of Asias of the nucleocapsid with surface amorphous layers cladding
Titanium oxide and its can inexpensive controllable preparation Asia titanium oxide pure phase under cryogenic preparation method.
On the one hand, the present invention provides a kind of sub- titanium oxide with nucleocapsid, the Asia titanium oxide has nucleocapsid knot
Structure, surface are coated with sub- titanium oxide amorphous layer.
Central Asia titanium oxide of the present invention has the nucleocapsid of unique surface Asia titanium oxide amorphous layer cladding, not only has
Sub- titanium oxide is unique to have unique electricity, optical property, the conductivity of excellent thermal stability and superelevation also to have grain size
Small, the good performance such as 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.
Preferably, the grain size of the Asia 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 is promoted not notable, and amorphous layer blocked up (being more than 2nm) then leads to material
Electric conductivity reduces, and also reduces electrocatalysis characteristic.
Preferably, the chemical formula of the Asia titanium oxide is TiO, Ti2O3、Ti3O5、Ti4O7Or the sub- oxygen of other oxygen-containing vacancies
Change titanium.
On the other hand, the present invention also provides a kind of systems of the above-mentioned sub- titanium oxide for stating surface amorphous layers coated core-shell structure
Preparation Method is placed in using active metal as reducing agent in vacuum-tight quartz ampoule after evenly mixing using titanium dioxide as presoma,
Prior to keeping the temperature for the first stipulated time at 100~500 DEG C of the first temperature, then at the second regulation of heat preservation at 550~800 DEG C of second temperature
Time restores titanium dioxide to obtain sub- titanium oxide using active metal.
The present invention is uniformly mixed as the active metal of presoma and different metering ratios using titanium dioxide and is placed on vacuum tightness
Quartz ampoule in be heated to being heated to after the first temperature stipulated time the time as defined in second temperature heat preservation, utilize active gold
Belong to reduction titanium dioxide to obtain sub- titanium oxide.In the present invention, under negative pressure (vacuum), using heating active metal, make gold
Belong to and titanium dioxide reacts, titanium dioxide is restored, to obtain sub- titanium oxide.The present invention uses two heat treatment holding temperatures：
First temperature keeps the temperature the stipulated time under lower temperature (100~500 DEG C) and realizes being sufficiently mixed for active metal and titanium dioxide
Uniformly, reaction can be made more uniform, it is ensured that generate sub- titanium oxide pure phase；Second temperature is at higher temperature (550~800 DEG C)
The lower heat preservation stipulated time, which will provide enough thermodynamical reactions, can make reduction reaction carry out completely, it is final realize sub- titanium oxide can
It controls standby.Wherein, the ordered arrangement for destroying atom during restoring titanium dioxide due to active metal, to form amorphous
Layer.The method of the invention can directly be handled titanium dioxide powder on a large scale, obtain the sub- oxidation of high catalytic activity
Titanium valve body.
Preferably, controlling the molar ratio of the active metal and titanium dioxide in (1.6~0.2)：It can be changed in 1 to adjust
State O/Ti ratios in sub- titanium oxide.
Preferably, 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.
Preferably, prior to keeping the temperature 2~48 hours at 100~500 DEG C of the first temperature, at 550~800 DEG C of second temperature
Heat preservation 2~48 hours.
Preferably, be first warming up to the first temperature with 1~5 DEG C/min of rate, then with 1~5 DEG C/min of rate from the
One temperature is warming up to second temperature.
Preferably, first temperature is 400~500 DEG C.
Preferably, the second temperature is 550~700 DEG C.
Preferably, the vacuum degree of the quartz ampoule is less than 30Pa, preferably smaller than 1Pa.
Preferably, the sub- titanium oxide being prepared is put into etching liquid, unreacted active metal and generation are removed
Active metal oxide.
Also, preferably, 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 common 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 that crystalline phase is controllable, titanium dioxide powder of controllable crystal, high catalytic performance.The present invention is using active gold
Belong to reduction titanium dioxide and prepare the sub- titania meterial with unique surface amorphous layers coated core-shell structure, not only there is sub- oxygen
Change the unique electricity of titanium, optical property, the conductivity of excellent thermal stability and superelevation, also have grain size is small, specific surface area is high,
The good performances such as microscopic structural units are controllable, can be used for catalyst and catalyst carrier, high-effective conductive material and prepare high
Imitate rechargeable battery etc..
Description of the drawings
Fig. 1 shows that the XRD photos of the sub- titanium oxide of the method synthesis of the present invention, wherein a are that TiO prepared by embodiment 2 is pure
Phase, b are Ti prepared by embodiment 12O3Pure phase；C is Ti prepared by embodiment 33O5Pure phase, d are Ti prepared by embodiment 44O7It is pure
Phase；
Fig. 2 shows the transmission electron microscope pictures of sub- titanium oxide prepared by the embodiment of the present invention 1, can clearly be seen from picture
The cladding for observing surface amorphous layers shows its unique nucleocapsid；
Fig. 3 a show the high resolution electron microscopy picture of sub- titanium oxide prepared by the embodiment of the present invention 1；
Fig. 3 b show the corresponding lattice of the high resolution electron microscopy picture (Fig. 3 a) of the sub- titanium oxide of the method synthesis of the present invention
Diffraction spot；
Property of the sub- titanium dioxide powder that the method that Fig. 4 shows the present invention synthesizes as the catalyst of electrocatalytic oxidation reduction reaction
Energy test chart, a are different sub- titanium oxide (wherein Ti under the same scan rate that linear voltammetry measures2O3It is made for embodiment 1
It is standby) electrocatalytic oxidation reducing property, b be embodiment 4 prepare Ti4O7Electrocatalytic oxidation under rotating disk electrode (r.d.e) different rotating speeds
Reducing property；
Fig. 5 shows that Asia is prepared in sub- titanium dioxide powder prepared by the embodiment of the present invention 4 and common high-temperature hydrogen reduction
Catalyst performance comparison diagram of the titanium dioxide powder as electrocatalytic oxidation reduction reaction.
Specific implementation mode
It is further illustrated the present invention 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 inexpensive controllable preparation Asia titanium oxide pure phase.Titanium dioxide is restored using active metal, in relative low temperature condition
(550 DEG C) controllable preparations for realizing sub- titanium oxide.The sub- titanium oxide prepared under this cryogenic conditions has unique surface amorphous
The nucleocapsid of layer cladding, has 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 not limited to the different morphologies such as ball, stick, band, pipe and irregular polygon.
In the present invention, the grain size 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, finally obtained sub- titanium oxide is nano particle.
Titanium dioxide can be purchased from commercialization, can also voluntarily prepare.In an example, nanometer ultrafine titania
Preparation method include：Titanium tetrachloride is hydrolyzed in ice water, can regulate and control titanium dioxide by control reaction condition receives
Techniques known may be used in the grain size of rice grain, specific control method.
The active metal of titanium dioxide and different metering ratios is uniformly mixed.The described active metal amount can be according to waiting making
Standby sub- titanium oxide suitably selects.The molar ratio of the active metal and titanium dioxide may generally be (1.6~0.22)：1.It can
O/Ti ratios in the sub- titanium oxide are adjusted by controlling the molar ratio of active metal and titanium dioxide.When the active metal and
The molar 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 molar 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 molar 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
Molar ratio be (0.23-0.28):When 1, gained Asia titanium oxide chemical formula is Ti4O7.In the present invention, active metal includes but not
It is limited at least one of lithium, magnesium, calcium, potassium, strontium, barium, Na, Al, Zn, Fe, Sn, Pb etc..
The stoichiometry of active metal and titanium dioxide has a major impact the preparation of sub- titanium oxide pure phase.Stoichiometry mistake
The high or too low preparation for being unfavorable for sub- titanium oxide pure phase, can lead to the mixed phase for generating sub- titanium oxide.
Powder after mixing is placed in vacuum-tight quartz ampoule.As an example, one end is added in powder
The quartz ampoule of opening, then vacuumizes tube sealing.In the present invention, the control of vacuum degree (negative pressure) in quartz ampoule is excellent less than 30Pa
Choosing is less than 1Pa.
Vacuum degree can have a major impact the preparation of sub- titanium oxide pure phase.Vacuum degree is inadequate, remaining air in quartz ampoule
In oxygen will participate in reacting, the reaction that is deviates anticipated chemical metering ratio, can lead to the mixed phase for generating sub- titanium oxide.
After being placed in vacuum-tight quartz ampoule, prior to being kept the temperature at 100~500 DEG C of the first temperature (the first heat treatment temperature)
First stipulated time kept the temperature for the second stipulated time at 550~800 DEG C of second temperature (the second heat treatment temperature), made active
Metal restores titanium dioxide to obtain sub- titanium oxide.As an example, after vacuum sealing tube, sample is heat-treated, is made
Active metal restores titanium dioxide, and Asia titanium oxide is made.The heat treatment is preferably 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
Rate be warming up to the first temperature.Second temperature is warming up to from the first temperature with 1~5 DEG C/min of rate again.
Heat treatment postcooling obtains sample, and cooling includes but not limited to quenching, air-cooled, furnace cooling.
Etching method can be used in the metal oxide for removing the metal not reacted completely and reaction generation, i.e., will be after cooling
Material is put into etching liquid, removes metal and metal oxide.The etching liquid include but 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 be reasonably selected according to used metal so that metal and reaction generate metal oxide completely remove.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 common tube sealing equipment that extensive system inexpensive under sub- titanium oxide cryogenic conditions can be realized
It is standby.
Asia titanium oxide prepared in accordance with the present invention has the nucleocapsid of unique surface cladding amorphous layer.The sub- oxidation
Titanium has nucleocapsid, and surface is coated with sub- titanium oxide amorphous layer.The grain size of the Asia 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 uniformly mixed as the active metal of presoma and different metering ratios using titanium dioxide and is placed on
It is heated to the time as defined in second temperature heat preservation after being heated to for the first temperature stipulated time in vacuum-tight quartz ampoule, is made
Active metal restores titanium dioxide 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, TiO, Ti is prepared2O3、Ti3O5、Ti4O7And other anoxic Asia titanium oxide.The present invention is mainly
The amount of active metal is adjusted to realize controllable reduction, but if second temperature is too low, kinetics is too slow, reaction cannot
It carries out completely.As for the first temperature primarily to reaction is more uniform.The sub- Titanium dioxide nanoparticle of gained has unique
The nucleocapsid of surface amorphous layers cladding.Sub- titanium oxide prepared by the present invention not only has that sub- titanium oxide is unique unique electricity
It learns, optical property, the conductivity of excellent thermal stability and superelevation, also with grain size is small, specific surface area is high, microscopic structural units
The good performance such as controllable, 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 nucleocapsid with surface amorphous layers cladding 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 nucleocapsid with surface amorphous layers cladding is prepared
It is as follows：
(1) using titanium dioxide as presoma, using active metal as reducing agent, wherein respectively with different molar percents
Metal：TiO2It is uniform to weigh the ground and mixed in mortar；
(2) uniformly mixed powder is added in the quartz ampoule of one end open, connects vacuum pump, vacuum degree is made to be less than
30Pa then utilizes oxyhydrogen flame rifle to melt quartz ampoule open end and seals；
(3) vacuum-tight quartz ampoule is placed in Muffle furnace, the heating rate of 1 DEG C/min is raised to the first temperature from 30 DEG C
Degree keeps the temperature the stipulated time, and is raised to second temperature from the first temperature with the heating rate of 1 DEG C/min, after keeping the temperature the stipulated time with
Furnace cooling is but；
(4) vacuum tightness quartz ampoule is opened, gained black powder and water are mixed and stirred 0.5~48 hour, removal part is not
The metal reacted completely；
(5) it is added in the dilute hydrochloric acid of 1M and is mixed 0.5~48 hour after filtering the solution after stirring, add deionized water
Washing is filtered to filtrate and is in neutrality, and 60 DEG C of drying of low temperature, which are taken out, obtains the sub- titanium oxide of surface amorphous layers coated core-shell structure,
Different stoichiometric ratios corresponds respectively to different sub- titanium oxide pure phases；
(6) by gained sample assembly electrode.
Referring to the XRD photos of Fig. 1, the method for showing the present invention sub- titanium oxide being prepared；Therefrom visible different items
The sub- titanium oxide being prepared under part corresponds to TiO phases, Ti respectively2O3Phase, Ti3O5Phase, Ti4O7Phase embodies the controllable of this method
Standby property；
Referring to Fig. 2, the transmission electron microscope picture of the sub- titanium oxide of the method synthesis of the present invention is shown, it can be clear from picture
The clear cladding for observing surface amorphous layers, shows its unique nucleocapsid, and sub- titan oxide particles size is 50nm or so；
Referring to Fig. 3 a and Fig. 3 b, the high resolution electron microscopy picture (Fig. 3 a) of the sub- titanium oxide of the method synthesis of the present invention is shown
And its corresponding lattice diffraction spot (Fig. 3 b), the really sub- titanium oxide pure phase therefrom proved and with surface amorphous layers cladding
Nucleocapsid.
Referring to Fig. 4, sub- titanium dioxide powder the urging as electrocatalytic oxidation reduction reaction of the method synthesis of the present invention is shown
The performance test figure of agent, a figures are the electro-catalysis of different Asia titanium oxide under the same scan rate that linear voltammetry measures in Fig. 4
Hydrogen reduction performance, b figures are Ti in 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, show prepared by the sub- titanium dioxide powder of the method synthesis of the present invention and common high-temperature hydrogen reduction
Obtain catalyst performance comparison diagram of the sub- titanium dioxide powder as electrocatalytic oxidation reduction reaction, it can be determined that the tool that the present invention obtains
There is the sub- titanium oxide of the nucleocapsid of surface amorphous layers cladding to show small overpotential, big saturation current shows that its is excellent
Electrocatalytic oxidation reducing property.
Embodiment is enumerated further below so that the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood 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 all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary concrete numerical value.If without specified otherwise, institute in the embodiment of the present 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) uniformly mixed powder is added in the quartz ampoule of one end open, connects vacuum pump, vacuum degree is made to be less than 1Pa,
It then utilizes oxyhydrogen flame rifle to melt quartz ampoule open end to seal；
(3) vacuum-tight quartz ampoule is placed in Muffle furnace, the heating rate of 1 DEG C/min is raised to 450 DEG C from 30 DEG C, protects
Temperature 6 hours, and 550 DEG C are raised to from 450 DEG C with the heating rate of 1 DEG C/min, furnace cooling after heat preservation 6 hours；
(4) vacuum tightness quartz ampoule is opened, gained black powder and water are mixed and stirred 6 hours, removal part is not completely anti-
The metal answered；
(5) it is added in the dilute hydrochloric acid of 1M and is mixed 6 hours after filtering the solution after stirring, deionized water washing is added to take out
Filter to filtrate is in neutrality, and 60 DEG C of drying of low temperature, which are taken out, obtains the Ti of surface amorphous layers coated core-shell structure2O3。
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) uniformly mixed powder is added in the quartz ampoule of one end open, connects vacuum pump, vacuum degree is made to be less than 1Pa,
It then utilizes oxyhydrogen flame rifle to melt quartz ampoule open end to seal；
(3) vacuum-tight quartz ampoule is placed in Muffle furnace, the heating rate of 1 DEG C/min is raised to 450 DEG C from 30 DEG C, protects
Temperature 6 hours, and 550 DEG C are raised to from 450 DEG C with the heating rate of 1 DEG C/min, furnace cooling after heat preservation 6 hours；
(4) vacuum tightness quartz ampoule is opened, gained black powder and water are mixed and stirred 6 hours, removal part is not completely anti-
The metal answered；
(5) it is added in the dilute hydrochloric acid of 1M and is mixed 6 hours after filtering the solution after stirring, deionized water washing is added to take out
Filter to filtrate is in neutrality, and 60 DEG C of drying of low temperature, which are taken out, obtains the TiO of surface amorphous layers coated core-shell structure.
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) uniformly mixed powder is added in the quartz ampoule of one end open, connects vacuum pump, vacuum degree is made to be less than 1Pa,
It then utilizes oxyhydrogen flame rifle to melt quartz ampoule open end to seal；
(3) vacuum-tight quartz ampoule is placed in Muffle furnace, the heating rate of 1 DEG C/min is raised to 450 DEG C from 30 DEG C, protects
Temperature 6 hours, and 550 DEG C are raised to from 450 DEG C with the heating rate of 1 DEG C/min, furnace cooling after heat preservation 6 hours；
(4) vacuum tightness quartz ampoule is opened, gained black powder and water are mixed and stirred 6 hours, removal part is not completely anti-
The metal answered；
(5) it is added in the dilute hydrochloric acid of 1M and is mixed 6 hours after filtering the solution after stirring, deionized water washing is added to take out
Filter to filtrate is in neutrality, and 60 DEG C of drying of low temperature, which are taken out, obtains the Ti of surface amorphous layers coated core-shell structure3O5。
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) uniformly mixed powder is added in the quartz ampoule of one end open, connects vacuum pump, vacuum degree is made to be less than 1Pa,
It then utilizes oxyhydrogen flame rifle to melt quartz ampoule open end to seal；
(3) vacuum-tight quartz ampoule is placed in Muffle furnace, the heating rate of 1 DEG C/min is raised to 450 DEG C from 30 DEG C, protects
Temperature 6 hours, and 550 DEG C are raised to from 450 DEG C with the heating rate of 1 DEG C/min, furnace cooling after heat preservation 6 hours；
(4) vacuum tightness quartz ampoule is opened, gained black powder and water are mixed and stirred 6 hours, removal part is not completely anti-
The metal answered；
(5) it is added in the dilute hydrochloric acid of 1M and is mixed 6 hours after filtering the solution after stirring, deionized water washing is added to take out
Filter to filtrate is in neutrality, and 60 DEG C of drying of low temperature, which are taken out, obtains the Ti of surface amorphous layers coated core-shell structure4O7。
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) uniformly mixed powder is added in the quartz ampoule of one end open, connects vacuum pump, vacuum degree is made to be less than 1Pa,
It then utilizes oxyhydrogen flame rifle to melt quartz ampoule open end to seal；
(3) vacuum-tight quartz ampoule is placed in Muffle furnace, the heating rate of 1 DEG C/min is raised to 500 DEG C from 30 DEG C, protects
Temperature 6 hours, and 600 DEG C are raised to from 500 DEG C with the heating rate of 1 DEG C/min, furnace cooling after heat preservation 6 hours；
(4) vacuum tightness quartz ampoule is opened, gained black powder and water are mixed and stirred 6 hours, removal part is not completely anti-
The metal answered；
(5) it is added in the dilute hydrochloric acid of 1M and is mixed 6 hours after filtering the solution after stirring, deionized water washing is added to take out
Filter to filtrate is in neutrality, and 60 DEG C of drying of low temperature, which are taken out, obtains the Ti of surface amorphous layers coated core-shell structure2O3。
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) uniformly mixed powder is added in the quartz ampoule of one end open, connects vacuum pump, vacuum degree is made to be less than 1Pa,
It then utilizes oxyhydrogen flame rifle to melt quartz ampoule open end to seal；
(3) vacuum-tight quartz ampoule is placed in Muffle furnace, the heating rate of 1 DEG C/min is raised to 450 DEG C from 30 DEG C, protects
Temperature 6 hours, and 700 DEG C are raised to from 450 DEG C with the heating rate of 1 DEG C/min, furnace cooling after heat preservation 6 hours；
(4) vacuum tightness quartz ampoule is opened, gained black powder and water are mixed and stirred 6 hours, removal part is not completely anti-
The metal answered；
(5) it is added in the dilute hydrochloric acid of 1M and is mixed 6 hours after filtering the solution after stirring, deionized water washing is added to take out
Filter to filtrate is in neutrality, and 60 DEG C of drying of low temperature, which are taken out, obtains the Ti of surface amorphous layers coated core-shell structure2O3。
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) uniformly mixed powder is added in the quartz ampoule of one end open, connects vacuum pump, vacuum degree is made to be less than 1Pa,
It then utilizes oxyhydrogen flame rifle to melt quartz ampoule open end to seal；
(3) vacuum-tight quartz ampoule is placed in Muffle furnace, the heating rate of 1 DEG C/min is raised to 450 DEG C from 30 DEG C, protects
Temperature 6 hours, and 550 DEG C are raised to from 450 DEG C with the heating rate of 1 DEG C/min, furnace cooling after heat preservation 6 hours；
(4) vacuum tightness quartz ampoule is opened, gained black powder and water are mixed and stirred 6 hours, removal part is not completely anti-
The metal answered；
(5) it is added in the dilute hydrochloric acid of 1M and is mixed 6 hours after filtering the solution after stirring, deionized water washing is added to take out
Filter to filtrate is in neutrality, and 60 DEG C of drying of low temperature, which are taken out, obtains the Ti of surface amorphous layers coated core-shell structure2O3。
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) uniformly mixed powder is added in the quartz ampoule of one end open, connects vacuum pump, vacuum degree is made to be less than 1Pa,
It then utilizes oxyhydrogen flame rifle to melt quartz ampoule open end to seal；
(3) vacuum-tight quartz ampoule is placed in Muffle furnace, the heating rate of 1 DEG C/min is raised to 450 DEG C from 30 DEG C, protects
Temperature 6 hours, and 550 DEG C are raised to from 450 DEG C with the heating rate of 1 DEG C/min, furnace cooling after heat preservation 6 hours；
(4) vacuum tightness quartz ampoule is opened, gained black powder and water are mixed and stirred 6 hours, removal part is not completely anti-
The metal answered；
(5) it is added in the dilute hydrochloric acid of 1M and is mixed 6 hours after filtering the solution after stirring, deionized water washing is added to take out
Filter to filtrate is in neutrality, and 60 DEG C of drying of low temperature, which are taken out, obtains the Ti of surface amorphous layers coated core-shell structure2O3。
The Ti with surface amorphous layers coated core-shell structure being prepared through the embodiment of the present invention 12O3XRD diagram piece such as
It is Ti in Fig. 1 shown in b2O3Pure phase, involved Ti in 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 nucleocapsid, 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 3a and Figure 3b shows, it was demonstrated that are strictly sub- titanium oxide pure phase and are coated with surface amorphous layers
Nucleocapsid.
The Ti with surface amorphous layers coated core-shell structure that method through the present invention is prepared2O3It is 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, sub- titanium dioxide powder and the preparation of common high-temperature hydrogen reduction prepared by the embodiment of the present invention 4 is shown
It is (commercially available to obtain sub- titanium dioxide powder：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 the present invention obtained has surface amorphous layers cladding
The sub- titanium oxide of nucleocapsid 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, be prepared with surface amorphous layers coated core-shell structure
Sub- titanium oxide not only has that sub- titanium oxide is unique unique electricity, optical property, the electricity of excellent thermal stability and superelevation
Conductance also has the good performances such as grain size is small, specific surface area is high, microscopic structural units are controllable.The tool that the present invention is prepared
There is the sub- titanium oxide of surface amorphous layers coated core-shell structure to have broad application prospects in being catalyzed energy storage field.
Claims (10)
1. a kind of sub- titanium oxide with nucleocapsid, which is characterized in that the Asia titanium oxide has nucleocapsid, surface packet
It is covered with sub- titanium oxide amorphous layer；The grain size of the Asia titanium oxide is 5nm~5 μm, and the thickness of sub- titanium oxide amorphous layer is 1~2nm.
2. Asia titanium oxide according to claim 1, which is characterized in that the chemical formula of the Asia titanium oxide is TiO, Ti2O3、
Ti3O5、Ti4O7Or the sub- titanium oxide of other oxygen-containing vacancies.
3. a kind of preparation method of sub- titanium oxide as claimed in claim 1 or 2, which is characterized in that with titanium dioxide be forerunner
Body is placed in using active metal as reducing agent in vacuum-tight quartz ampoule after evenly mixing, prior to 100~500 DEG C of the first temperature
First stipulated time of lower heat preservation was kept the temperature for the second stipulated time at 550~800 DEG C of second temperature, is restored using active metal
Titanium dioxide is to obtain the sub- titanium oxide.
4. preparation method according to claim 3, which is characterized in that control mole of the active metal and titanium dioxide
Than（1.6~0.2）：It is can be changed in 1 to adjust O/Ti ratios in the sub- titanium oxide.
5. preparation method according to claim 3, which is characterized in that the active metal be sodium, aluminium, zinc, iron, tin, lead,
At least one of lithium, magnesium, calcium, potassium, strontium, barium.
6. preparation method according to claim 3, which is characterized in that prior to heat preservation 2 at 100~500 DEG C of the first temperature~
48 hours, 2~48 hours are kept the temperature at 550~800 DEG C of second temperature.
7. preparation method according to claim 3, which is characterized in that the vacuum degree of the quartz ampoule is less than 30Pa.
8. preparation method according to claim 7, which is characterized in that the vacuum degree of the quartz ampoule is less than 1Pa.
9. according to the preparation method described in any one of claim 3-8, which is characterized in that put the sub- titanium oxide being prepared
Enter in etching liquid, removes the active metal oxide of unreacted active metal and generation.
10. preparation method according to claim 9, which is characterized 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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| CN107720808A (en) * | 2017-09-29 | 2018-02-23 | 张家港江苏科技大学产业技术研究院 | A kind of method of low temperature preparation high-purity Nano-class Asia titanium oxide |
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| CN108774738B (en) * | 2018-07-02 | 2020-09-01 | 重庆大学 | Hydrogen reduction TiO2Combined molten salt electrolysis of Ti4O7Method for preparing metallic titanium |
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| CN109701510A (en) * | 2019-01-28 | 2019-05-03 | 广东朗研科技有限公司 | A kind of preparation method of Magneli phase oxidation titanium mesopore surfaces |
| CN111762811B (en) * | 2019-04-02 | 2021-06-15 | 中国科学院上海硅酸盐研究所 | Method for preparing black titanium oxide loaded conductive TiO with specific proportion by disproportionating and decomposing titanium suboxide |
| CN110980803B (en) * | 2020-01-07 | 2020-11-06 | 重庆大学 | Controllable synthesis method of high-purity phase titanium suboxide |
| CN112838226B (en) * | 2021-01-22 | 2022-12-16 | 中汽创智科技有限公司 | Anti-reversal catalyst, preparation method and application |
| CN112973742A (en) * | 2021-02-10 | 2021-06-18 | 哈尔滨工业大学 | Low-dimensional bismuthate/reduced titanium dioxide composite material for efficient photolysis of water to produce hydrogen and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102817020A (en) * | 2012-08-20 | 2012-12-12 | 浙江南都电源动力股份有限公司 | Titanium-based titanium oxide plate and manufacturing method thereof |
| CN104032355A (en) * | 2014-06-20 | 2014-09-10 | 中南大学 | Method for preparing semimetallic state conductive titanium black nano-tube array |
| CN105058916A (en) * | 2015-07-20 | 2015-11-18 | 昆明理工大学 | Electrode material with intermediate Ti4O7 coating |
| CN106242585A (en) * | 2016-09-29 | 2016-12-21 | 四川大学 | A kind of sub-titanium oxide spherical powder and preparation method thereof |
| CN106241861A (en) * | 2016-07-19 | 2016-12-21 | 四川大学 | A kind of bar-shaped sub-titanium oxide powder and preparation method thereof |
| CN106337158A (en) * | 2016-09-29 | 2017-01-18 | 四川大学 | Spherical titanium black powder and preparation methods thereof |
-
2017
- 2017-03-07 CN CN201710131497.4A patent/CN106976905B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102817020A (en) * | 2012-08-20 | 2012-12-12 | 浙江南都电源动力股份有限公司 | Titanium-based titanium oxide plate and manufacturing method thereof |
| CN104032355A (en) * | 2014-06-20 | 2014-09-10 | 中南大学 | Method for preparing semimetallic state conductive titanium black nano-tube array |
| CN105058916A (en) * | 2015-07-20 | 2015-11-18 | 昆明理工大学 | Electrode material with intermediate Ti4O7 coating |
| CN106241861A (en) * | 2016-07-19 | 2016-12-21 | 四川大学 | A kind of bar-shaped sub-titanium oxide powder and preparation method thereof |
| CN106242585A (en) * | 2016-09-29 | 2016-12-21 | 四川大学 | A kind of sub-titanium oxide spherical powder and preparation method thereof |
| CN106337158A (en) * | 2016-09-29 | 2017-01-18 | 四川大学 | Spherical titanium black powder and preparation methods thereof |
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