CN102872774A - Titanium dioxide (shell)-dopant (core) composite material and preparation method thereof - Google Patents

Titanium dioxide (shell)-dopant (core) composite material and preparation method thereof Download PDF

Info

Publication number
CN102872774A
CN102872774A CN2011101931505A CN201110193150A CN102872774A CN 102872774 A CN102872774 A CN 102872774A CN 2011101931505 A CN2011101931505 A CN 2011101931505A CN 201110193150 A CN201110193150 A CN 201110193150A CN 102872774 A CN102872774 A CN 102872774A
Authority
CN
China
Prior art keywords
alloy
titanium dioxide
shell
oxide
nuclear
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN2011101931505A
Other languages
Chinese (zh)
Inventor
张�林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN2011101931505A priority Critical patent/CN102872774A/en
Publication of CN102872774A publication Critical patent/CN102872774A/en
Pending legal-status Critical Current

Links

Images

Landscapes

  • Catalysts (AREA)

Abstract

The invention discloses a titanium dioxide (shell)-dopant (core) composite material, characterized in that: titanium dioxide and dopant form a core-shell structure, and titanium dioxide is used as the shell, and the dopant is used as the core. The preparation method disclosed herein comprises the following steps: 1, carrying out mono dispersion on the dopant or its precursor; 2, wrapping the dopant; and 3, conducting post-treatment. According to the invention, the material disclosed herein can be prepared with high efficiency, low environmental pollution in preparation process, low energy consumption, and low process cost, can be produced in bulk, and the method disclosed herein can be widely applied in the field of titanium dioxide (shell)-dopant (core) composite material production.

Description

Titanium dioxide (shell)-alloy (nuclear) composite and preparation method thereof
Technical field
The present invention relates to titanium dioxide (shell)-alloy (nuclear) composite and preparation method thereof.
Background technology
Titanium dioxide (TiO 2), nontoxic pollution-free can be by organic pollution and prepare super hydrophilic automatically cleaning interface etc. in ultraviolet excitation sterilizing, the degraded environment, is the core substance in the field such as photocatalyst.But TiO 2Bandwidth (Eg) be 3.2eV (electronics is energized into the luminous energy that conduction band Conduction band needs from valence band Valence band), excite TiO 2Electronics is to absorb the luminous energy that surpasses 3.2eV with the prerequisite of opening photocatalyst reaction, this make the visible light that accounts for sunshine power spectrum 43% (380nm＜λ＜760nm) hang back, and account for the sunshine power spectrum approximately 5% ultraviolet light (luminous energy of λ＜380nm) just have above 3.2eV excites TiO 2Electronics also carries out photocatalyst reaction.It is found that through the element such as nitrogen (N), sulphur (S), cerium (Ce), silver (Ag), platinum (Pt), carbon (C), iron (Fe) or zinc oxide (ZnO), magnesia (MgO), tungsten oxide (WO 3), aluminium oxide (Al 2O 3) etc. the titanium dioxide after compound doped also can be produced photocatalyst activity by excited by visible light, this has widened TiO undoubtedly greatly 2Practicality.But from disclosed document and patent, find above-mentioned various alloys or enter TiO 2Lattice or and TiO 2Particle simply mixes or covers TiO 2The surface, and the patent of titanium dioxide (shell)-alloy (nuclear) composite is relatively less.
Application number is Degussa's patent of 01109511.3, when titanium dioxide is produced in pyrolysis, by spraying metal salt solution aerosol mode, only four kinds of products of zinc oxide, platinum oxide, magnesia and alumina doped titanium dioxide have been done patent protection, but product not titanium dioxide (shell)-alloy (nuclear) form of composite; Application number is the patent of invention of 200410099227.3 Jieshijie Novel Materials Co., Ltd, Shanghai, discloses " nano hollow microsphere of composite titania/inorganic carbon and its preparation method and application "; Application number is Zhejiang University's patent of invention of 200510061719.7, utilizes conventional wet chemistry method and high-energy ultrasonic etc., has prepared a kind of titanium dioxide parcel sulfide of core-shell structure or the nanometer, composite semiconductor photocatalyst of selenides; Application number is Industrial Technology Research Institute's patent of invention of 200510117598.3, at the surfaces of metal nanoparticles deposition of titanium oxide; Application number is University Of Dalian's patent of invention of 200710012315.8, discloses " a kind of preparation method of magnetic carrying of titanium dioxide photocatalyst ", at cobalt ferrite (CoFe 2O 4) wrap up titanium dioxide on the magnetic carrier; Application number is Shaanxi Tech Univ's patent of invention of 200710017764.1, discloses " synthetic method of shell starch microsphere "; Application number is Agricultural University Of South China's patent of invention of 200710027809.3, the colloidal sol that utilizes positive four butyl esters of metatitanic acid and ammonium ceric nitrate to mix, preparation cerium doped titanium dioxide (Ce-TiO 2) and load on and form composite photo-catalyst on the silica gel, cerium and titanium dioxide simply mix, and are not the core-shell structure form of titanium dioxide (shell)-alloy (nuclear); Application number is Shanghai Silicate Inst., Chinese Academy of Sciences's patent of 200710039531.1 and 200710173111.2, discloses respectively " Zinc oxide/titanium dioxide composite photo-catalyst, preparation and the application of core/shell structure " and " sol-gel method for preparing of earth silicon/titanic oxide hollow microballoon "; Application number is brilliant sharp porcelain industry (Beijing) Co., Ltd patent of invention of 200810212079.9, utilize metatitanic acid, the tungstenic aqueous solution and ammoniacal liquor etc. to prepare the tungstenic titanium dioxide powder, but be not titanium dioxide (shell)-alloy (nuclear) form of composite; Application number is Shanghai Haojia Nano Technology Co., Ltd.'s patent of invention of 200810200192.5 and 200810200196.3, only at " a kind of in cawk, blanc fixe, kaolin or the mica; particle diameter is 200 orders～12500 orders " upper deposition of titanium oxide, and do not relate to shell nuclear formula TiO 2Other alloy; Application number is 200810114788.3 Chalco Co., Ltd patent of invention, discloses " alumina group/nano titanium dioxide-nucleus/shell structure composite microballoons and preparation method thereof "; Application number is Inner Mongol University of Technology's patent of invention of 200810115333.3, at SILICA FUME surface parcel titanium dioxide shell; Application number is University Of Tianjin's patent of invention of 200910229191.8, discloses " method of preparing cuprous oxide/titanium dioxide core-shell structure array film through AC electro-deposition "; Application number is 200910049772.3 Donghua University, discloses " preparation of the polystyrene/titanium dioxide composite photocatalyst of core/shell structure "; Application number is 200910063398.2 Xiaogan College patent of invention, discloses " a kind of preparation method of nano silicon dioxide coated by nano titanium dioxide "; Application number is Chinese Aluminium Co., Ltd's patent of invention of 200910087741.7, discloses " a kind of preparation method of nickel ferrite based magnetic loaded type titanium dioxide photo-catalyst "; 201010117236.5 the Changchun University of Science and Technology's patent of invention with 201010117273.6 discloses respectively " a kind of method for preparing zinc titanate@titanium dioxide multi nano-cable " and " a kind of preparation method of nickel titanate@titanium dioxide multi nano-cable "; Application number is Changchun University of Science and Technology's patent of invention of 201010117247.3, discloses " a kind of method for preparing the tin dioxide titanium dioxide nano cable "; Application number is Heilongjiang University's patent of invention of 201010231365.7, discloses " carbon-titanium dioxide chromatography of core-shell structure is preparation method and the application of phase fixedly "; Application number is University Of Tianjin's patent of invention of 201010278619.0, discloses the method for doping magnetic particles of ferroferric oxide " a kind of in titania nanotube "; Application number is No.52 Inst., Ministry of Chinese Weapons Industry's patent of invention of 201010519320.X, discloses " a kind of Ni/TiO with electromagnetic coupled effect 2Base emr fluid and preparation method thereof "; In addition, some patent is take other material as shell, titanium dioxide is implemented parcel, just in time opposite with the shell nuclear order of " titanium dioxide (shell)-alloy (nuclear) composite " of this patent, be 200610117441.5 and Shanghai dongsheng New Materials Co., Ltd's patent of 200610117442.X etc. such as application number.
Except above-mentioned patent, do not find so far the patent that other is relevant with " titanium dioxide (shell)-alloy (nuclear) composite ".
In sum, all relate in the patent of invention of " modifying titania-doped " so far, and the alloy that consists of core-shell structure with titanium dioxide only is vanadium oxide (V 2O 5), argent (Ag), barium sulfate (BaSO 4), the sulfuration every (CdS), cadmium selenide (CdSe), kaolin Al 2(Si 2O 5) (OH) 4, mica KAl 2(AlSi 3O 10) (OH) 2, carbon (C), SILICA FUME (Si), nickel (Ni), silica (SiO 2), iron oxide (Fe 2O 3), tri-iron tetroxide (Fe 3O 4), cuprous oxide (Cu 2O), cupric oxide (CuO), zinc oxide (ZnO), tin oxide (SnO 2), nickel ferrite based magnetic loaded (NiFe 2O 4), cobalt ferrite (CoFe 2O 4), zinc titanate (ZnTiO 3), nickel titanate (NiTiO 3), zinc ferrite (ZnFe 2O 4), aluminium oxide (Al 2O 3), polystyrene, and the alloy that does not consist of core-shell structure with titanium dioxide is cerium (Ce), tungsten oxide (WO 3), blue tungsten oxide (W 20O 58), purple tungsten oxide (W 18O 49), platinum oxide (PtO 2), magnesia (MgO) etc.Preparation titanium dioxide (shell)-alloy (nuclear) composite has that raw material cheapness, technique are brief, pollution less with the advantages such as cost is low, market prospects are wide.Yet except above-mentioned patent, the patent of this class titanium dioxide (shell)-alloy (nuclear) composite and document are but still not abundant so far, can not provide sufficient technological guidance for enterprise produces.
Summary of the invention
The present invention seeks to development and address the above problem, and cost is low, technique is brief, pollute less, multiple titanium dioxide (shell) that can suitability for industrialized production-alloy (nuclear) composite and preparation method thereof.
Titanium dioxide of the present invention (shell)-alloy (nuclear) composite is characterized in that titanium dioxide and alloy are core-shell structure, and titanium dioxide (TiO 2) for the shell alloy is nuclear, alloy is defined as one or more in the following material:
Tungstic acid (WO 3), blue tungsten oxide (W 20O 58), purple tungsten oxide (W 18O 49), iron titanate (FeTiO 3), ferrous tungstate (FeWO 4), Manganese Ferrite (MnFe 2O 4), barium monoxide (Bi 2O 3), cerium sesquioxide (Ce 2O 3), cerium oxide (CeO 2), lanthana (La 2O 3), iron oxide hydroxide (FeOOH), manganese titanate (MnTiO 3), antimony oxide (Sb 2O 3), antimony doped tin oxide (ATO), fluorine doped tin oxide (FTO), Al-Doped ZnO (AZO), tin-doped indium oxide (ITO), mix tin zinc oxide (ZTO), Zirconium-doped yttria (YZO), gallium-doped zinc oxide (GZO), mix zinc indium oxide (IZO), mix gallium indium zinc oxide (IZGO), bismuth tungstate (Bi 2WO 6), pucherite (BiVO 4), niobium oxide (Nb 2O 5), strontium titanates (SrTiO 3), the alkaline earth aluminate of rear-earth-doped activation or the silicate (MOaAl of rear-earth-doped activation 2O 3BSiO 2: RE, a=0～7 wherein, b=0～10, M is one or more in the metallic elements such as calcium Ca, strontium Sr, barium Ba, magnesium Mg, zinc Zn, RE is one or more rare earth elements, for example the europium dysprosium magnesium silicate strontium Sr that mixes and activate 2MgSi 2O 7: Eu, Dy etc.), the luminescent powder of parcel tungsten oxide (or iron oxide, silica) thin layer.
The present invention is achieved through the following technical solutions:
Preparation titanium dioxide (shell)-alloy (nuclear) composite comprises following three steps.
The first step, single alloy or its presoma of disperseing
With alloy or its presoma (micron order or nano level ball, rod, pipe, particle etc.; commercially available or the self-control; its preparation method is not within this patent protection), with the supersonic gas atomizing or be diffused in the liquid and other medium, form monodispersed alloy or its presoma.
Second step, parcel mixes
Monodispersed alloy or its presoma are introduced in the reactor, imported again the titanium-containing compound that can generate nano titanium oxide, mix rear initiation reaction, preparation titanium dioxide (shell)-alloy (nuclear) composite.
The 3rd step, post processing
High annealing is optimized the degree of crystallinity of titanium dioxide (shell)-alloy (nuclear) composite, improves its photocatalyst activity.Titanium dioxide (shell)-alloy (nuclear) composite is made powdery product or be dispersed in formation coating fluid product or immobilized in other body surface formation photocatalyst material in the liquid.
The present invention has the following advantages:
Through enforcement of the present invention, when reducing environmental pollution, reduce energy consumption and reducing process costs, prepare dynamical multiple titanium dioxide (shell)-alloy (nuclear) composite, can not produce secondary pollution.
Description of drawings
Below in conjunction with accompanying drawing the present invention is further introduced, but not as limiting to the invention.
Fig. 1 is titanium dioxide (the shell)-image of alloy (nuclear) composite under SEM.
Fig. 2 is titanium dioxide (the shell)-image of alloy (nuclear) composite under transmission electron microscope.
In the drawings, 1 titanium dioxide shell, 2 alloys nuclear.
The specific embodiment
Multiple titanium dioxide (shell) among the present invention-alloy (nuclear) composite is characterized in that titanium dioxide and alloy are core-shell structure, and titanium dioxide is that shell and alloy are nuclear, and their preparation method is:
The first step, single alloy or its presoma of disperseing.
Second step, parcel mixes.
The 3rd step, post processing.
" alloy " in the first step is defined as one or more in the following compound:
Tungstic acid (WO 3), blue tungsten oxide (W 20O 58), purple tungsten oxide (W 18O 49), iron titanate (FeTiO 3), ferrous tungstate (FeWO 4), Manganese Ferrite (MnFe 2O 4), barium monoxide (Bi 2O 3), cerium sesquioxide (Ce 2O 3), cerium oxide (CeO 2), lanthana (La 2O 3), iron oxide hydroxide (FeOOH), manganese titanate (MnTiO 3), antimony oxide (Sb 2O 3), antimony doped tin oxide (ATO), fluorine doped tin oxide (FTO), Al-Doped ZnO (AZO), tin-doped indium oxide (ITO), mix tin zinc oxide (ZTO), Zirconium-doped yttria (YZO), gallium-doped zinc oxide (GZO), mix zinc indium oxide (IZO), mix gallium indium zinc oxide (IZGO), bismuth tungstate (Bi 2WO 6), pucherite (BiVO 4), niobium oxide (Nb 2O 5), strontium titanates (SrTiO 3), the alkaline earth aluminate of rear-earth-doped activation or the silicate (MOaAl of rear-earth-doped activation 2O 3BSiO 2: RE, a=0～7 wherein, b=0～10, M is one or more in the metallic elements such as calcium Ca, strontium Sr, barium Ba, magnesium Mg, zinc Zn, RE is one or more rare earth elements, for example the europium dysprosium magnesium silicate strontium Sr that mixes and activate 2MgSi 2O 7: Eu, Dy etc.), the luminescent powder of parcel tungsten oxide (or iron oxide, silica) thin layer.
Fig. 1 is TiO 2 Nano particle shell 1 is wrapped in the pictorial diagram that spherical alloy is examined 2 surfaces, and large figure is that SEM is taken, and upper right corner illustration is the enlarged image that transmission electron microscope is taken.
Be TiO among Fig. 2 2 Nano particle shell 1 is wrapped in the pictorial diagram that the clavate alloy is examined 2 surfaces, and transmission electron microscope is taken.
Embodiment 1:TiCl 4Flame hydrolysis prepares titanium dioxide (shell)-alloy (nuclear) composite
The first step is got 1 mole of alloy or its presoma (W for example 20O 58Or its presoma WCl 6), ultrasonic atomizatio forms the gas phase single particle and imports in the suitable reactor by oxygen in aerosol generator.Second step is with the titanium tetrachloride (TiCl after 1～10 mole of gasification 4) import to (TiCl in the reactor by hydrogen 4Molal quantity is with W 20O 58Deng alloy or its presoma WCl 6Particle size is 1～10 adjustment).TiCl in the reactor 4, hydrogen and oxygen flow be controlled as TiCl 4: H 2: O 2=1: 2: 1 (molal quantity ratio), evenly mixing and ignition reaction, oxyhydrogen flame high temperature generates water and facilitates TiCl 4At W 20O 58Deng alloy or its presoma WCl 6The moment hydrolysis of gas phase single particle surface, WCl simultaneously 6Generate W Deng presoma also pyrohydrolysis 20O 58Deng alloy, end product is TiO 2-W 20O 58Deng titanium dioxide (shell)-alloy (nuclear) particle and accessory substance HCl gas, the latter extracts and makes the byproducts such as hydrochloric acid, TiO out by low pressure cooling system 2-W 20O 58From reactor, isolate by cyclone separator or filter plant Deng titanium dioxide (shell)-alloy (nuclear) pressed powder.The 3rd step, the titanium dioxide of this explained hereafter (shell)-alloy (nuclear) composite has good degree of crystallinity not need again high annealing, can be directly for powdery product or utilize the tables of equipment such as ultrasonic wave to be dispersed in to form the coating fluid product in the liquid such as water or utilize that inorganic bond etc. is immobilized forms photocatalyst material in other body surface.The main chemical reactions equation of this technique is that (doping represents W 20O 58Deng alloy):
TiCl 4(g)+2H 2(g)+O 2(g)→TiO 2(s)+4HCl(g)
TiO 2(Shell)+doping(Core)→TiO 2-doping
Embodiment 2:TiCl 4Gaseous oxidation prepares titanium dioxide (shell)-alloy (nuclear) composite
The first step is got 1 mole of alloy or its presoma (Bi for example 2O 3Or its precursor B iCl 3), ultrasonic atomizatio forms the gas phase single particle and imports in the suitable reactor by oxygen in aerosol generator.Second step is with the titanium tetrachloride (TiCl after 1～10 mole of gasification 4) import to (TiCl in the reactor by nitrogen 4Molal quantity is with Bi 2O 3Deng alloy or its precursor B iCl 3Particle size is 1～10 adjustment).TiCl in the control reactor 4: O 2=1: 1 (molal quantity ratio) evenly mixed and ignition reaction TiCl 4Oxidation generates TiO 2And be deposited on Bi 2O 3Deng alloy or its precursor B iCl 3Gas phase single particle surface, BiCl simultaneously 3Generate Bi Deng presoma also high-temperature oxydation 2O 3Deng alloy, end product is TiO 2-Bi 2O 3Deng titanium dioxide (shell)-alloy (nuclear) particle and accessory substance Cl 2, the latter extracts byproducts such as making hypochlorous acid, TiO out by low pressure cooling system 2-Bi 2O 3From reactor, isolate by cyclone separator or filter plant Deng titanium dioxide (shell)-alloy (nuclear) pressed powder.The 3rd step, the titanium dioxide of this explained hereafter (shell)-alloy (nuclear) composite has good degree of crystallinity not need again high annealing, can be directly for powdery product or utilize the tables of equipment such as ultrasonic wave to be dispersed in to form the coating fluid product in the liquid such as water or utilize that inorganic bond etc. is immobilized forms photocatalyst material in other body surface.The main chemical reactions equation of this technique is that (doping represents Bi 2O 3Deng alloy):
TiCl 4(g)+O 2(g)→TiO 2(s)+2Cl 2(g)
TiO 2(Shell)+doping(Core)→TiO 2-doping
Embodiment 3:TiCl 4Liquid-phase hydrolysis prepares titanium dioxide (shell)-alloy (nuclear) composite
The first step is got 1 mole of alloy or its presoma (Sb for example 2O 3Or its presoma SbCl 3), ultrasonic being dispersed in the liquid mediums such as water forms single particle.Second step adds 1～10 mole of titanium tetrachloride (TiCl gradually 4) liquid (TiCl in reactor 4Molal quantity is with Sb 2O 3Deng alloy or its presoma SbCl 3Particle size is 1～10 adjustment), TiCl in the control reactor 4: H 2O=1: 1 (molal quantity ratio), TiCl 4Hydrolysis generates TiO 2And be deposited on Sb 2O 3Deng alloy or its presoma SbCl 3Liquid phase single particle surface, SbCl simultaneously 3Also be hydrolyzed generation Sb Deng presoma 2O 3Deng alloy, end product is TiO 2-Sb 2O 3Deng titanium dioxide (shell)-alloy (nuclear) particle and accessory substance HCl, the former isolates rear drying from reactor, and HCl can be made into the byproducts such as hydrochloric acid.The 3rd step, the titanium dioxide of this explained hereafter (shell)-alloy (nuclear) composite needs 450-500 ℃ of calcining annealing optimizing degree of crystallinity, can be directly for powdery product or utilize the tables of equipment such as ultrasonic wave to be dispersed in to form the coating fluid product in the liquid such as water or utilize that inorganic bond etc. is immobilized forms photocatalyst material in other body surface.The main chemical reactions equation of this technique is that (doping represents Sb 2O 3Deng alloy):
TiCl 4+2H 2O→TiO 2+4HCl
TiO 2(Shell)+doping(Core)→TiO 2-doping
Embodiment 4: the thermal decomposition of titanium alkoxide gas phase prepares titanium dioxide (shell)-alloy (nuclear) composite
The first step is got 1 mole of alloy or its presoma (the magnesium silicate strontium that mix to activate of europium dysprosium for example, Sr 2MgSi 2O 7: Eu, Dy), ultrasonic atomizatio forms the gas phase single particle and imports in the thermal decomposition furnace by carrier gas in aerosol generator, carrier gas is helium, nitrogen or argon gas, below identical.Second step is with the organic titanium alkoxide after 1～10 mole of gasification, for example tetrabutyl titanate Ti (OC 4H 9) 4, import to by carrier gas that (the tetrabutyl titanate molal quantity is with Sr in the thermal decomposition furnace 2MgSi 2O 7: Eu, the alloy such as Dy or its presoma particle size are 1～10 adjustment).Start pyrolysis after evenly mixing, titanium alkoxide pyrolytic generates TiO 2And be deposited on Sr 2MgSi 2O 7: Eu, the gas phase single particle surface of the alloys such as Dy, end product is TiO 2-(Sr 2MgSi 2O 7: Eu, Dy) etc. titanium dioxide (shell)-alloy (nuclear) particle and accessory substance alkene.The latter extracts out by low pressure cooling system and makes other byproduct, TiO 2-(Sr 2MgSi 2O 7: Eu, Dy) etc. titanium dioxide (shell)-alloy (nuclear) product isolate from reactor by cyclone separator or filter plant.The 3rd step, the titanium dioxide of this explained hereafter (shell)-alloy (nuclear) composite needs 450-500 ℃ of calcining annealing optimizing degree of crystallinity, can be directly for powdery product or utilize the tables of equipment such as ultrasonic wave to be dispersed in to form the coating fluid product in the liquid such as water or utilize that inorganic bond etc. is immobilized forms photocatalyst material in other body surface.The main chemical reactions equation of this technique is that (doping represents Sr 2MgSi 2O 7: Eu, the alloys such as Dy):
Ti(OC 4H 9) 4(g)→TiO 2(s)+2H 2O(g)+4C 4H 8(g)
TiO 2(Shell)+doping(Core)→TiO 2-doping
Embodiment 5: titanium alkoxide vapor phase hydrolysis prepares titanium dioxide (shell)-alloy (nuclear) composite
The first step is got 1 mole of alloy or its presoma (for example antimony doped tin oxide ATO), and ultrasonic atomizatio forms the gas phase single particle and imports in the reactor with carrier gas in aerosol generator, and carrier gas is the mist of nitrogen and steam.Second step is with the titanium alkoxide after 1～10 mole of gasification, for example tetrabutyl titanate Ti (OC 4H 9) 4Import reacting furnace (tetrabutyl titanate molal quantity with the alloy such as ATO or its presoma particle size 1～10 adjustment) with nitrogen, titanium alkoxide in the control reactor: water=1: 2 (molal quantity ratio), begin the vapor phase hydrolysis reaction after evenly mixing, titanium alkoxide vapor phase hydrolysis generates TiO 2And being deposited on the gas phase single particle surface of the alloys such as ATO, end product is TiO 2The titanium dioxide such as-ATO (shell)-alloy (nuclear) particle and by-product alcohol, the latter extracts out by low pressure cooling system and makes other byproduct, TiO 2The titanium dioxide such as-ATO (shell)-alloy (nuclear) product is isolated from reactor by cyclone separator or filter plant.The 3rd step, the titanium dioxide of this explained hereafter (shell)-alloy (nuclear) composite needs 450-500 ℃ of calcining annealing optimizing degree of crystallinity, can be directly for powdery product or utilize the tables of equipment such as ultrasonic wave to be dispersed in to form the coating fluid product in the liquid such as water or utilize that inorganic bond etc. is immobilized forms photocatalyst material in other body surface.The main chemical reactions equation of this technique is (doping represents the alloys such as ATO, and R represents alkyl):
Ti(OR) 4(g)+4H 2O→Ti(OH) 4(s)+4ROH(g)
Ti(OH) 4(s)→TiO 2·H 2O(g)+H 2O
TiO 2·H 2O(g)→TiO 2+H 2O(g)
TiO 2(Shell)+doping(Core)→TiO 2-doping
Embodiment 6: titanium alkoxide liquid-phase hydrolysis prepares titanium dioxide (shell)-alloy (nuclear) composite
The first step is got 1 mole of alloy or its presoma (strontium titanates SrTiO for example 3), ultrasonic being dispersed in the liquid mediums such as water forms single particle.Second step adds 1～10 mole of titanium alkoxide in reactor, for example tetrabutyl titanate Ti (OC gradually 4H 9) 4(titanium alkoxide molal quantity is with strontium titanates SrTiO 3Deng the alloy particle size 1～10 adjustment), titanium alkoxide in the control reactor: water=1: 2 (molal quantity ratio), titanium hydrolysis of alkoxide generate TiO 2And be deposited on SrTiO 3On the liquid phase single particle surface of alloy, end product is TiO 2-SrTiO 3Deng titanium dioxide (shell)-alloy (nuclear) particle and by-product alcohol, the latter makes other byproduct after centrifugation, and titanium dioxide (shell)-alloy (nuclear) is isolated rear drying from reactor.The 3rd step, the TiO of this explained hereafter 2-SrTiO 3Need 450-500 ℃ of calcining annealing optimizing degree of crystallinity Deng titanium dioxide (shell)-alloy (nuclear) composite, can be directly for powdery product or utilize the tables of equipment such as ultrasonic wave to be dispersed in to form the coating fluid product in the liquid such as water or utilize that inorganic bond etc. is immobilized forms photocatalyst material in other body surface.The main chemical reactions equation of this technique is that (doping represents SrTiO 3Deng alloy, R represents alkyl):
Ti(OR) 4(g)+2H 2O→TiO 2(s)+4ROH(g)
TiO 2(Shell)+doping(Core)→TiO 2-doping
Embodiment 7: the titanyl sulfate vapor phase hydrolysis prepares titanium dioxide (shell)-alloy (nuclear) composite
The first step is got 1 mole of alloy or its presoma and (is for example wrapped up the luminescent powder of tungsten oxide thin layer, be labeled as WO 3-luminescent powder), ultrasonic atomizatio forms the gas phase single particle and imports in the reactor with carrier gas in aerosol generator, and carrier gas is air or oxygen.Second step is with the titanyl sulfate (TiOSO after 1～10 mole of gasification 4) import to (TiOSO in the reactor by hydrogen 4Molal quantity with the alloy particle size such as luminescent powder of parcel tungsten oxide thin layer 1～10 adjustment), TiOSO in the control reactor 4: H 2: O 2=2: 2: 1 (molal quantity ratio), evenly mixing and ignition reaction, the titanyl sulfate pyrohydrolysis generates TiO 2And the gas phase single particle that is deposited on the alloys such as luminescent powder that wrap up the tungsten oxide thin layer is surperficial, and end product is TiO 2-(WO 3-luminescent powder) titanium dioxide (shell)-alloy (nuclear) particle and the accessory substance H such as 2SO 4, the latter makes the byproducts such as sulfuric acid after centrifugation, and titanium dioxide (shell)-alloy (nuclear) pressed powder is isolated from reactor by cyclone separator or filter plant subsequently.The 3rd step, the TiO of this explained hereafter 2-(WO 3-luminescent powder) etc. titanium dioxide (shell)-alloy (nuclear) composite need not calcined annealing, can be directly for powdery product or utilize the tables of equipment such as ultrasonic wave to be dispersed in to form the coating fluid product in the liquid such as water or utilize that inorganic bond etc. is immobilized forms photocatalyst material in other body surface.The main chemical reactions equation of this technique is (alloys such as luminescent powder of doping representative parcel tungsten oxide thin layer, R represents alkyl):
2TiOSO 4(g)+2H 2(g)+O 2(g)→2TiO 2+2H 2SO 4
TiO 2(Shell)+doping(Core)→TiO 2-doping
Embodiment 8: the titanyl sulfate liquid-phase hydrolysis prepares titanium dioxide (shell)-alloy (nuclear) composite
The first step is got 1 mole of alloy or its presoma (bismuth tungstate Bi for example 2WO 6), ultrasonic being dispersed in the liquid mediums such as water forms single particle.Second step adds 1～10 mol sulfuric acid oxygen titanium (TiOSO gradually 4) (the titanyl sulfate molal quantity is with Bi in reactor 2WO 6Deng the alloy particle size 1～10 adjustment), control reactor in TiOSO 4: H 2O=1: 1 (molal quantity ratio), the titanyl sulfate hydrolysis generates TiO 2And be deposited on Bi 2WO 6On the liquid phase single particle surface of alloy, end product is TiO 2-Bi 2WO 6Deng titanium dioxide (shell)-alloy (nuclear) particle and accessory substance H 2SO 4, the latter makes the byproducts such as sulfuric acid, TiO after centrifugation 2-Bi 2WO 6From reactor, separate rear dry Deng titanium dioxide (shell)-alloy (nuclear).The 3rd step, the titanium dioxide of this explained hereafter (shell)-alloy (nuclear) composite needs 450-500 ℃ of calcining annealing optimizing degree of crystallinity, can be directly for powdery product or utilize the tables of equipment such as ultrasonic wave to be dispersed in to form the coating fluid product in the liquid such as water or utilize that inorganic bond etc. is immobilized forms photocatalyst material in other body surface.The main chemical reactions equation of this technique is that (doping represents Bi 2WO 6Deng alloy, R represents alkyl):
TiOSO 4+H 2O→TiO 2+H 2SO 4
TiO 2(Shell)+doping(Core)→TiO 2-doping
The described multiple titanium dioxide of this patent (shell)-alloy (nuclear) composite is eight kinds of explained hereafter in the available above specific embodiment all, and the taken amount of each raw material enlarges in proportion with the reactor size or dwindles, and does not affect the quality of product.
Usefulness of the present invention is high, during preparation environmental pollution low, process costs is low, can the industrialization volume production, can be widely used in titanium dioxide (shell)-alloy (nuclear) composite and make the field.

Claims (2)

1. titanium dioxide (shell)-alloy (nuclear) composite is characterized in that titanium dioxide and alloy are core-shell structure, and titanium dioxide (TiO 2) for the shell alloy is nuclear, alloy is defined as one or more in the following material:
Tungstic acid (WO 3), blue tungsten oxide (W 20O 58), purple tungsten oxide (W 18O 49), iron titanate (FeTiO 3), ferrous tungstate (FeWO 4), Manganese Ferrite (MnFe 2O 4), barium monoxide (Bi 2O 3), cerium sesquioxide (Ce 2O 3), cerium oxide (CeO 2), lanthana (La 2O 3), iron oxide hydroxide (FeOOH), manganese titanate (MnTiO 3), antimony oxide (Sb 2O 3), antimony doped tin oxide (ATO), fluorine doped tin oxide (FTO), Al-Doped ZnO (AZO), tin-doped indium oxide (ITO), mix tin zinc oxide (ZTO), Zirconium-doped yttria (YZO), gallium-doped zinc oxide (GZO), mix zinc indium oxide (IZO), mix gallium indium zinc oxide (IZGO), bismuth tungstate (Bi 2WO 6), pucherite (BiVO 4), niobium oxide (Nb 2O 5), strontium titanates (SrTiO 3), the alkaline earth aluminate of rear-earth-doped activation or the silicate (MOaAl of rear-earth-doped activation 2O 3BSiO 2: RE, a=0～7 wherein, b=0～10, M is one or more in the metallic elements such as calcium Ca, strontium Sr, barium Ba, magnesium Mg, zinc Zn, RE is one or more rare earth elements, for example the europium dysprosium magnesium silicate strontium Sr that mixes and activate 2MgSi 2O 7: Eu, Dy etc.), the luminescent powder of parcel tungsten oxide (or iron oxide, silica) thin layer.
Titanium dioxide (shell)-alloy (nuclear) composite manufacture method is characterized in that:
The first step, single alloy or its presoma of disperseing
With alloy or its presoma (micron order or nano level ball, rod, pipe, particle etc.; commercially available or the self-control; its preparation method is not within this patent protection), with the supersonic gas atomizing or be diffused in the liquid and other medium, form monodispersed alloy or its presoma.
Second step, parcel mixes
Monodispersed alloy or its presoma are introduced in the reactor, imported again the titanium-containing compound that can generate nano titanium oxide, mix rear initiation reaction, preparation titanium dioxide (shell)-alloy (nuclear) composite.
The 3rd step, post processing
High annealing is optimized the degree of crystallinity of titanium dioxide (shell)-alloy (nuclear) composite, improves its photocatalyst activity.Titanium dioxide (shell)-alloy (nuclear) composite is made powdery product or be dispersed in formation coating fluid product or immobilized in other body surface formation photocatalyst material in the liquid.
2. titanium dioxide according to claim 1 (shell)-alloy (nuclear) composite is characterized in that: microscopic appearance comprises and is not limited to micron order or nano level ball, rod, pipe, particle etc.
CN2011101931505A 2011-07-11 2011-07-11 Titanium dioxide (shell)-dopant (core) composite material and preparation method thereof Pending CN102872774A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2011101931505A CN102872774A (en) 2011-07-11 2011-07-11 Titanium dioxide (shell)-dopant (core) composite material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2011101931505A CN102872774A (en) 2011-07-11 2011-07-11 Titanium dioxide (shell)-dopant (core) composite material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN102872774A true CN102872774A (en) 2013-01-16

Family

ID=47474420

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2011101931505A Pending CN102872774A (en) 2011-07-11 2011-07-11 Titanium dioxide (shell)-dopant (core) composite material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN102872774A (en)

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103232089A (en) * 2013-04-25 2013-08-07 太原理工大学 Method for carrying out photocatalytic degradation on waste water of explosives and powders based on magnetic carrier nano functional particles
CN103773223A (en) * 2014-01-10 2014-05-07 北京航空航天大学 Preparation method of core-shell structural high-transparency low-radiation heat-insulating composite nanometer coating
CN104759295A (en) * 2015-03-07 2015-07-08 兰州交通大学 A preparing method of a TiO2/PANI/MnFe2O4 photocatalytic magnetic fluid by a low-temperature hydrothermal method
JP2015163394A (en) * 2014-01-28 2015-09-10 シャープ株式会社 Photocatalyst material and method for producing the same
CN105163848A (en) * 2013-08-22 2015-12-16 夏普株式会社 Photocatalyst material
CN105420603A (en) * 2015-11-05 2016-03-23 安徽银球轴承有限公司 Sintered metal powder bearing with good heat resistance and high lubricating property and preparation method of sintered metal powder bearing
CN107057549A (en) * 2017-05-27 2017-08-18 新疆新光保环保科技有限公司 A kind of preparation method of the insulating mold coating for high-transparent glass of superhydrophilic self-cleaning
CN107144611A (en) * 2017-06-30 2017-09-08 盐城工学院 A kind of optical electro-chemistry detection method of sulfur dioxide
CN107308733A (en) * 2017-05-19 2017-11-03 浙江帝恒实业有限公司 A kind of air purifier composite screen and preparation method thereof
CN108295836A (en) * 2017-12-27 2018-07-20 佛山科学技术学院 A kind of preparation method of nucleocapsid ATO/ earth silicon/titanic oxide composite materials
CN108298551A (en) * 2017-12-27 2018-07-20 佛山科学技术学院 A kind of preparation method of core-shell structure copolymer-nuclear structure mesoporous molecular sieve nanocomposite
CN108587449A (en) * 2018-04-27 2018-09-28 上海大学 A kind of Cr@ZnO@TiO capsule of nano and preparation method thereof and a kind of gel coat high-strength steel
CN109201034A (en) * 2017-07-06 2019-01-15 龙岩紫荆创新研究院 A kind of hud typed denitrating catalyst and preparation method thereof
CN109294282A (en) * 2018-09-30 2019-02-01 滁州市开金绢云母有限公司 A kind of preparation method of novel nano sericite powder
CN109712752A (en) * 2018-12-30 2019-05-03 新沂博瑞工业设计有限公司 A kind of flame retardant type power cable
CN110038560A (en) * 2019-04-28 2019-07-23 河南大学 A kind of sea urchin shape hollow platinum/titanium dioxide nano material, preparation method and application of oxygen-containing vacancy
CN110270332A (en) * 2019-07-22 2019-09-24 福州大学 A kind of magnetism TiO2(R) composite photo-catalyst and preparation method thereof
CN111363428A (en) * 2020-03-23 2020-07-03 苏州鼎奕通材料科技有限公司 Fingerprint-preventing and pollution-preventing environment-friendly coating and preparation method thereof
CN111774053A (en) * 2020-07-06 2020-10-16 重庆工程职业技术学院 Method for preparing dysprosium-doped nano-sheet bismuth tungstate photocatalyst
CN112473733A (en) * 2020-12-01 2021-03-12 贵州省化工研究院 Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst and application thereof
CN113786838A (en) * 2021-09-22 2021-12-14 杭州诚洁环保有限公司 Core-shell nano composite material and preparation method and application thereof
WO2022047813A1 (en) * 2020-09-01 2022-03-10 中认英泰检测技术有限公司 Organic wastewater treatment method based on multi-element co-doped tio2 nano photocatalytic material
CN114832825A (en) * 2022-05-18 2022-08-02 东南大学 Preparation method of catalyst with spherical shell separation double-coating structure
CN115044908A (en) * 2022-06-08 2022-09-13 中国科学院海洋研究所 Manganese ferrite modified titanium dioxide heterojunction photo-anode and preparation method and application thereof
CN115611373A (en) * 2022-09-15 2023-01-17 山东大学 FeOOH/In-BiVO 4 (L) photoelectric anode material and preparation method and application thereof
CN115845928A (en) * 2022-11-30 2023-03-28 辽宁大学 MOFs-derived cerium-based catalyst with core-shell structure and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009040553A2 (en) * 2007-09-28 2009-04-02 Nanoco Technologies Limited Core shell nanoparticles and preparation method thereof
CN101618351A (en) * 2009-08-06 2010-01-06 上海理工大学 Nanometer or micrometer structure composite material and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009040553A2 (en) * 2007-09-28 2009-04-02 Nanoco Technologies Limited Core shell nanoparticles and preparation method thereof
CN101618351A (en) * 2009-08-06 2010-01-06 上海理工大学 Nanometer or micrometer structure composite material and preparation method thereof

Cited By (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103232089B (en) * 2013-04-25 2014-07-30 太原理工大学 Method for carrying out photocatalytic degradation on waste water of explosives and powders based on magnetic carrier nano functional particles
CN103232089A (en) * 2013-04-25 2013-08-07 太原理工大学 Method for carrying out photocatalytic degradation on waste water of explosives and powders based on magnetic carrier nano functional particles
US20160107145A1 (en) * 2013-08-22 2016-04-21 Sharp Kabushiki Kaisha Photocatalyst material
CN110354844A (en) * 2013-08-22 2019-10-22 夏普株式会社 Photocatalyst material
US10576459B2 (en) * 2013-08-22 2020-03-03 Sharp Kabushiki Kaisha Photocatalyst material
CN105163848A (en) * 2013-08-22 2015-12-16 夏普株式会社 Photocatalyst material
CN103773223A (en) * 2014-01-10 2014-05-07 北京航空航天大学 Preparation method of core-shell structural high-transparency low-radiation heat-insulating composite nanometer coating
CN103773223B (en) * 2014-01-10 2016-01-27 北京航空航天大学 A kind of heat insulation composite nano-coating preparation method of high transparency Low emissivity of nucleocapsid structure
JP2015163394A (en) * 2014-01-28 2015-09-10 シャープ株式会社 Photocatalyst material and method for producing the same
CN105873677A (en) * 2014-01-28 2016-08-17 夏普株式会社 Photocatalyst material and method for producing same
US10507454B2 (en) 2014-01-28 2019-12-17 Sharp Kabushiki Kaisha Photocatalyst material and method for producing same
JP2019181469A (en) * 2014-01-28 2019-10-24 シャープ株式会社 Photocatalytic material and method for producing the same
CN104759295A (en) * 2015-03-07 2015-07-08 兰州交通大学 A preparing method of a TiO2/PANI/MnFe2O4 photocatalytic magnetic fluid by a low-temperature hydrothermal method
CN105420603A (en) * 2015-11-05 2016-03-23 安徽银球轴承有限公司 Sintered metal powder bearing with good heat resistance and high lubricating property and preparation method of sintered metal powder bearing
CN107308733A (en) * 2017-05-19 2017-11-03 浙江帝恒实业有限公司 A kind of air purifier composite screen and preparation method thereof
CN107308733B (en) * 2017-05-19 2018-08-03 丁海军 A kind of air purifier composite screen and preparation method thereof
CN107057549A (en) * 2017-05-27 2017-08-18 新疆新光保环保科技有限公司 A kind of preparation method of the insulating mold coating for high-transparent glass of superhydrophilic self-cleaning
CN107057549B (en) * 2017-05-27 2019-10-22 新疆新光保环保科技有限公司 A kind of preparation method of the insulating mold coating for high-transparent glass of superhydrophilic self-cleaning
CN107144611A (en) * 2017-06-30 2017-09-08 盐城工学院 A kind of optical electro-chemistry detection method of sulfur dioxide
CN109201034A (en) * 2017-07-06 2019-01-15 龙岩紫荆创新研究院 A kind of hud typed denitrating catalyst and preparation method thereof
CN108295836B (en) * 2017-12-27 2020-09-18 佛山科学技术学院 Preparation method of ATO/silicon dioxide/titanium dioxide composite material with core-shell structure
CN108298551A (en) * 2017-12-27 2018-07-20 佛山科学技术学院 A kind of preparation method of core-shell structure copolymer-nuclear structure mesoporous molecular sieve nanocomposite
CN108295836A (en) * 2017-12-27 2018-07-20 佛山科学技术学院 A kind of preparation method of nucleocapsid ATO/ earth silicon/titanic oxide composite materials
CN108298551B (en) * 2017-12-27 2020-09-18 佛山科学技术学院 Preparation method of mesoporous molecular sieve nanocomposite with core-shell-core structure
CN108587449A (en) * 2018-04-27 2018-09-28 上海大学 A kind of Cr@ZnO@TiO capsule of nano and preparation method thereof and a kind of gel coat high-strength steel
CN109294282A (en) * 2018-09-30 2019-02-01 滁州市开金绢云母有限公司 A kind of preparation method of novel nano sericite powder
CN109712752A (en) * 2018-12-30 2019-05-03 新沂博瑞工业设计有限公司 A kind of flame retardant type power cable
CN110038560A (en) * 2019-04-28 2019-07-23 河南大学 A kind of sea urchin shape hollow platinum/titanium dioxide nano material, preparation method and application of oxygen-containing vacancy
CN110270332A (en) * 2019-07-22 2019-09-24 福州大学 A kind of magnetism TiO2(R) composite photo-catalyst and preparation method thereof
CN110270332B (en) * 2019-07-22 2021-06-01 福州大学 Magnetic TiO2(R) composite photocatalyst and preparation method thereof
CN111363428A (en) * 2020-03-23 2020-07-03 苏州鼎奕通材料科技有限公司 Fingerprint-preventing and pollution-preventing environment-friendly coating and preparation method thereof
CN111774053A (en) * 2020-07-06 2020-10-16 重庆工程职业技术学院 Method for preparing dysprosium-doped nano-sheet bismuth tungstate photocatalyst
WO2022047813A1 (en) * 2020-09-01 2022-03-10 中认英泰检测技术有限公司 Organic wastewater treatment method based on multi-element co-doped tio2 nano photocatalytic material
US11534741B2 (en) 2020-09-01 2022-12-27 Cqc Intime Testing Technology Co., Ltd. Organic wastewater treatment method based on multi-element co-doping TiO2 nano photocatalytic material
CN112473733A (en) * 2020-12-01 2021-03-12 贵州省化工研究院 Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst and application thereof
CN112473733B (en) * 2020-12-01 2022-07-22 贵州省化工研究院 Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst and application thereof
CN113786838A (en) * 2021-09-22 2021-12-14 杭州诚洁环保有限公司 Core-shell nano composite material and preparation method and application thereof
CN113786838B (en) * 2021-09-22 2023-06-27 杭州诚洁环保有限公司 Core-shell nanocomposite and preparation method and application thereof
CN114832825A (en) * 2022-05-18 2022-08-02 东南大学 Preparation method of catalyst with spherical shell separation double-coating structure
CN114832825B (en) * 2022-05-18 2024-02-09 东南大学 Preparation method of spherical shell separation double-coating structure catalyst
CN115044908A (en) * 2022-06-08 2022-09-13 中国科学院海洋研究所 Manganese ferrite modified titanium dioxide heterojunction photo-anode and preparation method and application thereof
CN115044908B (en) * 2022-06-08 2023-09-12 中国科学院海洋研究所 Manganese ferrite modified titanium dioxide heterojunction photo-anode and preparation method and application thereof
CN115611373A (en) * 2022-09-15 2023-01-17 山东大学 FeOOH/In-BiVO 4 (L) photoelectric anode material and preparation method and application thereof
CN115611373B (en) * 2022-09-15 2024-06-28 山东大学 FeOOH/In-BiVO4(L) photoanode material and preparation method and application thereof
CN115845928A (en) * 2022-11-30 2023-03-28 辽宁大学 MOFs-derived cerium-based catalyst with core-shell structure and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN102872774A (en) Titanium dioxide (shell)-dopant (core) composite material and preparation method thereof
Sivasamy et al. Synthesis of Gd2O3/CdO composite by sol-gel method: Structural, morphological, optical, electrochemical and magnetic studies
Fu et al. A facile coating method to construct uniform porous α-Fe2O3@ TiO2 core-shell nanostructures with enhanced solar light photocatalytic activity
CN108275719A (en) A kind of TiO that Phase Proportion is controllable2The preparation and application of heterojunction material
Wang et al. TiO2 modified g-C3N4 with enhanced photocatalytic CO2 reduction performance
Wang et al. Novel magnetic BaFe12O19/g-C3N4 composites with enhanced thermocatalytic and photo-Fenton activity under visible-light
Pan et al. Nanophotocatalysts via microwave-assisted solution-phase synthesis for efficient photocatalysis
US10766787B1 (en) Production of mixed metal oxide nanostructured compounds
CN100402467C (en) Method for preparing Nano composite material of stannic oxide / titanium dioxide
Abdelkader et al. Synthesis, characterization and UV-A light photocatalytic activity of 20 wt% SrO–CuBi2O4 composite
CN101850980B (en) Method for preparing silicon dioxide cladding silver-doped zinc oxide nano crystal
Xu et al. Synthesis of LaFeO3/Bi3NbO7 pn heterojunction photocatalysts with enhanced visible-light-responsive activity for photocatalytic reduction of Cr (Ⅵ)
CN113249091B (en) ATO (antimony tin oxide) coated cesium tungsten bronze composite nano powder and preparation method thereof
Dammala et al. Synthesis of biphasic nanomaterials based on ZnO and SnO2: Application towards photocatalytic degradation of acid red dye
CN101941731B (en) Preparation method of void type nano-sheet zinc oxide and activated carbon load complex
CN102886279A (en) Preparation method for coating metal nanoparticles on surface of nano-titania
Xie et al. Synthesis and characterization of Bi2SiO5-coated Ag/AgBr photocatalyst with highly efficient decontamination of organic pollutants
Liu et al. Preparation, Functionality, and Application of Metal Oxide‐coated Noble Metal Nanoparticles
CN108295836A (en) A kind of preparation method of nucleocapsid ATO/ earth silicon/titanic oxide composite materials
Fang et al. Effect of crystalline/amorphous structure on light absorption and carrier separationof CeO2-TiO2 heterojunctions
CN101279719A (en) Preparation for nano-oxide powder
Xu et al. From titanates to TiO 2 nanostructures: controllable synthesis, growth mechanism, and applications
CN110711581A (en) Copper-based composite metal oxide mesomorphic microsphere and preparation method and application thereof
Jiang et al. Effect of Bi/Ti ratio on (Na0. 5Bi0. 5) TiO3/Bi4Ti3O12 heterojunction formation and photocatalytic performance
CN103272592A (en) Preparation method of one-dimensional silver-loaded titanium dioxide nanorod photocatalyst

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C05 Deemed withdrawal (patent law before 1993)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20130116