CN101773838B - Silver nanoparticle-dispersed cobalt oxide functional thin film material and preparation method - Google Patents

Silver nanoparticle-dispersed cobalt oxide functional thin film material and preparation method Download PDF

Info

Publication number
CN101773838B
CN101773838B CN201010034474XA CN201010034474A CN101773838B CN 101773838 B CN101773838 B CN 101773838B CN 201010034474X A CN201010034474X A CN 201010034474XA CN 201010034474 A CN201010034474 A CN 201010034474A CN 101773838 B CN101773838 B CN 101773838B
Authority
CN
China
Prior art keywords
film
solution
silver
mother solution
preparation
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.)
Expired - Fee Related
Application number
CN201010034474XA
Other languages
Chinese (zh)
Other versions
CN101773838A (en
Inventor
张波萍
王士京
李顺
赵翠华
严丽平
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.)
University of Science and Technology Beijing USTB
Original Assignee
University of Science and Technology Beijing USTB
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 University of Science and Technology Beijing USTB filed Critical University of Science and Technology Beijing USTB
Priority to CN201010034474XA priority Critical patent/CN101773838B/en
Publication of CN101773838A publication Critical patent/CN101773838A/en
Application granted granted Critical
Publication of CN101773838B publication Critical patent/CN101773838B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Abstract

The invention relates to a silver nanoparticle-dispersed cobalt oxide functional thin film material and a preparation method, and belongs to the field of photocatalysis. The material is characterized in that the general formula of chemical compositions of the thin film material is Agx / (Co3O4) 1-x, wherein x indicates the mole fraction of constituent element of Ag, and x ranges from 0.01 to 0.85. In the process, cobalt nitrate and silver nitrate are used as raw materials, and ethylene glycol monomethyl ether is used as a solvent; a precursor solution with accurate stoichiometric proportion and uniform compositions is synthesized by chemical solution method, and film is coated on a glass substrate by a spin coater, and finally the Agx / (Co3O4) 1-x composite film is obtained by thermal decomposition and annealing. Silver nanoparticles are uniformly dispersed in a cobalt oxide matrix, and the diameter of the silver particle is 1- 500nm; and the film can observe the plasma resonance absorption peaks of metal particles at a wave band of 350-450nm, and the film has excellent photocatalytic properties under the irradiation of visible light.

Description

A kind of silver nanoparticle-dispersed cobalt oxide functional thin-film material and preparation method
Technical field
The invention belongs to photocatalysis field; Propose a kind of silver nanoparticle-dispersed cobalt oxide plasma resonance type photo-catalysis function thin-film material especially, related to the design and the preparation technology of nano-metal particle dispersal oxide conductor photocatalysis film material with function.
Background technology
The appearance of the outburst that is accompanied by energy crisis in the world wide and ecological deterioration problem etc., energy and environment become 21 century face of mankind and two significant problems needing to be resolved hurrily.Multiphase photocatalysis has the room temperature deep reaction and directly utilizes solar energy to drive special performances such as reaction as light source, as a kind of ideal environment pollution control technology and clear energy sources production technology, causes people's growing interest in recent years.
Light-catalyzed reaction utilizes luminous energy to carry out material and transforms, and is one of multiple mode of light and interaction between substances.Material carries out chemical reaction under light and catalyst act on simultaneously, luminous energy is changed into chemical energy and promotes organic synthetic and organic matter degradation.The exploitation of photo-catalysis function thin-film material has overcome the some shortcomings that photochemical catalyst exists (being difficult for engineering problems such as fixing, use back difficult separation and recycling like the powdery photochemical catalyst) in practical application, also widened the range of application of photocatalysis technology simultaneously.Particularly Japanese in developed country; The commercialization research and development progress of photo-catalysis function material rapidly; There has been a large amount of Related products to succeed in developing and introduce to the market, like surperficial plated with photocatalysis agent film and have ceramic tile, china sanitary ware, windshield and bathroom mirror, glass pane and a building glass that decomposes the kitchen fume function with long-term maintenance surface cleaning with anti-mist function with sterilizing function.These photocatalytic product are widely used in fields such as building, automobile, medical treatment, national defence.China is also fewer in the application of photocatalysis field, remains further to be developed.
People [Koichi Awazu such as Japan scholar Koichi Awazu; Et al., J.AM.CHEM.SOC., 2008; 130; 1676-1680.] notion of Plasmonic Photocatalysis (plasma resonance photocatalysis) has been proposed in 2008 first, this plasma resonance type photochemical catalyst is the modification to semiconductor catalyst, by SiO 2Precipitate last layer TiO again on the coating of the nucleocapsid structure that clad nano Ag particle is formed 2, reducing catalytic performance to prevent that Ag simple substance is oxidized, the organic speed of this kind photocatalysis film material degradation is TiO 2About 7 times of film, shown excellent photocatalytic performance.Plasma resonance type photo-catalysis function thin-film material has utilized the surface plasma body resonant vibration sink effect of metallic, has improved absorbing properties effectively through absorbing visible light.Light induced electron is to the metallic particles enrichment in photocatalytic process, and photohole has promoted separating of light induced electron and hole to the semiconductor grain surface migration, has reduced the recombination rate of the two, thereby has increased substantially photocatalysis efficiency.The plasma resonance type photo-catalysis function thin-film material of at present relevant silver metal particles dispersed cobalt oxide does not also appear in the newspapers.
Summary of the invention
The object of the invention provides a kind of metallic silver particles dispersed cobalt oxide photocatalysis composite film, through composition, optimization sol evenning machine whirl coating, coating layer thickness and this film of Technology for Heating Processing preparation of control precursor solution.With (the Ag+SiO that has reported 2)/TiO 2Laminated film is compared, and in the good catalysis characteristics of maintenance, this invented technology route is simple, and equipment needed thereby is simple, and required cost is low, and is easy to operate, and can accurately control the stoichiometric proportion of film.
A kind of silver nanoparticle-dispersed cobalt oxide functional thin-film material and preparation method, it is Ag that its film chemical becomes to be grouped into general formula x/ (Co 3O 4) 1-x, wherein x representes the molar fraction of Ag component, the span of x is 0.01≤x≤0.85.The present invention adopts chemical solution method to prepare Ag x/ (Co 3O 4) 1-xLaminated film; Silver nano-grain is dispersed in the cobaltosic oxide matrix; The silver particle diameter is 1～500nm; Film is observed the plasma resonance absworption peak of metallic particles at 350～450nm wave band, and the absorbance that is coated in organic dyestuff on the film through detection finds that this film has excellent photocatalytic performance under radiation of visible light.
The present invention is with cobalt nitrate; Silver nitrate is a raw material, and ethylene glycol monoemethyl ether is a solvent, adopts the metering of chemical solution method synthetic chemistry than accurate, the uniform precursor solution of composition; Adopt sol evenning machine on glass substrate, to film then, obtain Ag at last through thermal decomposition and annealing in process x/ (Co 3O 4) 1-xLaminated film.Concrete steps are:
(1) preparation precursor solution: at first according to Ag x/ (Co 3O 4) 1-x(wherein x representes the molar fraction of Ag component; The span of x is 0.01≤x≤0.85) stoichiometric proportion take by weighing the cobalt nitrate and the silver nitrate of respective amount, join respectively and prepare mother solution (concentration of Co mother solution is 3 times of Ag mother solution concentration) in the ethylene glycol monoemethyl ether solvent; On magnetic stirrer, stirred 1～3 hour, ageing 6～10 hours obtains red transparent Co mother solution and water white Ag mother solution again; Measure the Co mother solution and the Ag mother solution of respective volume then according to the x value, two kinds of solution are mixed, on magnetic stirrer, stirred 1～5 hour, ageing 6～10 hours forms the red transparent Ag with certain viscosity corresponding proportion x/ (Co 3O 4) 1-xPrecursor solution;
(2) preparation film: adopt sol evenning machine on glass substrate, to film.Before the even glue,, remove top impurity, put it in the drying box then and dry substrate ultrasonic cleaning in distilled water, ethanol, acetone successively; With the Ag for preparing x/ (Co 3O 4) 1-xPrecursor solution is coated on the dry substrate; Begin even glue then, the speed with 300～800rpm turned round 3～30 seconds earlier, and the speed with 2000～3100rpm turned round 10～80 seconds again; Whenever even glue once carries out thermal decomposition process one time in the back on heating plate, to remove the organic matter in the film; Heat decomposition temperature is 50～300 ℃, and the time is 0.5～3 minute; Next coating film is carried out by above-mentioned same steps as in sample cooling back, and film thickness is controlled at 1～500nm.Film after the end, place heat-treatment furnace to anneal in sample, 300～600 ℃ of annealing temperatures, annealing atmosphere is an air, annealing temperature retention time 10～200 minutes.
The main feature of the present invention's technology is: in prepared film; The silver uniform particles is scattered in the oxide matrix, and the plasma resonance absworption peak of silver metal particles has appearred in laminated film in optical absorption map, and optical absorption map is as shown in Figure 1; And nano metal surface plasma body resonant vibration effect and conductor photocatalysis effect have been combined; Responding to visible light has excellent photocatalytic performance, and the light degradation collection of illustrative plates is as shown in Figure 2.
Ag x/ (Co 3O 4) 1-xThe evaluation experimental condition of the light absorption of photochemical catalyst and photocatalysis performance is following:
The optical absorption intensity of ultraviolet-visible spectrophotometer testing film under different-waveband adopted in the light absorption evaluation;
In the photocatalysis evaluation experimental, adopting the 500W high pressure xenon lamp is the optical filter of 400nm as light source with by wavelength, with methylene blue solution as the simulating pollution thing.Experiment at first evenly is coated in methylene blue solution on the photocatalysis film, and system leaves standstill 20min foundation absorption-dissociation equilibrium under the situation of lucifuge then.Scribble the methylene blue film and measure its absorbance at regular intervals with radiation of visible light, absorbance numerical value records through ultraviolet-visible spectrophotometer.The characteristic absorption peak of known methylene blue records the absorbance of film at the 580nm place at λ=580nm, with the absorbance contrast of initial concentration, calculates the degradation rate of methylene blue on the different light time point.The photo-catalysis function film of silver particle-dispersed cobaltosic oxide demonstrates good surface plasma body resonant vibration and absorbs and photocatalysis characteristic, has extraordinary application prospect.
Description of drawings
A kind of Ag that Fig. 1 designs for the present invention x/ (Co 3O 4) 1-xAbsorbance collection of illustrative plates under the laminated film different-waveband, this figure explanation Ag x/ (Co 3O 4) 1-xLaminated film has the plasma resonance sink effect.
The Ag that Fig. 2 designs for the present invention x/ (Co 3O 4) 1-xBe coated with the variation collection of illustrative plates of methylene blue solution absorbance on the different light time point on the laminated film, this figure explanation Ag x/ (Co 3O 4) 1-xLaminated film has excellent photocatalytic performance.
The specific embodiment:
In the experimentation, it is pure that all chemicals of using are commercially available analysis.
Embodiment 1
Take by weighing the cobalt nitrate (Co (NO of 0.8731g 3) 26H 2O) and the silver nitrate (AgNO of 0.1699g 3) join respectively in the 10ml ethylene glycol monoemethyl ether solvent, on magnetic stirrer, stirred 3 hours ageing 6 hours; Obtaining concentration is the Co mother solution of 0.3mol/L and the Ag mother solution of 0.1mol/L; Measure the Co mother solution of 9.9ml and the Ag mother solution of 0.1ml then, two kinds of solution are mixed, on magnetic stirrer, stirred 5 hours again; Ageing 8 hours makes Ag 0.01/ (Co 3O 4) 0.99Precursor solution.Before the even glue, with substrate ultrasonic cleaning in distilled water, ethanol, acetone successively, put it in the drying box then and dry, dry back applies the Ag that one deck has prepared 0.01/ (Co 3O 4) 0.99Precursor solution is on substrate.When sparing glue, the speed with 300rpm turned round 3 seconds earlier, and the speed with 3000rpm turned round 10 seconds again, carried out thermal decomposition process one time behind the even glue, and heat decomposition temperature is 300 ℃, and the time is 30 seconds, applies the Ag of predetermined number of layers then again by above-mentioned steps 0.01/ (Co 3O 4) 0.99Precursor solution is on above-mentioned substrate.Film after the end, place heat-treatment furnace to anneal in sample, 550 ℃ of annealing temperatures, annealing temperature retention time 30 minutes obtains Ag at last 0.01/ (Co 3O 4) 0.99Laminated film.
Embodiment 2
Take by weighing the cobalt nitrate (Co (NO of 0.8731g 3) 26H 2O) and the silver nitrate (AgNO of 0.1699g 3) join respectively in the 10ml ethylene glycol monoemethyl ether solvent, on magnetic stirrer, stirred 3 hours ageing 6 hours; Obtaining concentration is the Co mother solution of 0.3mol/L and the Ag mother solution of 0.1mol/L; Measure the Co mother solution of 9ml and the Ag mother solution of 1ml then, two kinds of solution are mixed, on magnetic stirrer, stirred 5 hours again; Ageing 8 hours makes Ag 0.1/ (Co 3O 4) 0.9Precursor solution.Before the even glue, with substrate ultrasonic cleaning in distilled water, ethanol, acetone successively, put it in the drying box then and dry, dry back applies the Ag that one deck has prepared 0.1/ (Co 3O 4) 0.9Precursor solution is on substrate.When sparing glue, the speed with 300rpm turned round 3 seconds earlier, and the speed with 3000rpm turned round 10 seconds again, carried out thermal decomposition process one time behind the even glue, and heat decomposition temperature is 300 ℃, and the time is 30 seconds, applies the Ag of predetermined number of layers then again by above-mentioned steps 0.1/ (Co 3O 4) 0.9Precursor solution is on above-mentioned substrate.Film after the end, place heat-treatment furnace to anneal in sample, 550 ℃ of annealing temperatures, annealing temperature retention time 30 minutes obtains Ag at last 0.1/ (Co 3O 4) 0.9Laminated film.
Embodiment 3
Take by weighing the cobalt nitrate (Co (NO of 0.8731g 3) 26H 2O) and the silver nitrate (AgNO of 0.1699g 3) join respectively in the 10ml ethylene glycol monoemethyl ether solvent, on magnetic stirrer, stirred 3 hours ageing 6 hours; Obtaining concentration is the Co mother solution of 0.3mol/L and the Ag mother solution of 0.1mol/L; Measure the Co mother solution of 5.5ml and the Ag mother solution of 4.5ml then, two kinds of solution are mixed, on magnetic stirrer, stirred 5 hours again; Ageing 8 hours makes Ag 0.45/ (Co 3O 4) 0.55Precursor solution.Before the even glue, with substrate ultrasonic cleaning in distilled water, ethanol, acetone successively, put it in the drying box then and dry, dry back applies the Ag that one deck has prepared 0.45/ (Co 3O 4) 0.55Precursor solution is on substrate.When sparing glue, the speed with 300rpm turned round 3 seconds earlier, and the speed with 3000rpm turned round 10 seconds again, carried out thermal decomposition process one time behind the even glue, and heat decomposition temperature is 300 ℃, and the time is 30 seconds, applies the Ag of predetermined number of layers then again by above-mentioned steps 0.45/ (Co 3O 4) 0.55Precursor solution is on above-mentioned substrate.Film after the end, place heat-treatment furnace to anneal in sample, 550 ℃ of annealing temperatures, annealing temperature retention time 30 minutes obtains Ag at last 0.45/ (Co 3O 4) 0.55Laminated film.
Embodiment 4
Take by weighing the cobalt nitrate (Co (NO of 0.8731g 3) 26H 2O) and the silver nitrate (AgNO of 0.1699g 3) join respectively in the 10ml ethylene glycol monoemethyl ether solvent, on magnetic stirrer, stirred 3 hours ageing 6 hours; Obtaining concentration is the Co mother solution of 0.3mol/L and the Ag mother solution of 0.1mol/L; Measure the Co mother solution of 1.5ml and the Ag mother solution of 8.5ml then, two kinds of solution are mixed, on magnetic stirrer, stirred 5 hours again; Ageing 8 hours makes Ag 0.85/ (Co 3O 4) 0.15Precursor solution.Before the even glue, with substrate ultrasonic cleaning in distilled water, ethanol, acetone successively, put it in the drying box then and dry, dry back applies the Ag that one deck has prepared 0.85/ (Co 3O 4) 0.15Precursor solution is on substrate.When sparing glue, the speed with 300rpm turned round 3 seconds earlier, and the speed with 3000rpm turned round 10 seconds again, carried out thermal decomposition process one time behind the even glue, and heat decomposition temperature is 300 ℃, and the time is 30 seconds, applies the Ag of predetermined number of layers then again by above-mentioned steps 0.85/ (Co 3O 4) 0.15Precursor solution is on above-mentioned substrate.Film after the end, place heat-treatment furnace to anneal in sample, 550 ℃ of annealing temperatures, annealing temperature retention time 30 minutes obtains Ag at last 0.85/ (Co 3O 4) 0.15Laminated film.

Claims (1)

1. a silver nanoparticle-dispersed cobalt oxide functional thin-film material is characterized in that it is Ag that chemical composition is formed general formula x/ (Co 3O 4) 1-x, wherein x representes the molar fraction of Ag element, the span of x is 0.01≤x≤0.85; The silver nano-grain of diameter Distribution in 1～500nm scope is dispersed in the cobaltosic oxide matrix; Film is observed the plasma resonance absworption peak of metallic particles in 350～450nm wavelength band; The absorbance that is coated in organic dyestuff on the film through detection finds that this film has excellent photocatalytic performance under radiation of visible light;
The preparation method of described silver nanoparticle-dispersed cobalt oxide functional thin-film material; With cobalt nitrate; Silver nitrate is a raw material, and ethylene glycol monoemethyl ether is a solvent, adopts the metering of chemical solution method synthetic chemistry than accurate, the uniform precursor solution of composition; Adopt sol evenning machine on glass substrate, to film then, obtain Ag at last through thermal decomposition and annealing in process x/ (Co 3O 4) 1-xLaminated film; Concrete steps are:
(1) preparation precursor solution: at first according to Ag x/ (Co 3O 4) 1-xStoichiometric proportion take by weighing the cobalt nitrate and the silver nitrate of respective amount, join respectively in the ethylene glycol monoemethyl ether solvent and prepare mother solution, the concentration of Co mother solution is 3 times of Ag mother solution concentration; On magnetic stirrer, stirred 1～3 hour, ageing 6～10 hours obtains red transparent Co mother solution and water white Ag mother solution again; Measure the Co mother solution and the Ag mother solution of respective volume then according to the x value, two kinds of solution are mixed, on magnetic stirrer, stirred 1～5 hour, ageing 6～10 hours forms the red transparent Ag with certain viscosity corresponding proportion x/ (Co 3O 4) 1-xPrecursor solution;
(2) preparation film: adopt sol evenning machine on glass substrate, to film; Before the even glue,, remove top impurity, put it in the drying box then and dry substrate ultrasonic cleaning in distilled water, ethanol, acetone successively; With the Ag for preparing x/ (Co 3O 4) 1-xPrecursor solution is coated on the dry substrate; Begin even glue then, the speed with 300～800rpm turned round 3～30 seconds earlier, and the speed with 2000～3100rpm turned round 10～80 seconds again; Whenever even glue once carries out thermal decomposition process one time in the back on heating plate, to remove the organic matter in the film; Heat decomposition temperature is 50～300 ℃, and the time is 0.5～3 minute; Next coating film is carried out by above-mentioned same steps as in sample cooling back, and film thickness is controlled at 1～500nm; Film after the end, place heat-treatment furnace to anneal in sample, 300～600 ℃ of annealing temperatures, annealing atmosphere is an air, annealing temperature retention time 10～200 minutes.
CN201010034474XA 2010-01-21 2010-01-21 Silver nanoparticle-dispersed cobalt oxide functional thin film material and preparation method Expired - Fee Related CN101773838B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201010034474XA CN101773838B (en) 2010-01-21 2010-01-21 Silver nanoparticle-dispersed cobalt oxide functional thin film material and preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201010034474XA CN101773838B (en) 2010-01-21 2010-01-21 Silver nanoparticle-dispersed cobalt oxide functional thin film material and preparation method

Publications (2)

Publication Number Publication Date
CN101773838A CN101773838A (en) 2010-07-14
CN101773838B true CN101773838B (en) 2012-05-09

Family

ID=42510502

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201010034474XA Expired - Fee Related CN101773838B (en) 2010-01-21 2010-01-21 Silver nanoparticle-dispersed cobalt oxide functional thin film material and preparation method

Country Status (1)

Country Link
CN (1) CN101773838B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109273277B (en) * 2018-10-23 2020-04-14 东北大学秦皇岛分校 Preparation method of nano Ag embedded multi-stage electrode material
CN109321959B (en) * 2018-10-23 2019-10-25 东北大学秦皇岛分校 A kind of Electrochemical preparation method of nanometer Ag embedded electrode material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5688442A (en) * 1994-03-11 1997-11-18 Agency Of Industrial Science & Technology Nonlinear optical materials and process for producing the same
CN100392431C (en) * 2006-07-26 2008-06-04 北京科技大学 Process for producing nano copper particle dispersed silica optical thin film
CN101376568A (en) * 2008-10-13 2009-03-04 北京科技大学 Nano-silver particle dispersed cobalt oxide optical film and preparation thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5688442A (en) * 1994-03-11 1997-11-18 Agency Of Industrial Science & Technology Nonlinear optical materials and process for producing the same
CN100392431C (en) * 2006-07-26 2008-06-04 北京科技大学 Process for producing nano copper particle dispersed silica optical thin film
CN101376568A (en) * 2008-10-13 2009-03-04 北京科技大学 Nano-silver particle dispersed cobalt oxide optical film and preparation thereof

Also Published As

Publication number Publication date
CN101773838A (en) 2010-07-14

Similar Documents

Publication Publication Date Title
Yao et al. Microporous Ni-doped TiO2 film photocatalyst by plasma electrolytic oxidation
Bonanni et al. Conversion of colloidal ZnO− WO3 heteroaggregates into strongly blue luminescing ZnWO4 xerogels and films
Chen et al. Preparation and enhanced photoelectrochemical performance of coupled bicomponent ZnO− TiO2 nanocomposites
Kenanakis et al. Growth of c-axis oriented ZnO nanowires from aqueous solution: the decisive role of a seed layer for controlling the wires’ diameter
Chandiran et al. Quantum-confined ZnO nanoshell photoanodes for mesoscopic solar cells
Saarenpaa et al. Self-assembled porphyrins on modified zinc oxide nanorods: development of model systems for inorganic–organic semiconductor interface studies
CN105664935A (en) Three dimensional ordered meso-porous Au-TiO2/IO-SiO2 film visible light photocatalyst and preparation method thereof
CN102664215B (en) Method for preparing zinc selenide photoelectric film
CN106669716A (en) Preparation method of Cu2O/CuO/WO3 composite heterojunction thin film
CN110487772B (en) Three-dimensional SnO2Ag NPs Raman enhanced substrate and preparation method and application thereof
CN101773838B (en) Silver nanoparticle-dispersed cobalt oxide functional thin film material and preparation method
CN102254704A (en) Dye sensitized noble metal deposited titanium dioxide light anode and preparation method thereof
CN101767019B (en) Gold nano particle-dispersed cobaltosic oxide functional thin-film material and preparation method
CN102336528B (en) Vanadium dioxide film, its preparation and its application
CN102437209B (en) A kind of photoelectrocatalysithin thin film and preparation method thereof
CN105461044A (en) Method for degrading methylene blue solution
CN110270355A (en) A kind of preparation method of glass fabric load bismuth oxyiodide photocatalyst film
Liu et al. Significantly Enhanced Photoluminescence Performance of Ni x S y (NiS and Ni9S8)/ZnO Nanorods by a Hydrothermal Method
CN109092330B (en) CdSQDs@CdIn2S4/CdWO4Preparation of the Material
CN103736494A (en) Preparation method of ternary oxide film structure with visible light photoelectric catalysis effect
CN101767007B (en) Film material with function of copper nano particles dispersed in cobaltosic oxide and preparation method
CN101502793B (en) Method for preparing ZnO and CdO heterogeneous nanostructured oxide material
CN100411739C (en) Method for preparing nano titanium dioxide film
CN103435268B (en) There is under indoor visible light irradiation the preparation method of photocatalysis glass
CN104941696B (en) A kind of nano-TiO2The preparation method and products obtained therefrom of mixed crystal thin film

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20120509

Termination date: 20160121

EXPY Termination of patent right or utility model