CN108559512A - A kind of preparation method of photosensitive upper conversion composite material - Google Patents
A kind of preparation method of photosensitive upper conversion composite material Download PDFInfo
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- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7772—Halogenides
- C09K11/7773—Halogenides with alkali or alkaline earth metal
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7772—Halogenides
Abstract
The invention discloses a kind of preparation methods of photosensitive upper conversion composite material, belong to photoelectric field.The composite material is the photosensitive upper conversion composite material formed with the carrier loaded nano-titanium dioxide of hafnium modified RE doped fluoride, and the wherein addition of hafnium is 0.2 20mol% of Tricationic amount in fluoride carrier；By TiF4Or the titanium in butyl titanate is with oxide（TiO2）Form be loaded to hafnium modification rare-earth-doped fluoride carrier on, TiO2Load capacity and the molar ratio of carrier are 0.1 1.The modified RE doped fluoride carrier of difference hafnium content produced by the present invention has different Up-conversion emission spectral signatures, and after loading composite nano titanium dioxide, good photo absorption property is presented in gained composite material, and has preferable photoelectric sensitivity difference.
Description
Technical field
The invention belongs to photoelectric fields, more specifically to a kind of preparation method of photosensitive upper conversion composite material.
Background technology
Up-conversion luminescence is a nonlinear process, is converted after more than one low energy longer-wave photons energy is absorbed
Emit for a high energy short-wave photons, i.e., long-wave radiation is converted by shortwave radiation by multi-photon mechanism, realizes low-energy light
The conversion of wave direction high-energy light wave.In recent years, the up-conversion luminescent material of rare earth ion codope is concerned, wherein with activation
Ion Er3+Doped substrate hexagonal phase yttrium fluoride natrium（NaYF4）It is highest due to having low phonon energy and up-conversion luminescence efficiency
Feature, it is particularly eye-catching.It is included in medicine, life science, solar cell, display technology and catalyst etc. have extensively
Wealthy application prospect.However, because NaYF4: Er3+Up-conversion luminescence performance it is bad cause its application also have very big limitation.Mesh
Before, Up-conversion Intensity is improved by research by a relatively large margin, improves the up-conversion fluorescence service life；Main improved method
It is the size for adjusting matrix granule, particle surface modification, plasmon absorption enhancing, intense light source, which is saturated, to be excited, and energy turns
Be moved away from son and sensitized ions codope and build nanometer nuclear shell nano-structure etc..The up-conversion fluorescence service life of common reporter is often with upper
The enhancing of switching emission and accordingly extend.Although longer fluorescence lifetime is also beneficial to numerous applications, on certain fields
It converts luminous intensity to increase, while fluorescence lifetime shortens but with better application value.This is because die-away time longer meeting
Lead to hesitation, up-conversion luminescent material answering in 3D display, temperature sensor and dynamic detection field may be limited
With.So optimizing rear-earth-doped host material, upper conversion may be increased to obtain stronger intensity and service life appropriate
Luminescent material is more applied.
It is well known that doping is a kind of exploitation material novelty value and more useful categories for many functional materials
The important approach of property.For regulating and controlling rare earth codope hexagonal phase NaYF4Regulate and control Up-conversion emission bands of a spectrum feature and improves shortwave
Luminous intensity be still crystal field symmetry and neighbouring sensitization residing for challenge rare earth up-conversion luminescence performance and a rare earth ion and
The property of energy transfer ion has close relationship.Different radii and valence state Heteroatom doping can effective modulation matrix structure crystalline substances
Field symmetry and the ion with specific band structure may also participate in the energy transmission of rare earth ion up-conversion luminescence.Another party
Face, in early stage the 1970s, Japanese researchers Fujishima and Honda, which just have proven to titanium dioxide, has a series of light
Electrochemical properties.In the research of early stage, they construct an electrochemical cell, and electrode is by titanium dioxide and is dipped in water
Platinum is interconnected by area load and is formed.Oxide electrode is irradiated by light, they have monitored from metal electrode to external circuit
There is electric current to flow through, they infer that the electrons inside titanium dioxide out form electric current by photon excitation, that is, have photoproduction electricity
Phenomenon (1-1-1).It being flowed to by monitoring current, they infer has occurred oxidation (1-1-2) in oxide electrode, and in gold
Belong to electrode and reduction (1-1-3) has occurred.This is also shown that water possibly through the additional effect of visible light to be decomposed into hydrogen
And oxygen.
TiO2+2hν→2e-+2p+ (1-1-1)
2p++H2O→1/2O2+2H+ (1-1-2)
2e-+2H+→H2 (1-1-3)
Titanium dioxide has the gate that photoelectric discovery opens many new research application directions, including：1, using two
Titanium oxide eliminates the pollutant in environment as photochemical catalyst；2, the new method converted solar energy into electrical energy i.e. photoproduction
Electricity, such as dye-sensitized solar cells (DSSC)；3, solar hydrogen making.
But, with the opening that this fans new gate, researchers start to find that wider energy gap limits titanium dioxide
A series of application of semiconducting compounds such as titanium.The band structure of semiconductor is often the low energy valence band and one for being full of electronics by one
The higher energy conduction band of a sky is constituted, and the region between them is known as forbidden band, and the forbidden band of semiconductor is a discontinuity zone.It is general to use
The semiconductor of photocatalyst and solar cell is mostly the oxide and sulfide of metal, is with larger energy gap
Band gap is indicated with Eg.The light absorption threshold value of semiconductor is related with band gap, and relationship is represented by：
λg (nm)=1240/Eg(eV) (1-2)
By formula (1-2) it is found that light absorption wavelength threshold value λ g and band gap Eg is inversely proportional.
It follows that wider energy gap means that titanium dioxide can only utilize ultraviolet light.Ultraviolet light is only in sunlight
In occupy about 4%, and about 50% cannot be occupied respectively in sunlight by the visible light and near infrared light that titanium dioxide directly utilizes
With 46%.Then, how to remove to efficiently use these photons for being less than energy gap energy, for by titanium dioxide in optical electro-chemistry
The problem of being a essence for the further application in field.Later, researchers put forward a new idea：Upper conversion is sent out
Light is applied in optical electro-chemistry field to solve the problems, such as this.Daisheng Zhang etc. are prepared for NaYF4:Yb, Tm/TiO2
Core/Shell nano-particle materials have done the research that the differential responses time simply regulates and controls in nucleocapsid different thickness of the shells.
Tong hui Yu etc. are prepared for NaYbF4:Tm3+@TiO2Core-shell structure material, the photoelectric effect and its photoelectric current having to it are big
It is small to have carried out particular study.Wanjun Wang etc. are prepared for α-NaYF4:Yb,Tm@TiO2 core-shell structure
Supported on reduced graphene oxide materials, have carried out photoelectric current size to it and have compared, methylene blue MB,
The research of methyl orange MO and the lower mechanism of phenol degrading and scavenger characterization.It can be seen that upper conversion composite semiconductor material tool
Have has potential researching value and application prospect in light-sensitive material field.The present invention selects Hf4+Codope hexagonal phase NaYF4:
Yb3+, Er3+, Hf4+Doping significantly improve NaYF4: Yb3+, Er3+Emitted luminescence intensity and modulation its fluorescence lifetime, then will
Hf4+Codope hexagonal phase NaYF4: Yb3+With TiO2It is compound to prepare the upper conversion photosensitized composite material that responded to infrared light.
Invention content
The purpose of the present invention is to provide a kind of preparation methods of photosensitive upper conversion composite material, especially with hafnium modified RE
Fluoride is the preparation method of carrier loaded titanium-dioxide photo composite.The present invention passes through controlling reaction temperature, raw material ratio
Example and Hf4+The means such as ion doping regulation and control synthesize the rear-earth-doped fluorine yttrium acid sodium micron material with different Up-conversion emission intensity
Material recycles water bath heating in its area load TiO2Nano particle prepares fluorine yttrium acid sodium composite titanium dioxide material, can
As a kind of effective light-sensitive material.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of preparation method of photosensitive upper conversion composite material, specifically includes following steps：
（One）The preparation of hafnium modified RE doped fluoride carrier：
1）Trivalent metal oxide and rare earth oxide are weighed respectively, is dissolved in a heated condition with nitric acid, are configured to respectively
The Tricationic solution of 1mol/L and the rare-earth ion solution of 1mol/L, it is spare；
2）Weigh HfF4、HfO2Or HfO (OH)2, hydrofluoric acid dissolution is used in a heated condition, is configured to the HfF of 1mol/L4Solution,
It is spare as support modification agent；
3）Surfactant and chelating agent are weighed respectively, are dissolved with water or ethyl alcohol under room temperature, are configured to the surface of 1mol/L respectively
The chelating agent solution of activator solution and 1mol/L, it is spare；
4）A polytetrafluoroethylene beaker is taken, water or ethyl alcohol are added inward, is then respectively adding step 3）The surface-active of preparation
Agent solution and chelating agent solution；Then step 1 is added dropwise respectively under agitation）The Tricationic solution of preparation and dilute
Native solion；A dropping step 2 again after stirring）The HfF of preparation4Solution；Alkali metal fluoride solution or hydrogen are added dropwise under stiring
NH is added dropwise after continuing stirring in fluorspar acid solution4F or NH4HF2Solution；Then mixed solution pH value is adjusted to 3- with ammonium hydroxide or hydrofluoric acid
4, after continuing stirring, mixed solution is moved in polytetrafluoroethylene (PTFE) autoclave, is reacted 8-16 hours at 150-190 DEG C, is reacted
After, it takes out and distinguishes centrifuge washing three times with hexamethylene and deionized water, then dry in an oven, it is dilute to obtain hafnium modification
Native doped fluoride carrier；
（Two）The preparation of photosensitive upper conversion composite material：
With TiF4Or TiCl4For titanium source, by itself and step（One）Hafnium modified RE doped fluoride carrier mixing obtained, passes through
The photosensitive upper conversion composite material of titanium dichloride load is made in the method for heating water bath；Or using butyl titanate as titanium source, by it
With step（One）It is negative that titanium dioxide is made after calcining under an inert gas in hafnium modified RE doped fluoride carrier mixing obtained
The photosensitive upper conversion composite material carried；
Step 1）Described in trivalent metal oxide be Y2O3、Sc2O3、Bi2O3And Gd2O3Any one of；The rare earth
Oxide is Yb2O3With Er2O3、Tm2O3And Ho2O3Any one of mixture or Nd2O3With Er2O3、Tm2O3And Ho2O3
Any one of mixture.
The surfactant is one or more in CTAB, ethylene glycol, P123 and oleic acid.
The chelating agent is EDTA dilithium salts, EDETATE DISODIUM, dipotassium EDTA salt, bis- rubidium salt of EDTA, bis- cesium salts of EDTA
Any one of with EDTA diaminos.
Step 4）In, when the rare earth ion of addition includes Yb3+When, the additive amount of rare earth ion is the 5- of Tricationic
30mol%；When the rare earth ion of addition includes Nd3+When, the additive amount of rare earth ion is the 0.5-3mol% of Tricationic.
Step 4）In, Hf4+Additive amount be Tricationic 0.2-20mol%.
Step 4）Described in alkali metal fluoride be any one of LiF, NaF, KF, RbF and CsF；The alkali gold
The concentration for belonging to fluoride aqueous solution and hydrofluoric acid solution is 1mol/L.
Step（Two）In the photosensitive upper conversion composite material of titanium dichloride load obtained, the titanium dioxide of load and fluorination
The molar ratio of object carrier is 0.1-1.
Step（Two）In, with TiF4Or TiCl4The tool of the photosensitive upper conversion composite material of titanium dichloride load is prepared for titanium source
Body process is：By TiF4Or TiCl4It is dissolved in the deionized water of 50mL under 35 DEG C of water bath conditions, is configured to the clarification of 0.08M
Solution；0.1g steps are weighed again（One）Hafnium modified RE doped fluoride carrier obtained pours into TiF4Or TiCl4In solution,
12-24h is heated under 40-60 DEG C of water bath condition, and is stirred continuously；Products obtained therefrom is finally used into absolute ethyl alcohol and deionized water respectively
Centrifuge washing is primary, and centrifugal speed is 6000~8000 rpm, and after drying in an oven, and drying temperature is 60 DEG C, when dry
Between be 12h；Grinding is collected, and the photosensitive upper conversion composite material of titanium dichloride load is made.
Step（Two）In, the tool of the photosensitive upper conversion composite material of titanium dichloride load is prepared using butyl titanate as titanium source
Body process is：It weighs butyl titanate to be dissolved in the ethyl alcohol of 50mL, is configured to 0.1M solution of tetrabutyl titanate；Then it weighs
0.1g steps（One）Hafnium modified RE doped fluoride support dispersion obtained forms suspension in the water of 20mL；Then exist
Solution of tetrabutyl titanate is added to the suspension of hafnium modified RE doped fluoride carrier under stirring condition in the form of spraying
In, continue to stir 0.5-2h after adding, be then centrifuged for simultaneously drying in an oven, centrifugal speed is 6000~8000 rpm, dry
Temperature is 60 DEG C, drying time 12h；1-5h finally is calcined under nitrogen atmosphere at 500-600 DEG C, titanium dichloride load is made
Photosensitive upper conversion composite material.
The beneficial effects of the present invention are：The modified RE doped fluoride carrier tool of difference hafnium content produced by the present invention
There is different Up-conversion emission spectral signatures, after loading composite nano titanium dioxide, gained composite material is presented good light and rings
Performance is answered, and there is preferable photoelectric sensitivity difference.
Description of the drawings
Fig. 1 is the XRD spectrum of photosensitive upper conversion composite material prepared by embodiment 1, characterizes its phase character；
Fig. 2 be embodiment 1 prepare photosensitive upper conversion composite material with TiO2The compound front and back stereoscan photograph compared,
In（a）For the stereoscan photograph of compound preceding sample,（b）For Hf6 and TiO2The stereoscan photograph of sample after compound；
Fig. 3 is the Up-conversion emission collection of illustrative plates of photosensitive upper conversion composite material prepared by embodiment 1, characterizes its optical property；
Fig. 4 is the electrochemistry i-t curves of photosensitive upper conversion composite material prepared by embodiment 1, characterizes its opto-electronic conversion performance.
Specific implementation mode
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited only to these embodiments.
Embodiment 1
Photosensitized composite material chemical formula：NaYF4:Yb/Er&TiO2, preparation process includes the following steps：
1) carrier（NaYF4）Synthesis
Configuration concentration is the Y (NO of 1mol/L first3)3, NaF, NH4HF2, EDTA (disodium) solution and a concentration of 0.1mol/L
Yb (NO3)3, Er (NO3)3, HfF4Solution.With Yb3+, Er3+Two kinds of rare earth ion parts replace Y3+, substitution mole be respectively
Quantitative 5% and quantitative 3%, then with Hf4+Ionic compartmentation part Y3+, substituted mole is variable 0%, 2%, 4%, 6%, 8%.By Yb
(NO3)3, Er (NO3)3Respectively quantify 0.5ml and 0.3ml, Y (NO3)3For variable 0.92ml, 0.9ml, 0.88ml, 0.86ml,
0.84ml, corresponding HfF4For variable 0ml, 0.2ml, 0.4ml, 0.6ml, 0.8ml.Then by the molten of five set different ratio
Liquid is added drop-wise to dropwise in 1.5mlEDTA solution, is stirred 30min, is denoted as solution A.By 1mlNaF and 1.5mlNH4HF2In 25ml second
Obtained solution B after being dissolved in alcohol.Then solution B is added drop-wise to dropwise in the solution A being stirred continuously, then uses HF (or NaOH)
The pH value of AB mixed solutions is adjusted to 3, continues to stir 30min.Solution after stirring is packed into the polytetrafluoro of five identical capacity
In ethylene water heating kettle, it is put into baking oven, is heated to 190 DEG C, keeps the temperature 8 hours, then natural cooling causes room temperature.It is first clear with hexamethylene
It washes 3 times, then with washes of absolute alcohol 3 times, is finally cleaned 3 times with deionized water.The sample that cleaning obtains is put into 60 DEG C of baking ovens
In, it is collected after drying and obtains NaYF4：The sample of different Hf incorporations is pressed Hf incorporations by Yb/Er/Hf up-conversion luminescent materials
It is denoted as Hf0, Hf2, Hf4, Hf6, Hf8 respectively.
2) fluorine yttrium acid sodium composite titanium dioxide（NaYF4&TiO2）The synthesis of light-sensitive material, by five parts of 0.4954g TiF4
It is dissolved separately in the deionized water of 50mL under 35 DEG C of water bath conditions, is configured to the clear solution of 0.08M, then by step 1）It prepares
Material weigh 0.1g respectively and pour into corresponding TiF respectively4It in solution, is stirred continuously under 50 DEG C of water bath conditions, heat preservation is for 24 hours.
Then use second alcohol and water centrifuge washing primary respectively the product after reaction, and in an oven after 60 DEG C of dryings, grinding is collected, will
Products obtained therefrom is denoted as Hf0＆TiO successively by Hf doping concentrations2、Hf2&TiO2、Hf4&TiO2、Hf6&TiO2、Hf8&TiO2。
3）Photoelectric effect test is carried out to composite material, process is as follows：By blocking stainless (steel) wire be cut into piecewise 2cm ×
After the small pieces of 6cm, successively using respectively cleaning one time of dilute NaOH, deionized water and absolute ethyl alcohol, it is put into baking oven and is dried at 60 DEG C
It is dry.The composite material synthesized by 0.01g is equably applied on processed stainless (steel) wire respectively, is dripped on the composite
Enter a drop adhensive membrane solution, forms the white thin layer of 2cm × 0.4cm, be put into baking oven the drying at 60 DEG C, will finally dry
The stainless (steel) wire containing sample along longitudinal direction doubling carry out tabletting, the pressurize 2min at 10MPa.Stainless steel to handle well later
Net is carried out using Ag/AgCl as reference electrode in electrochemical workstation as working electrode using platinum electrode as to electrode
I-t curves（Current versus time curve）Test.
Embodiment 2
Photosensitized composite material chemical formula：NaYF4:Yb/Tm&TiO2, preparation process includes the following steps：
1) carrier（NaYF4）Synthesis
Configuration concentration is the Y (NO of 1mol/L first3)3, NaF, NH4HF2, EDTA (disodium) solution and a concentration of 0.1mol/L
Yb (NO3)3, Tm (NO3)3, HfF4Solution.With Yb3+, Er3+Two kinds of rare earth ion parts replace Y3+, substitution mole be respectively
Quantitative 5% and quantitative 3%, then with Hf4+Ionic compartmentation part Y3+, substituted mole is variable 0%, 2%, 4%, 6%, 8%.By Yb
(NO3)3, Er (NO3)3Respectively quantify 0.5ml and 0.3ml, Y (NO3)3For variable 0.92ml, 0.9ml, 0.88ml, 0.86ml,
0.84ml, corresponding HfF4For variable 0ml, 0.2ml, 0.4ml, 0.6ml, 0.8ml.Then by the molten of five set different ratio
Liquid is added drop-wise to dropwise in 1.5mlEDTA solution, is stirred 30min, is denoted as solution A.By 1ml NaF and 1.5ml NH4HF2In 25ml
Obtained solution B after being dissolved in ethyl alcohol.Then solution B is added drop-wise to dropwise in the solution A being stirred continuously, then use HF (or
NaOH the pH value of AB mixed solutions) is adjusted to 3, continues to stir 30min.By the poly- of solution five identical capacity of loading after stirring
In tetrafluoroethene water heating kettle, it is put into baking oven, is heated to 190 DEG C, keeps the temperature 8 hours, then natural cooling causes room temperature.First use hexamethylene
Alkane cleans 3 times, then with washes of absolute alcohol 3 times, is finally cleaned 3 times with deionized water.The sample that cleaning obtains is put into 60 DEG C
It is collected in baking oven, after drying and obtains NaYF4：Yb/Tm/Hf up-conversion luminescent materials are mixed the sample of different Hf incorporations by Hf
Enter amount and is denoted as Hf0, Hf2, Hf4, Hf6, Hf8 respectively.
2) fluorine yttrium acid sodium composite titanium dioxide（NaYF4&TiO2）The synthesis of light-sensitive material, by five parts of 0.4954g TiF4
It is dissolved separately in the deionized water of 50mL under 35 DEG C of water bath conditions, is configured to the clear solution of 0.08M, then by step 1）It prepares
Material weigh 0.1g respectively and pour into corresponding TiF respectively4It in solution, is stirred continuously, is kept the temperature for 24 hours under 50 DEG C of water bath conditions,.
Then use second alcohol and water centrifuge washing primary respectively the product after reaction, and in an oven after 60 DEG C of dryings, grinding is collected, will
Products obtained therefrom is denoted as Hf0＆TiO successively by Hf doping concentrations2、Hf2&TiO2、Hf4&TiO2、Hf6&TiO2、Hf8&TiO2。
3）Photoelectric effect test is carried out to composite material, process is as follows：By blocking stainless (steel) wire be cut into piecewise 2cm ×
After the small pieces of 6cm, successively using respectively cleaning one time of dilute NaOH, deionized water and absolute ethyl alcohol, it is put into baking oven and is dried at 60 DEG C
It is dry.The composite material synthesized by 0.01g is equably applied on processed stainless (steel) wire respectively, is dripped on the composite
Enter a drop adhensive membrane solution, forms the white thin layer of 2cm × 0.4cm, be put into baking oven the drying at 60 DEG C, will finally dry
The stainless (steel) wire containing sample along longitudinal direction doubling carry out tabletting, the pressurize 2min at 10MPa.Stainless steel to handle well later
Net is carried out using Ag/AgCl as reference electrode in electrochemical workstation as working electrode using platinum electrode as to electrode
I-t curves（Current versus time curve）Test.
Embodiment 3
Photosensitized composite material chemical formula：YF3:Yb/Er&TiO2, preparation process includes the following steps：
1) carrier（YF3）Synthesis
Configuration concentration is the Y (NO of 1mol/L first3)3, HF, NH4HF2, EDTA (diamino) solution and a concentration of 0.1mol/L
Yb (NO3)3, Er (NO3)3, HfF4Solution.With Yb3+, Er3+Two kinds of rare earth ion parts replace Y3+, substitution mole be respectively
Quantitative 5% and quantitative 3%, then with Hf4+Ionic compartmentation part Y3+, substituted mole is variable 0%, 2%, 4%, 6%, 8%.By Yb
(NO3)3, Er (NO3)3Respectively quantify 0.5ml and 0.3ml, Y (NO3)3For variable 0.92ml, 0.9ml, 0.88ml, 0.86ml,
0.84ml, corresponding HfF4For variable 0ml, 0.2ml, 0.4ml, 0.6ml, 0.8ml.Then by the molten of five set different ratio
Liquid is added drop-wise to dropwise in 1.5ml EDTA solution, is stirred 30min, is denoted as solution A.By 1ml NaF and 1.5ml NH4HF2In 25ml
Obtained solution B after being dissolved in ethyl alcohol.Then solution B is added drop-wise to dropwise in the solution A being stirred continuously, then uses HF (or ammonia
Water) pH value of AB mixed solutions is adjusted to 3, continue to stir 30min.Solution after stirring is packed into poly- the four of five identical capacity
In vinyl fluoride water heating kettle, it is put into baking oven, is heated to 190 DEG C, keeps the temperature 8 hours, then natural cooling causes room temperature.First use hexamethylene
Cleaning 3 times, then with washes of absolute alcohol 3 times, finally cleaned 3 times with deionized water.The sample that cleaning obtains is put into 60 DEG C of bakings
It is collected in case, after drying and obtains YF3：The sample of different Hf incorporations is pressed Hf incorporations by Yb/Er/Hf up-conversion luminescent materials
It is denoted as Hf0, Hf2, Hf4, Hf6, Hf8 respectively.
2) fluorine yttrium acid sodium composite titanium dioxide（YF3&TiO2）The synthesis of light-sensitive material, by five parts of 0.4954g TiF435
It is dissolved separately in the deionized water of 50mL under DEG C water bath condition, is configured to the clear solution of 0.08M, then by step 1）It prepares
Material weighs 0.1g and pours into corresponding TiF respectively respectively4It in solution, is stirred continuously, is kept the temperature for 24 hours under 50 DEG C of water bath conditions,.So
Use second alcohol and water centrifuge washing primary respectively the product after reaction afterwards, and in an oven after 60 DEG C of dryings, grinding is collected, by institute
It obtains product and is denoted as Hf0＆TiO successively by Hf doping concentrations2、Hf2&TiO2、Hf4&TiO2、Hf6&TiO2、Hf8&TiO2。
3）Photoelectric effect test is carried out to composite material, process is as follows：By blocking stainless (steel) wire be cut into piecewise 2cm ×
After the small pieces of 6cm, respectively cleaning one time of weak aqua ammonia, deionized water and absolute ethyl alcohol is used successively, is put into baking oven and is dried at 60 DEG C
It is dry.The composite material synthesized by 0.01g is equably applied on processed stainless (steel) wire respectively, is dripped on the composite
Enter a drop adhensive membrane solution, forms the white thin layer of 2cm × 0.4cm, be put into baking oven the drying at 60 DEG C, will finally dry
The stainless (steel) wire containing sample along longitudinal direction doubling carry out tabletting, the pressurize 2min at 10MPa.Stainless steel to handle well later
Net is carried out using Ag/AgCl as reference electrode in electrochemical workstation as working electrode using platinum electrode as to electrode
I-t curves（Current versus time curve）Test.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification should all belong to the covering scope of the present invention.
Claims (10)
1. a kind of preparation method of photosensitive upper conversion composite material, it is characterised in that：Specifically include following steps：
（One）The preparation of hafnium modified RE doped fluoride carrier：
1）Trivalent metal oxide and rare earth oxide are weighed respectively, is dissolved in a heated condition with nitric acid, are configured to respectively
The Tricationic solution of 1mol/L and the rare-earth ion solution of 1mol/L, it is spare；
2）Weigh HfF4、HfO2Or HfO (OH)2, hydrofluoric acid dissolution is used in a heated condition, is configured to the HfF of 1mol/L4Solution,
It is spare as support modification agent；
3）Surfactant and chelating agent are weighed respectively, are dissolved with water or ethyl alcohol under room temperature, are configured to the surface of 1mol/L respectively
The chelating agent solution of activator solution and 1mol/L, it is spare；
4）A polytetrafluoroethylene beaker is taken, water or ethyl alcohol are added inward, is then respectively adding step 3）The surface-active of preparation
Agent solution and chelating agent solution；Then step 1 is added dropwise respectively under agitation）The Tricationic solution of preparation and dilute
Native solion；A dropping step 2 again after stirring）The HfF of preparation4Solution；Alkali metal fluoride solution or hydrogen are added dropwise after agitation
Fluorspar acid solution；Continue that NH is added dropwise under stirring condition4F or NH4HF2Solution；Then use ammonium hydroxide or hydrofluoric acid by mixed solution pH value tune
To 3-4, after continuing stirring, mixed solution is moved in polytetrafluoroethylene (PTFE) autoclave, is reacted 8-16 hours at 150-190 DEG C,
After reaction, it takes out and distinguishes centrifuge washing three times with hexamethylene and deionized water, then dry in an oven, obtain hafnium and change
Property rare-earth-doped fluoride carrier；
（Two）The preparation of photosensitive upper conversion composite material：
With TiF4Or TiCl4For titanium source, by itself and step（One）Hafnium modified RE doped fluoride carrier mixing obtained, passes through
The photosensitive upper conversion composite material of titanium dichloride load is made in the method for heating water bath；Or using butyl titanate as titanium source, by it
With step（One）It is negative that titanium dioxide is made after calcining under an inert gas in hafnium modified RE doped fluoride carrier mixing obtained
The photosensitive upper conversion composite material carried；
Step 1）Described in trivalent metal oxide be Y2O3、Sc2O3、Bi2O3And Gd2O3Any one of；The rare earth oxygen
Compound is Yb2O3With Er2O3、Tm2O3And Ho2O3Any one of mixture or Nd2O3With Er2O3、Tm2O3And Ho2O3In
Any mixture.
2. the preparation method of photosensitive upper conversion composite material according to claim 1, it is characterised in that：It lives on the surface
Property agent be CTAB, ethylene glycol, P123 and oleic acid in it is one or more.
3. the preparation method of photosensitive upper conversion composite material according to claim 1, it is characterised in that：The chelating agent
For any one of EDTA dilithium salts, EDETATE DISODIUM, dipotassium EDTA salt, bis- rubidium salt of EDTA, bis- cesium salts of EDTA and EDTA diaminos.
4. the preparation method of photosensitive upper conversion composite material according to claim 1, it is characterised in that：Step 4）In, when
The rare earth ion of addition includes Yb3+When, the additive amount of rare earth ion is the 5-30mol% of Tricationic；When addition rare earth from
Attached bag contains Nd3+When, the additive amount of rare earth ion is the 0.5-3mol% of Tricationic.
5. the preparation method of photosensitive upper conversion composite material according to claim 1, it is characterised in that：Step 4）In, Hf4+
Additive amount be Tricationic 0.2-20mol%.
6. the preparation method of photosensitive upper conversion composite material according to claim 1, it is characterised in that：Step 4）Described in
Alkali metal fluoride be any one of LiF, NaF, KF, RbF and CsF；The alkali metal fluoride solution and hydrofluoric acid
The concentration of solution is 1mol/L.
7. the preparation method of photosensitive upper conversion composite material according to claim 1, it is characterised in that：Step（Two）It is made
Titanium dichloride load photosensitive upper conversion composite material in, the titanium dioxide of load and the molar ratio of fluoride carrier are 0.1-
1。
8. the preparation method of photosensitive upper conversion composite material according to claim 1, it is characterised in that：Step（Two）In,
With TiF4Or TiCl4For titanium source prepare titanium dichloride load it is photosensitive it is upper conversion composite material detailed process be：By TiF4Or
TiCl4It is dissolved in the deionized water of 50mL under 35 DEG C of water bath conditions, is configured to the clear solution of 0.08M；0.1g is weighed again
Step（One）Hafnium modified RE doped fluoride carrier obtained pours into TiF4Or TiCl4In solution, in 40-60 DEG C of water bath condition
Lower heating 12-24h, and be stirred continuously；Finally use absolute ethyl alcohol and deionized water centrifuge washing primary respectively products obtained therefrom, and
After drying in an oven, grinding is collected, and the photosensitive upper conversion composite material of titanium dichloride load is made.
9. the preparation method of photosensitive upper conversion composite material according to claim 1, it is characterised in that：Step（Two）In,
Prepared by titanium source of butyl titanate titanium dichloride load it is photosensitive it is upper conversion composite material detailed process be：Weigh metatitanic acid four
Butyl ester is dissolved in the ethyl alcohol of 50mL, is configured to 0.1M solution of tetrabutyl titanate；Then 0.1g steps are weighed（One）Hafnium obtained
Modified RE doped fluoride support dispersion forms suspension in the water of 20mL；
Then solution of tetrabutyl titanate is added to hafnium modified RE doped fluoride load in the form of spraying under agitation
In the suspension of body, continues to stir 0.5-2h after adding, be then centrifuged for simultaneously drying in an oven, finally the nitrogen at 500-600 DEG C
1-5h is calcined under gas atmosphere, the photosensitive upper conversion composite material of titanium dichloride load is made.
10. the preparation method of photosensitive upper conversion composite material according to claim 8 or claim 9, it is characterised in that：Described
Centrifugal speed is 6000~8000 rpm, and drying temperature is 60 DEG C after centrifugation, drying time 12h.
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