CN108587601A - A kind of rear-earth-doped Au@TiO2Core-shell structured nanomaterials and preparation and application - Google Patents
A kind of rear-earth-doped Au@TiO2Core-shell structured nanomaterials and preparation and application Download PDFInfo
- Publication number
- CN108587601A CN108587601A CN201810533950.9A CN201810533950A CN108587601A CN 108587601 A CN108587601 A CN 108587601A CN 201810533950 A CN201810533950 A CN 201810533950A CN 108587601 A CN108587601 A CN 108587601A
- Authority
- CN
- China
- Prior art keywords
- core
- earth
- tio
- doped
- shell structured
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
- C09K11/7701—Chalogenides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
- C09K11/7767—Chalcogenides
- C09K11/7769—Oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
Abstract
The invention belongs to field of light emitting materials, and in particular to a kind of rear-earth-doped Au@TiO2Core-shell structured nanomaterials and preparation and application.The present invention mixes soluble gold salt solution and citric acid three sodium solution, is stirred to react；Ascorbic acid solution is added, the reaction was continued for stirring；Then TiF is added4Solution, carries out hydro-thermal reaction, and centrifugation, washing obtain Au@TiO2Core-shell structured nanomaterials；By Au@TiO2Core-shell structured nanomaterials are dispersed in water；Then rare-earth chloride solution is added, carries out hydro-thermal reaction, centrifuge washing obtains rear-earth-doped Au@TiO2Core-shell structured nanomaterials.The material has the emission band of wider upper conversion and lower excitation threshold；In addition, the multi-functional also with photothermal conversion and photocatalysis etc., has important potential using value in solar cell, LED illumination, bio-sensing and field of environment protection.
Description
Technical field
The invention belongs to field of light emitting materials, and in particular to a kind of rear-earth-doped Au@TiO2Core-shell structured nanomaterials and
Preparation and application.
Background technology
In recent years, with the enhancing of people's environmental protection consciousness and the appearance of energy crisis, suitable green energy is found
Source substitutes the extensive concern that traditional energy receives scientific circles and industrial quarters.Solar cell capable of being converted to solar energy as a kind of
The photoelectric device of electric energy provides a kind of effective way obtaining green energy resource, becomes one of researcher focus of attention.
Prepare can efficiently use solar energy and the higher solar cell of efficiency at vast researcher research hotspot field.
In solar spectrum, most of light wave is located at visible and infrared band, and the light (800~1700nm) of wherein infrared band accounts about ratio
55~60%.In single solar cell, since most extinction material can not effectively absorb near infrared light, greatly limit
The light conversion efficiency of solar cell is made.
Up-conversion luminescent material is a kind of substance that VISIBLE LIGHT EMISSION can be converted infrared light to by multi-photon mechanism,
Efficiently to provide a kind of effective method using sunlight.However, the light of the solar cell currently based on up-conversion luminescence layer
Electric energy conversion efficiency is also relatively low, is substantially at the experimental study stage, some basic problem in science solve not yet, such as：
1) traditional rare earth up-conversion luminescent material emission spectrum is relatively narrow, can not be with the absorption spectra matched well of photosensitive material；2) at present
The luminous efficiency of up-conversion luminescent material is relatively low and excitation threshold is higher.In order to solve these Fundamental Aspects, researchers
Use different methods.For example, the rare earth ion that the new host material or doping for designing and developing low phonon energy is different；
Up-conversion nano material surface coats different substances, reduces the defect and dangling bonds of material surface；Design is compound with noble metal
Nanocomposite etc..Chinese invention patent (publication number CN105969347A) discloses a kind of Yb3+@Eu3+@Y3+It is co-doped with
Miscellaneous CaF2Up-conversion luminescent material, provide a kind of method obtaining upper conversion of white light under the excitation of~980nm near infrared lights,
The patent of invention mainly uses three kinds of rare earth ion doped methods, is prepared for a kind of white up-conversion luminescent material, does not have
It is related to noble metal nanometer material nucleocapsid.Chinese invention patent (publication number CN107163930A) discloses a kind of with core
The white light infrared up conversion composite luminescent material of shell structure, the upper conversion composite material are that the infrared up conversion of blue light-emitting is received
The characteristics of rice material is formed with the quantum dot with fluorescent red-orange characteristic, the patent of invention is to be with up-conversion nano material
Core, quanta point material are that shell prepares nucleocapsid.Document [J.Phys.Chem.C 2014,118,3258-3265] reports one
Kind Yb2O3Conversion nano compound material on@Au, during preparation, gold nanorods are gradually dissolved into small gold nano grain
It is dispersed in up-conversion nano material, which has the characteristics that broadband excitation and broadband emission.It is well known that noble metal nano
Material, especially gold nano-material, since with surface plasma resonance characteristic, the luminous intensity etc. of fluorophor can be enhanced,
As the hot spot of the research of luminescent material in recent years.It is above-mentioned had a document report as a result, some without utilizing noble metal nano
The preparation nanometer nuclear shell nano-structure of material, has plenty of and gold nano-material is dissolved into luminescent material, and prepared material does not have
Broadband emission or the property of Low threshold excitation.
Invention content
For overcome the deficiencies in the prior art and disadvantage, the primary purpose of the present invention is that providing a kind of rear-earth-doped Au@
TiO2The preparation method of core-shell structured nanomaterials.
Another object of the present invention is to provide the rear-earth-doped Au@TiO that above-mentioned preparation method is prepared2Nucleocapsid
Nano material.
It is still another object of the present invention to provide above-mentioned rear-earth-doped Au@TiO2The application of core-shell structured nanomaterials.
The purpose of the invention is achieved by the following technical solution：
A kind of rear-earth-doped Au@TiO2The preparation method of core-shell structured nanomaterials, comprises the following steps：
(1) soluble gold salt solution and citric acid three sodium solution are mixed, is stirred to react；It is molten that ascorbic acid (AA) is added
Liquid, the reaction was continued for stirring；Then TiF is added4Solution, carries out hydro-thermal reaction, and centrifuge washing obtains Au@TiO2Nuclear shell structure nano
Material；
(2) by Au@TiO made from step (1)2Core-shell structured nanomaterials are dispersed in water；Then rare-earth chlorination is added
Object solution, carries out hydro-thermal reaction, and centrifuge washing obtains rear-earth-doped Au@TiO2Core-shell structured nanomaterials；
Soluble gold salt described in step (1) is preferably HAuCl4；
The molar ratio of soluble gold salt, trisodium citrate and ascorbic acid described in step (1) is preferably 1:2:1.2；
The initial concentration of soluble gold salt solution, citric acid three sodium solution and ascorbic acid solution described in step (1)
Preferably 0.01M, 0.01M, 0.01M, wherein soluble gold salt solution, citric acid three sodium solution, ascorbic acid solution volume
Than being preferably 1:2:1.2；
The time being stirred to react described in step (1) is preferably 4~6min；
The stirring time that the reaction was continued described in step (1) is preferably 12~18min；
Soluble gold salt described in step (1) and TiF4Molar ratio be preferably 1:(6~24)；
TiF described in step (1)4Concentration after solution is added is preferably 0.002~0.008M；
The condition of hydro-thermal reaction described in step (1) is preferably 100~180 DEG C of 1~15h of reaction；
TiF described in step (1)4Molar ratio with the rare earth-iron-boron described in step (2) is preferably (6~24):
2.64；
Concentration is preferably 0.0006~0.001M after rare earth-iron-boron described in step (2) is added；
Concentration is more preferably 0.00088M after rare earth-iron-boron described in step (2) is added；
The rare earth-iron-boron described in step (2) is preferably YbCl3、ErCl3、TmCl3And HoCl3In at least
It is a kind of；
The rare earth-iron-boron described in step (2) is more preferably YbCl3With mixing for other rare earth-iron-borons
Close object, wherein YbCl3Molar ratio with other rare earth-iron-borons is preferably 10:1；
Other described rare earth-iron-borons are preferably ErCl3、TmCl3And HoCl3At least one of；
The condition of hydro-thermal reaction described in step (2) is preferably 100~180 DEG C of 3~15h of reaction；
Washing described in step (1) and (2) preferably uses deionized water or ethyl alcohol centrifuge washing 3~5 times；
A kind of rear-earth-doped Au@TiO2Core-shell structured nanomaterials are prepared by above-mentioned preparation method；
The rear-earth-doped Au@TiO2Core-shell structured nanomaterials are in solar cell, LED illumination, bio-sensing and ring
Application in the protection field of border；
The principle of the present invention：
In the prior art, the method usually in host material used in doping with rare-earth ions is coprecipitation, but in lemon
It is directly added into rare-earth ion solution and TiF in the gold nano-particle colloid solution that lemon acid is stablized4Solution, can cause citrate from
Son and rare earth ion are easy to form chelate, and F ion and rare earth ion are easy to generate rare earth fluoride, to be easy to cause Jenner
The reunion of rice grain and rare earth ion are difficult to incorporate into semiconductor substrate.The present invention is in Au@TiO2Core-shell structured nanomaterials
On the basis of, rear-earth-doped Au@TiO are further prepared using High temperature ion diffusion method2Core-shell structured nanomaterials, Ke Yiyou
Effect solves the above problems；Second, the present invention uses hydrothermal synthesis method, prepares Au@TiO2Core-shell structured nanomaterials, with biography
Microwave heating method of uniting and existing hydrothermal synthesis method (Rsc Advances, 2014,4 (7):It 3529-3535) compares, method
Simpler, easy to operate, equipment is simple.Third, the present invention by being accurately controlled experiment parameter, such as Doped ions concentration and
Type, TiF4The concentration etc. of solution, can be accurately controlled Doped ions concentration and type and TiO2The thickness of shell.4th,
The rear-earth-doped Au@TiO that the present invention is prepared2Core-shell structured nanomaterials are under the excitation of 980nm infrared lasers, lower
Under the conditions of excitation threshold, the Up-conversion emission of broad band may be implemented.
The present invention has the following advantages and effects with respect to the prior art：
(1) present invention is on gold nano grain surface by coating the controllable titanium oxide shell of a layer thickness, then utilize from
Rare earth ion doped gold nano grain@titanium oxide (the Au@TiO with broadband emission are prepared in sub- method of diffusion2) nucleocapsid
Structure nano material, the material can effectively improve the stability of gold nano grain, change the photocatalytic of titanium dioxide nano material
Matter.
(2) the present invention overcomes directly in TiO2In shell the problem of doping with rare-earth ions, solve on traditional rare earth
Changing luminous material emission spectrum is relatively narrow, can not be with the absorption spectra matched well of photosensitive material, and the problems such as excitation threshold is high is made
Rear-earth-doped Au@TiO2Core-shell structured nanomaterials have the emission band of wider upper conversion and lower excitation threshold；This
Outside, also there are the multi-functionals such as photothermal conversion and photocatalysis.
(3) preparation process of the present invention is simply easy to operate, does not need complicated equipment, is easy to produce in batches.
(4) rear-earth-doped Au@TiO produced by the present invention2Core-shell structured nanomaterials are in solar cell, LED illumination, biology
Sensing and field of environment protection have important potential using value.
Description of the drawings
Fig. 1 is sample preparation technology route map.
Fig. 2 is rear-earth-doped Au@TiO2The transmission electron microscope picture of core-shell structured nanomaterials.
Fig. 3 is rear-earth-doped TiO2The transmission electron microscope picture of hollow shell structure nano material.
Fig. 4 is gold nano grain made from comparative example 1, rear-earth-doped TiO made from comparative example 22Ghost knot
Rear-earth-doped Au@TiO made from structure nano material and embodiment 12The extinction spectra figure of core-shell structured nanomaterials.
Fig. 5 is rear-earth-doped TiO made from comparative example 22Rare earth made from hollow shell structure nano material and embodiment 1
Adulterate Au@TiO2Up-conversion luminescence spectrogram of the core-shell structured nanomaterials under the excitation of 980nm light；Wherein, (a)：It is rear-earth-doped
TiO2Hollow shell structure nano material, (b)：Rear-earth-doped Au@TiO2Core-shell structured nanomaterials.
Specific implementation mode
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
(1)Au@TiO2The preparation of core-shell structured nanomaterials：By the HAuCl of 1mL 0.01M4Solution and 2mL 0.01M's
Citric acid three sodium solution mixes, and is stirred to react 5min；Then the AA solution of 1.2mL 0.01M is added, is stirred to react 15min；It
The TiF of 2mL 0.06M is added afterwards4Solution, and system is diluted to 30mL, make TiF4A concentration of 0.004M；It finally will be above-mentioned anti-
Mixture is answered to be transferred in the hydrothermal reaction kettle that liner is 50mL, 100 DEG C of hydro-thermal reaction 15h；Product is collected by centrifugation, and spend from
Sub- water centrifuge washing three times, obtains Au@TiO2Core-shell structured nanomaterials；
(2) rear-earth-doped Au@TiO2The preparation of core-shell structured nanomaterials：By Au@TiO made from step (1)2Nucleocapsid knot
Structure nano material is dispersed to again in 15mL water, and the YbCl of 2.4mL 0.01M is then added3Solution and 0.24mL 0.01M's
ErCl3Solution, and system is diluted to 30mL, make a concentration of 0.00088M of rare earth-iron-boron；Finally by above-mentioned reaction mixture
It is transferred in the hydrothermal reaction kettle that liner is 50mL, 180 DEG C of hydro-thermal reaction 3h；Product is collected by centrifugation, deionized water is used in combination to centrifuge
Washing three times, obtains rear-earth-doped Au@TiO2Core-shell structured nanomaterials (preparation flow is shown in Fig. 1).
Embodiment 2
(1)Au@TiO2The preparation of core-shell structured nanomaterials：By the HAuCl of 1mL 0.01M4Solution and 2mL 0.01M's
Citric acid three sodium solution mixes, and is stirred to react 4min；Then the AA solution of 1.2mL 0.01M is added, is stirred to react 18min；It
The TiF of 3mL 0.02M is added afterwards4Solution, and system is diluted to 30mL, make TiF4A concentration of 0.002M；It finally will be above-mentioned anti-
Mixture is answered to be transferred in the hydrothermal reaction kettle that liner is 50mL, 120 DEG C of hydro-thermal reaction 12h；Product is collected by centrifugation, and spend from
Sub- water centrifuge washing four times obtains Au@TiO2Core-shell structured nanomaterials；
(2) rear-earth-doped Au@TiO2The preparation of core-shell structured nanomaterials：By Au@TiO made from step (1)2Nucleocapsid knot
Structure nano material is dispersed to again in 15mL water, and the YbCl of 2.4mL 0.01M is then added3Solution and 0.24mL 0.01M's
ErCl3Solution, and system is diluted to 30mL, make a concentration of 0.00088M of rare earth-iron-boron；Finally by above-mentioned reaction mixture
It is transferred in the hydrothermal reaction kettle that liner is 50mL, 160 DEG C of hydro-thermal reaction 5h；Product is collected by centrifugation, deionized water is used in combination to centrifuge
Washing four times, obtains rear-earth-doped Au@TiO2Core-shell structured nanomaterials.
Embodiment 3
(1)Au@TiO2The preparation of core-shell structured nanomaterials：By the HAuCl of 1mL 0.01M4Solution and 2mL 0.01M's
Citric acid three sodium solution mixes, and is stirred to react 6min；Then the AA solution of 1.2mL 0.01M is added, is stirred to react 12min；It
The TiF of 8mL 0.03M is added afterwards4Solution, and system is diluted to 30mL, make TiF4A concentration of 0.008M；It finally will be above-mentioned anti-
Mixture is answered to be transferred in the hydrothermal reaction kettle that liner is 50mL, 150 DEG C of hydro-thermal reaction 6h；Product is collected by centrifugation, and spend from
Sub- water centrifuge washing five times obtains Au@TiO2Core-shell structured nanomaterials；
(2) rear-earth-doped Au@TiO2The preparation of core-shell structured nanomaterials：By Au@TiO made from step (1)2Nucleocapsid knot
Structure nano material is dispersed to again in 15mL water, and the YbCl of 2.4mL 0.01M is then added3Solution and 0.24mL 0.01M's
ErCl3Solution, and system is diluted to 30mL, make a concentration of 0.00088M of rare earth-iron-boron；Finally by above-mentioned reaction mixture
It is transferred in the hydrothermal reaction kettle that liner is 50mL, 150 DEG C of hydro-thermal reaction 6h；Product is collected by centrifugation, deionized water is used in combination to centrifuge
Washing five times, obtains rear-earth-doped Au@TiO2Core-shell structured nanomaterials.
Embodiment 4
(1)Au@TiO2The preparation of core-shell structured nanomaterials：By the HAuCl of 1mL 0.01M4Solution and 2mL 0.01M's
Citric acid three sodium solution mixes, and is stirred to react 5min；Then the AA solution of 1.2mL 0.01M is added, is stirred to react 15min；It
The TiF of 3mL 0.04M is added afterwards4Solution, and system is diluted to 30mL, make TiF4A concentration of 0.004M；It finally will be above-mentioned anti-
Mixture is answered to be transferred in the hydrothermal reaction kettle that liner is 50mL, 160 DEG C of hydro-thermal reaction 4h；Product is collected by centrifugation, ethyl alcohol is used in combination
Centrifuge washing three times, obtains Au@TiO2Core-shell structured nanomaterials；
(2) rear-earth-doped Au@TiO2The preparation of core-shell structured nanomaterials：By Au@TiO made from step (1)2Nucleocapsid knot
Structure nano material is dispersed to again in 15mL water, and the YbCl of 2.4mL 0.01M is then added3Solution and 0.24mL 0.01M's
TmCl3Solution, and system is diluted to 30mL, make a concentration of 0.00088M of rare earth-iron-boron；Finally by above-mentioned reaction mixture
It is transferred in the hydrothermal reaction kettle that liner is 50mL, 100 DEG C of hydro-thermal reaction 15h；Product is collected by centrifugation, ethyl alcohol centrifuge washing is used in combination
Three times, rear-earth-doped Au@TiO are obtained2Core-shell structured nanomaterials.
Embodiment 5
(1)Au@TiO2The preparation of core-shell structured nanomaterials：By the HAuCl of 1mL 0.01M4Solution and 2mL 0.01M's
Citric acid three sodium solution mixes, and is stirred to react 5min；Then the AA solution of 1.2mL 0.01M is added, is stirred to react 15min；It
The TiF of 3mL 0.04M is added afterwards4Solution, and system is diluted to 30mL, make TiF4A concentration of 0.004M；It finally will be above-mentioned anti-
Mixture is answered to be transferred in the hydrothermal reaction kettle that liner is 50mL, 180 DEG C of hydro-thermal reaction 1h are collected by centrifugation product, ethyl alcohol is used in combination
Centrifuge washing four times obtains Au@TiO2Core-shell structured nanomaterials；
(2) rear-earth-doped Au@TiO2The preparation of core-shell structured nanomaterials：By Au@TiO made from step (1)2Nucleocapsid knot
Structure nano material is dispersed to again in 15mL water, and the YbCl of 2.4mL 0.01M is then added3Solution and 0.24mL 0.01M's
HoCl3Solution, and system is diluted to 30mL, make a concentration of 0.00088M of rare earth-iron-boron；Finally by above-mentioned reaction mixture
It is transferred in the hydrothermal reaction kettle that liner is 50mL, 180 DEG C of hydro-thermal reaction 3h；Product is collected by centrifugation, ethyl alcohol centrifuge washing is used in combination
Four times, obtain rear-earth-doped Au@TiO2Core-shell structured nanomaterials.
Comparative example 1
By the HAuCl of 1mL 0.01M4The citric acid three sodium solution of solution and 2mL 0.01M mix, and are stirred to react 5min；
Then the AA solution of 1.2mL 0.01M is added, is stirred to react 15min, obtains nano gold sol.
Comparative example 2
By rear-earth-doped Au@TiO made from embodiment 12Core-shell structured nanomaterials are added to the water, and after disperseing again, add
Enter 1mL hydrogen peroxide weak solutions, by the Au core complete oxidations in sample, obtains rear-earth-doped TiO2Hollow shell structure nano material (system
Standby flow is shown in Fig. 1).
Effect example
By rear-earth-doped Au@TiO made from embodiment 12It is dilute made from core-shell structured nanomaterials and comparative example 2
Soil doping TiO2Hollow shell structure nano material carries out transmission electron microscope detection respectively, as a result sees Fig. 2 and Fig. 3.Figure it is seen that
Rear-earth-doped Au@TiO made from embodiment 12Core-shell structured nanomaterials structural integrity, nucleocapsid is apparent, size uniform, point
It is good to dissipate property；From figure 3, it can be seen that rear-earth-doped TiO made from comparative example 22Hollow shell structure nanometer material structure is complete,
It is compared with before oxidation, in addition to golden core is oxidized away, without apparent structure change.
Fig. 4 is gold nano grain made from comparative example 1, rear-earth-doped TiO made from comparative example 22Ghost knot
Rear-earth-doped Au@TiO made from structure nano material and embodiment 12The extinction spectra figure of core-shell structured nanomaterials.Wherein, golden
The delustring peak of nano particle is consistent with the absorption peak of the gold nano grain usually prepared present in 520nm, illustrates successfully to prepare
Gold nano grain；Rear-earth-doped TiO2The extinction spectra of hollow shell structure nano material only shows TiO2Absorption peak, illustrate gold
Grain oxidation mutually coincide with transmission electron microscope results completely；It is compared with the Spectral Extinction of gold nano grain, rear-earth-doped Au@TiO2Core
There is apparent Red Shift Phenomena in the absorption peak of shell structural nano material, this is because TiO2After success coats gold nano grain,
Dielectric environment around gold nano grain is changed, and dielectric constant increases, therefore Red Shift Phenomena, explanation occurs in absorption peak
The present invention is successfully prepared rear-earth-doped Au@TiO2Core-shell structured nanomaterials.
Fig. 5 is rear-earth-doped TiO made from comparative example 22Rare earth made from hollow shell structure nano material and embodiment 1
Adulterate Au@TiO2Up-conversion luminescence spectrogram of the core-shell structured nanomaterials under the excitation of 980nm light.Wherein, rear-earth-doped TiO2It is empty
The up-conversion luminescence spectrum of shell structural nano material shows the emission spectrum of 530nm and 680nm or so, this and common Yb,
The emission spectrum of the up-conversion luminescence nanomaterial of Er codopes is similar, illustrates that rare earth ion is successfully incorporated into TiO2Host material
In；Rear-earth-doped Au@TiO2The upper conversion of the up-conversion luminescence spectrum of core-shell structured nanomaterials and common Yb, Er codopes are sent out
The emission spectrum of light nano material makes a big difference, and the broadband emission from 500~850nm occurs, and emission spectra covering is visible
Light and near infrared light wave band, this is because caused by the presence of gold nano grain, gold nano grain has plasma resonance characteristic,
Plasma resonance characteristic makes around gold nano grain local electric field enhance, under the action of electric field, it is rear-earth-doped upper turn
It changes emission spectrum and apparent variation has occurred.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (10)
1. a kind of rear-earth-doped Au@TiO2The preparation method of core-shell structured nanomaterials, it is characterised in that comprise the following steps：
(1) soluble gold salt solution and citric acid three sodium solution are mixed, is stirred to react；Be added ascorbic acid solution, stirring after
Continuous reaction；Then TiF is added4Solution, carries out hydro-thermal reaction, and centrifugation, washing obtain Au@TiO2Core-shell structured nanomaterials；
(2) by Au@TiO made from step (1)2Core-shell structured nanomaterials are dispersed in water；Then it is molten that rare earth-iron-boron is added
Liquid, carries out hydro-thermal reaction, and centrifuge washing obtains rear-earth-doped Au@TiO2Core-shell structured nanomaterials.
2. rear-earth-doped Au@TiO according to claim 12The preparation method of core-shell structured nanomaterials, it is characterised in that：
Soluble gold salt described in step (1) is HAuCl4。
3. rear-earth-doped Au@TiO according to claim 12The preparation method of core-shell structured nanomaterials, it is characterised in that：
The molar ratio of soluble gold salt, trisodium citrate and ascorbic acid described in step (1) is 1:2:1.2.
4. rear-earth-doped Au@TiO according to claim 12The preparation method of core-shell structured nanomaterials, it is characterised in that：
The time being stirred to react described in step (1) is 4~6min；
The stirring time that the reaction was continued described in step (1) is 12~18min.
5. rear-earth-doped Au@TiO according to claim 12The preparation method of core-shell structured nanomaterials, it is characterised in that：
Soluble gold salt described in step (1) and TiF4Molar ratio be 1:(6~24).
6. rear-earth-doped Au@TiO according to claim 12The preparation method of core-shell structured nanomaterials, it is characterised in that：
The condition of hydro-thermal reaction described in step (1) is 100~180 DEG C of 1~15h of reaction.
7. rear-earth-doped Au@TiO according to claim 12The preparation method of core-shell structured nanomaterials, it is characterised in that：
TiF described in step (1)4Molar ratio with the rare earth-iron-boron described in step (2) is (6~24):2.64.
8. rear-earth-doped Au@TiO according to claim 12The preparation method of core-shell structured nanomaterials, it is characterised in that：
The condition of hydro-thermal reaction described in step (2) is 100~180 DEG C of 3~15h of reaction.
9. a kind of rear-earth-doped Au@TiO2Core-shell structured nanomaterials, it is characterised in that described in any one of claim 1~8
Preparation method be prepared.
10. the rear-earth-doped Au@TiO described in claim 92Core-shell structured nanomaterials are passed in solar cell, LED illumination, biology
Application in sense and field of environment protection.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810533950.9A CN108587601B (en) | 2018-05-29 | 2018-05-29 | Rare earth doped Au @ TiO2Core-shell structure nano material, preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810533950.9A CN108587601B (en) | 2018-05-29 | 2018-05-29 | Rare earth doped Au @ TiO2Core-shell structure nano material, preparation and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108587601A true CN108587601A (en) | 2018-09-28 |
| CN108587601B CN108587601B (en) | 2020-08-11 |
Family
ID=63629461
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810533950.9A Active CN108587601B (en) | 2018-05-29 | 2018-05-29 | Rare earth doped Au @ TiO2Core-shell structure nano material, preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108587601B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109365800A (en) * | 2018-10-15 | 2019-02-22 | 黄河科技学院 | A kind of gold nano set square-titanium dioxide core-shell nano complex, preparation method and application |
| CN111437815A (en) * | 2020-05-06 | 2020-07-24 | 亳州市谯城区蓝鲸信息科技有限公司 | Preparation method of composite metal doped graphene titanium dioxide nano composite material |
| CN111812162A (en) * | 2020-06-23 | 2020-10-23 | 武汉工程大学 | Acetone gas sensor excited by visible light and preparation method thereof |
| CN111812163A (en) * | 2020-06-23 | 2020-10-23 | 武汉工程大学 | Semiconductor resistor type ethanol gas sensor and preparation method thereof |
| CN113117675A (en) * | 2021-04-10 | 2021-07-16 | 福州大学 | Rhodium-erbium composite metal photo-thermal catalyst and preparation method and application thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102965762A (en) * | 2012-10-24 | 2013-03-13 | 长春理工大学 | Method for preparing Er-Yb co-blended yttrium fluoride up-conversion luminescence hollow nanofibers |
| CN103102883A (en) * | 2013-01-14 | 2013-05-15 | 长春理工大学 | One-dimensional fluoride core-shell structure luminescent material and preparation method thereof |
| CN103252502A (en) * | 2012-02-17 | 2013-08-21 | 国家纳米科学中心 | Hollow core shell structure Au@TiO2 nano-composite material and preparation method thereof |
| CN103756668A (en) * | 2014-01-08 | 2014-04-30 | 上海大学 | Core-shell type rare earth up-conversion composite nanoparticle and preparation method thereof |
| CN105537583A (en) * | 2015-12-22 | 2016-05-04 | 哈尔滨工业大学 | Core-shell Au@TiO2 nano-particles and preparation method thereof |
| CN106141170A (en) * | 2015-02-02 | 2016-11-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | Gold nanorods/titanium dioxide core-shell nanostructured and one-step synthesis method method thereof |
| CN107170584A (en) * | 2017-06-02 | 2017-09-15 | 扬州大学 | The preparation method of compound nucleocapsid nano-hollow ball and its application in DSSC |
| CN107185565A (en) * | 2017-07-19 | 2017-09-22 | 合肥学院 | It is a kind of to photocatalyst material of the full spectral absorption of sunshine and preparation method thereof |
| CN107195462A (en) * | 2017-06-02 | 2017-09-22 | 扬州大学 | A kind of preparation method and applications of photosensitizer nano composite material |
| CN107384402A (en) * | 2017-07-24 | 2017-11-24 | 合肥工业大学 | A kind of preparation method and applications for being used to contaminate the hollow enhanced up-conversion of nucleocapsid of quick solar cell |
| CN107418554A (en) * | 2017-05-11 | 2017-12-01 | 洛阳理工学院 | A kind of gold nanorods and upper conversion nano crystalline substance composite nano materials and preparation method thereof |
-
2018
- 2018-05-29 CN CN201810533950.9A patent/CN108587601B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103252502A (en) * | 2012-02-17 | 2013-08-21 | 国家纳米科学中心 | Hollow core shell structure Au@TiO2 nano-composite material and preparation method thereof |
| CN102965762A (en) * | 2012-10-24 | 2013-03-13 | 长春理工大学 | Method for preparing Er-Yb co-blended yttrium fluoride up-conversion luminescence hollow nanofibers |
| CN103102883A (en) * | 2013-01-14 | 2013-05-15 | 长春理工大学 | One-dimensional fluoride core-shell structure luminescent material and preparation method thereof |
| CN103756668A (en) * | 2014-01-08 | 2014-04-30 | 上海大学 | Core-shell type rare earth up-conversion composite nanoparticle and preparation method thereof |
| CN106141170A (en) * | 2015-02-02 | 2016-11-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | Gold nanorods/titanium dioxide core-shell nanostructured and one-step synthesis method method thereof |
| CN105537583A (en) * | 2015-12-22 | 2016-05-04 | 哈尔滨工业大学 | Core-shell Au@TiO2 nano-particles and preparation method thereof |
| CN107418554A (en) * | 2017-05-11 | 2017-12-01 | 洛阳理工学院 | A kind of gold nanorods and upper conversion nano crystalline substance composite nano materials and preparation method thereof |
| CN107170584A (en) * | 2017-06-02 | 2017-09-15 | 扬州大学 | The preparation method of compound nucleocapsid nano-hollow ball and its application in DSSC |
| CN107195462A (en) * | 2017-06-02 | 2017-09-22 | 扬州大学 | A kind of preparation method and applications of photosensitizer nano composite material |
| CN107185565A (en) * | 2017-07-19 | 2017-09-22 | 合肥学院 | It is a kind of to photocatalyst material of the full spectral absorption of sunshine and preparation method thereof |
| CN107384402A (en) * | 2017-07-24 | 2017-11-24 | 合肥工业大学 | A kind of preparation method and applications for being used to contaminate the hollow enhanced up-conversion of nucleocapsid of quick solar cell |
Non-Patent Citations (1)
| Title |
|---|
| 王红玉等: "Au纳米粒子/TiO2：Er3+，Yb3+纳米复合膜中双模式荧光增强", 《南京邮电大学学报( 自然科学版)》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109365800A (en) * | 2018-10-15 | 2019-02-22 | 黄河科技学院 | A kind of gold nano set square-titanium dioxide core-shell nano complex, preparation method and application |
| CN111437815A (en) * | 2020-05-06 | 2020-07-24 | 亳州市谯城区蓝鲸信息科技有限公司 | Preparation method of composite metal doped graphene titanium dioxide nano composite material |
| CN111437815B (en) * | 2020-05-06 | 2021-05-18 | 江西联锴新材料有限公司 | Preparation method of composite metal doped graphene titanium dioxide nano composite material |
| CN111812162A (en) * | 2020-06-23 | 2020-10-23 | 武汉工程大学 | Acetone gas sensor excited by visible light and preparation method thereof |
| CN111812163A (en) * | 2020-06-23 | 2020-10-23 | 武汉工程大学 | Semiconductor resistor type ethanol gas sensor and preparation method thereof |
| CN111812163B (en) * | 2020-06-23 | 2022-11-29 | 武汉工程大学 | Semiconductor resistor type ethanol gas sensor and preparation method thereof |
| CN111812162B (en) * | 2020-06-23 | 2022-12-09 | 武汉工程大学 | Acetone gas sensor excited by visible light and preparation method thereof |
| CN113117675A (en) * | 2021-04-10 | 2021-07-16 | 福州大学 | Rhodium-erbium composite metal photo-thermal catalyst and preparation method and application thereof |
| CN113117675B (en) * | 2021-04-10 | 2022-04-08 | 福州大学 | Rhodium-erbium composite metal photo-thermal catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108587601B (en) | 2020-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108587601A (en) | A kind of rear-earth-doped Au@TiO2Core-shell structured nanomaterials and preparation and application | |
| Kumar et al. | Synthesis and characterization of Er3+-Yb3+ doped ZnO upconversion nanoparticles for solar cell application | |
| Wang et al. | Considerable photoluminescence enhancement of LiEu (MoO4) 2 red phosphors via Bi and/or Si doping for white LEDs | |
| CN110607176B (en) | Composite film with enhanced noble metal/semiconductor induced up-conversion | |
| CN111139063B (en) | Up-conversion nano material with greatly enhanced red light and preparation method thereof | |
| CN103881720A (en) | Method for preparing high-doping rare-earth upconversion fluorescence material by utilizing nuclear shell coating | |
| WO2021253711A1 (en) | Up-conversion nanowires and preparation method therefor and use thereof | |
| Liu et al. | CaF2: Ce3+/Yb3+ hollow spheres luminescence downconversion property optimize anti-reflective coatings for solar cells | |
| CN114836216B (en) | Rare earth nanocomposite capable of improving singlet oxygen generation, preparation method and application thereof | |
| CN104766901B (en) | A kind of photon crystal structure with enhancing and the upper transformational substance lighting function of regulation and preparation method thereof | |
| CN102146286B (en) | Tungstate matrix upper conversion white light emitting material and preparation method thereof | |
| Wei et al. | Color-converted white light-emitting diodes based on I-III-VI quantum dots: Package strategies and stability promotion | |
| Liu et al. | Construction of a novel pitaya-like CsxWO3@ NaYF4: Yb, Er particles with simultaneous colour tuning and upconversion luminescence enhancement | |
| Chen et al. | Optimizing concurrent extension of near-infrared and ultraviolet light harvesting of dye sensitized solar cells by introducing sandwich-nanostructured upconversion-core/inert-shell/downconversion-shell nanoparticles | |
| CN111019655B (en) | Up-conversion luminescent silica aerogel and preparation method thereof | |
| CN105238394B (en) | 3 mercaptopropionic acid human serum fluorescent au nanocluster materials and preparation method thereof | |
| CN102933688B (en) | Silicate luminescent materials and preparation methods thereof | |
| CN101875844B (en) | Nanomaterial capable of emitting white fluorescent light and preparation method thereof | |
| Zhang et al. | Plasmon-enhanced upconversion luminescence in pyrochlore phase YbxEr2-xTi2O7 thin film | |
| CN112538352B (en) | Efficient multicolor up-conversion luminescence composite film | |
| CN106311209B (en) | The application of Al and Ce codope raising ZnO micro-powder photocatalysis performance | |
| Xu et al. | Novel quantum dots: Water-based CdTeSe/ZnS and YAG hybrid phosphor for white light-emitting diodes | |
| Guo et al. | Near-infrared photocatalysis based on upconversion nanomaterials | |
| CN107312541A (en) | A kind of transition metal ions regulates and controls the preparation method of rare earth upconversion nano material morphology | |
| Huang et al. | Simultaneous excitation and emission enhancement of near-infrared quantum cutting in β-NaYF4: Er3+ nanoparticles by double plasmon modes of noble metals |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |