CN103316703A - High-efficiency near-infrared light compound photocatalyst and preparation method thereof - Google Patents
High-efficiency near-infrared light compound photocatalyst and preparation method thereof Download PDFInfo
- Publication number
- CN103316703A CN103316703A CN2013102841469A CN201310284146A CN103316703A CN 103316703 A CN103316703 A CN 103316703A CN 2013102841469 A CN2013102841469 A CN 2013102841469A CN 201310284146 A CN201310284146 A CN 201310284146A CN 103316703 A CN103316703 A CN 103316703A
- Authority
- CN
- China
- Prior art keywords
- infrared light
- catalyst
- near infrared
- luminescent material
- nayf
- 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
Images
Landscapes
- Catalysts (AREA)
Abstract
The invention belongs to the field of photocatalytic materials, and particularly relates to a near-infrared light compound photocatalyst and a preparation method thereof. The compound photocatalyst is formed by mechanically mixing an up-conversion luminescent material beta-NaYF4: Yb<3+>, Tm<3+> and a photocatalytic material Degussa P25, wherein the up-conversion material is used for absorbing near-infrared light which is converted, so that ultraviolet light is emitted, and the utilization of near-infrared light is realized by exciting the photocatalytic activity of TiO2, and the utilization efficiency of sunlight in light-catalyzed reaction is increased. The near-infrared light compound photocatalyst can be applied to the field of light catalysis environmental management.
Description
Technical field
The invention belongs to field of photocatalytic material, be specifically related to a kind of near infrared light composite photo-catalyst and preparation method thereof.
Background technology
Since 20 century 70s, the semiconductor light-catalyst technology is emerging growing up progressively.Along with industrial development, population increase, environmental problem is increasingly serious, and the countries in the world scholar has extensively carried out the semiconductor light-catalyst technology is applied to the environmental improvement field.TiO
2The catalysis material of extensive use in the photocatalysis technology, its main feature be inexpensive, nontoxic, high stability, can recycling utilization, do not produce secondary pollution, can directly utilize the electromotive force current potential in solar energy, light induced electron and hole high, salinity is high.But, TiO
2The wide E in forbidden band
gGreatly, can only absorbing wavelength less than the ultraviolet light of 387nm.This just so that the capacity usage ratio of sunshine only have about 4%, and in the solar energy approximately 48% visible light and approximately 44% near infrared light all be not utilized effectively, greatly limited TiO
2The application of photochemical catalyst in actual environment pollution control and solar energy utilization.
In order to improve TiO
2The photoresponse scope, Chinese scholars is to TiO
2Carried out a large amount of study on the modification, compound etc. such as metal ion mixing, precious metal surface deposition, semiconductor.These methods can make TiO
2Quantum yield improve, reduce its energy gap, enlarge the photoresponse scope, improve the utilization rate to solar energy.But the oxidation-reduction potential that reduces meeting reduction light induced electron and hole of energy gap reduces photocatalytic activity.
Up-conversion luminescent material is as a kind of material that can be converted to lower energy photon high-energy photon, and we are with itself and TiO
2(P-25) compound by certain combination, utilize the characteristic of up-conversion luminescent material, absorb near infrared light, then short wavelength's ultraviolet is sent in conversion, so that semiconductor indirect utilization near infrared light improves the comprehensive utilization ratio to solar energy.
Summary of the invention
The objective of the invention is: a kind of near infrared light composite photo-catalyst and preparation method thereof is provided, and the composite photo-catalyst solar energy utilization rate that makes is high, photocatalysis performance good, and is applied to the environmental improvement field.
The technical scheme that the present invention takes is:
A kind of efficient near infrared light composite photo-catalyst is characterized in that: this near infrared light composite photo-catalyst is by up-conversion luminescent material β-NaYF
4: Yb
3+, Tm
3+Form with catalysis material Degussa P25 mechanical mixture, Degussa P25 particle is adsorbed on up-conversion luminescent material β-NaYF
4: Yb
3+, Tm
3+The surface.
A kind of efficient near infrared light composite photo-catalyst is further characterized in that: up-conversion luminescent material β-NaYF
4: Yb
3+, Tm
3+Pattern be six regular prisms, its diameter is 2.0 ~ 4.0 um, length is 9 ~ 15 um.
A kind of preparation method of near infrared light composite photo-catalyst comprises the steps:
(1) gets a certain amount of EDTA in a certain amount of ultra-pure water and magnetic agitation 30min, then dropwise add respectively a certain amount of LnCl
3Storing solution, magnetic agitation 60min, then dropwise add a certain amount of NaF aqueous solution, magnetic agitation 60min, with this presoma move into a sealing with in the teflon-lined reactor, in 200 ℃ of Water Under thermal response 18h, then naturally cool to room temperature, with ultra-pure water and absolute ethyl alcohol 1:1 mixed solution washed product 3 ~ 5 times, then with 80 ℃ of dry 12h of sediment, then with product at N
2Atmosphere is protected lower 400 ℃ of calcining 90min, obtains up-conversion luminescent material β-NaYF after the grinding
4: Yb
3+, Tm
3+
(2) with a certain amount of up-conversion luminescent material β-NaYF
4: Yb
3+, Tm
3+Add in a certain amount of absolute ethyl alcohol with a certain amount of Degussa P25, ultrasonic dispersion certain hour, then magnetic agitation 24h uses ultra-pure water and absolute ethyl alcohol 1:1 mixed solution washed product 3 ~ 5 times, then with 80 ℃ of dry 12h of sediment, obtain the near infrared light composite photo-catalyst after the grinding.
EDTA and LnCl in the above-mentioned steps (1)
3Mol ratio be 1:1 ~ 1.5; LnCl
3In Ln
3+Be Y
3+, Yb
3+, Tm
3+, LnCl
3Y in the storing solution
3+: Yb
3+: Tm
3+Mol ratio be (0.994-x): x:0.006 (x=0 ~ 0.3); NaF and LnCl
3Mol ratio be 1:16 ~ 20.
Up-conversion luminescent material β-NaYF in the above-mentioned steps (2)
4: Yb
3+, Tm
3+With the mol ratio of Degussa P25 be 1:0.5 ~ 4.0.
Above-mentioned near infrared light composite photo-catalyst can be applicable to photocatalysis environmental improvement field.
Preparation method of the present invention is first with the synthetic up-conversion luminescent material β-NaYF of hydro-thermal method
4: Yb
3+, Tm
3+, then it is combined by the mode of mechanical mixture by a certain percentage with Degussa P25, prepare the near infrared light catalyst.Then prepared near infrared light composite photo-catalyst can excite Degussa P25 to produce catalytic activity so that near infrared light is converted to ultraviolet light, has indirectly expanded TiO
2The photoresponse scope.This provides a kind of new Technology Ways for utilizing near infrared light to be used for the semiconductor catalyst field, and day by day serious problem of environmental pollution is significant for solving.
Description of drawings
Fig. 1 is the SEM photo of the embodiment of the invention 1 product.
Fig. 2 is the SEM photo of the embodiment of the invention 2 products.
The specific embodiment
Further specify below in conjunction with instantiation and to illustrate the present invention.
Embodiment 1: the preparation of up-conversion luminescent material
Then the EDTA that gets 0.292g dropwise adds respectively a certain amount of LnCl in the ultra-pure water of 10mL and magnetic agitation 30min
3Storing solution, i.e. YCl
3(0.5M) 1.488mL, YbCl
3(0.5M) 0.5mL, TmCl
3(0.05M) 0.12mL, magnetic agitation 60min, the 16mmolNaF aqueous solution that then dropwise adds 10mL, magnetic agitation 60min, with this presoma move into a 50mL sealing with in the teflon-lined reactor, place 200 ℃ of lower hydro-thermal reaction 18h in the air dry oven, then naturally cool to room temperature, use ultra-pure water and absolute ethyl alcohol 1:1 mixed solution through desk centrifuge 10
4Rpm/10min centrifuge washing product 3～5 times is then put into sediment 80 ℃ of dry 12h of vacuum drying chamber, then product is put into box atmospheric resistance furnace, at N
2Atmosphere is protected lower 400 ℃ of calcining 90min, obtains up-conversion luminescent material β-NaYF after the grinding
4: Yb
3+, Tm
3+
Embodiment 2: the preparation of near infrared light composite photo-catalyst
With the up-conversion luminescent material of 50mg and the TiO of 50mg
2(P-25) add in the absolute ethyl alcohol of 50mL, the ultrasonic dispersion 30min time, then magnetic agitation 24h uses ultra-pure water and absolute ethyl alcohol 1:1 mixed solution through desk centrifuge 10
4Rpm/10min centrifuge washing product 3～5 times is then put into sediment 80 ℃ of dry 12h of vacuum drying chamber, obtains the near infrared light composite photo-catalyst after the grinding.
Embodiment 3: the performance of near infrared light composite photocatalyst for degrading methyl orange (MO)
Take by weighing the above-mentioned near infrared light catalyst that makes of 5mg in the MO of the 20ppm of 0.5mL, leave standstill 12h under the dark condition, to reach adsorption equilibrium.Then, under 980nm near-infrared laser irradiation, carry out the light degradation experiment, measure the absorbance of solution behind the degraded certain hour by spectrophotometric, look into absorbance-concentration standard curve table, calculate that the MO degradation rate is 53.8% behind the 3h.
Embodiment 4: the performance of near infrared light catalyst deactivation E.Coil-K12.
Take by weighing the above-mentioned near infrared light catalyst that makes of 1mg and contain 10 in 1mL
7In the E.Coil of CFU/mL-K12 bacterium liquid, leave standstill 1h under the dark condition, to reach adsorption equilibrium.Then, under 980nm near-infrared laser irradiation, carry out sterilization and record the bacteria living amount in the bacterium liquid behind the certain hour by colony counting method, and calculate sterilizing rate, sterilizing rate is 88.82% behind the 1.5h.
Claims (4)
1. efficient near infrared light composite photo-catalyst, it is characterized in that: this near infrared light composite photo-catalyst is by up-conversion luminescent material β-NaYF
4: Yb
3+, Tm
3+Form with catalysis material Degussa P25 mechanical mixture, Degussa P25 particle is adsorbed on up-conversion luminescent material β-NaYF
4: Yb
3+, Tm
3+The surface.
2. a kind of efficient near infrared light composite photo-catalyst as claimed in claim 1 is further characterized in that: up-conversion luminescent material β-NaYF
4: Yb
3+, Tm
3+Pattern be six regular prisms, its diameter is 2.0 ~ 4.0 um, length is 9 ~ 15 um.
3. a kind of efficient near infrared light composite photo-catalyst as claimed in claim 1, its preparation method is divided into two steps:
(1) gets a certain amount of EDTA magnetic agitation 30min in a certain amount of ultra-pure water, then dropwise add respectively a certain amount of LnCl
3Storing solution, magnetic agitation 60min, then dropwise add a certain amount of NaF aqueous solution, magnetic agitation 60min, with this presoma move into a sealing with in the teflon-lined reactor, in 200 ℃ of Water Under thermal response 18h, then naturally cool to room temperature, with ultra-pure water and absolute ethyl alcohol 1:1 mixed solution washed product 3 ~ 5 times, then sediment is placed 80 ℃ of dry 12h, then with product at N
2Atmosphere is protected lower 400 ℃ of calcining 90min, obtains up-conversion luminescent material β-NaYF after the grinding
4: Yb
3+, Tm
3+
(2) with up-conversion luminescent material β-NaYF
4: Yb
3+, Tm
3+Place by a certain percentage a certain amount of absolute ethyl alcohol with Degussa P25, ultrasonic dispersion certain hour, then magnetic agitation 24h uses ultra-pure water and absolute ethyl alcohol 1:1 mixed solution washed product 3 ~ 5 times, then with 80 ℃ of dry 12h of sediment, obtain the near infrared light composite photo-catalyst after the grinding.
4. a kind of efficient near infrared light composite photo-catalyst as claimed in claim 1, the feature of its preparation method also is: EDTA and LnCl
3Mol ratio be 1:1 ~ 1.5; LnCl
3In Ln
3+Be Y
3+, Yb
3+, Tm
3+, LnCl
3Y in the storing solution
3+: Yb
3+: Tm
3+Mol ratio be (0.994-x): x:0.006 (x=0 ~ 0.3); NaF and LnCl
3Mol ratio be 1:16 ~ 20; Up-conversion luminescent material β-NaYF
4: Yb
3+, Tm
3+With the mol ratio of Degussa P25 be 1:0.5 ~ 4.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310284146.9A CN103316703B (en) | 2013-07-08 | 2013-07-08 | High-efficiency near-infrared light compound photocatalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310284146.9A CN103316703B (en) | 2013-07-08 | 2013-07-08 | High-efficiency near-infrared light compound photocatalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103316703A true CN103316703A (en) | 2013-09-25 |
| CN103316703B CN103316703B (en) | 2015-07-15 |
Family
ID=49185917
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310284146.9A Active CN103316703B (en) | 2013-07-08 | 2013-07-08 | High-efficiency near-infrared light compound photocatalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103316703B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104588065A (en) * | 2015-02-09 | 2015-05-06 | 中国科学院城市环境研究所 | Rare-earth composite g-C3N4 graphene photocatalyst and preparation method thereof |
| CN106268884A (en) * | 2016-08-16 | 2017-01-04 | 福州大学 | A kind of rear-earth-doped NaYF4/ Au@CdS composite photo-catalyst and preparation method thereof |
| CN106540731A (en) * | 2016-09-29 | 2017-03-29 | 沈阳化工大学 | Plasma and the enhanced multiband responsive photocatalyst preparation method of upper conversion |
| CN107008464A (en) * | 2017-04-12 | 2017-08-04 | 河海大学 | A kind of visible light-responded NaYF4:The preparation method and application of La, Ce@TiO2 composites |
| CN108273530A (en) * | 2018-01-23 | 2018-07-13 | 莆田学院 | A kind of high magnetic near infrared light composite nano-catalyst and preparation method thereof |
| CN108579772A (en) * | 2018-04-25 | 2018-09-28 | 江南大学 | A kind of method of composite nano materials photocatalytic degradation deoxynivalenol |
| CN108620100A (en) * | 2017-03-23 | 2018-10-09 | 中国科学院城市环境研究所 | A kind of high magnetic near infrared light composite catalyst and preparation method thereof |
| CN108620098A (en) * | 2017-03-23 | 2018-10-09 | 中国科学院城市环境研究所 | A kind of magnetism near infrared light composite photo-catalyst prepares and its guard method |
| CN109603920A (en) * | 2018-12-18 | 2019-04-12 | 同济大学 | Cellulose-the TiO of excited by visible light2Composite photo-catalyst |
| CN111282572A (en) * | 2020-03-26 | 2020-06-16 | 辽宁大学 | Composite material with near-infrared light catalysis effect and preparation method and application thereof |
| CN111495396A (en) * | 2020-06-04 | 2020-08-07 | 江西理工大学 | Ultrasonic/microwave-assisted preparation of NaYF4:Yb3+,Tb3+/TiO2Method for preparing composite photocatalytic material |
| CN112892577A (en) * | 2021-01-29 | 2021-06-04 | 浙江大学 | Photo-thermal synergetic catalytic material capable of utilizing full-spectrum absorption of near-infrared light and preparation and application thereof |
-
2013
- 2013-07-08 CN CN201310284146.9A patent/CN103316703B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| DONG-XING XU ET AL.: "Advanced near-infrared-driven photocatalyst: Fabrication, characterization, and photocatalytical performance of β-NaYF4:Yb3+,Tm3+@TiO2 core@shell microcrystals", 《APPLIED CATALYSIS B:ENVIRONMENTAL》 * |
| YANNA TANG ET AL.: "NIR-Responsive Photocatalytic Activity and Mechanism of NaYF4:Yb,Tm@TiO2 Core-Shell Nanoparticles", 《ACS CATALYSIS》 * |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104588065A (en) * | 2015-02-09 | 2015-05-06 | 中国科学院城市环境研究所 | Rare-earth composite g-C3N4 graphene photocatalyst and preparation method thereof |
| CN106268884A (en) * | 2016-08-16 | 2017-01-04 | 福州大学 | A kind of rear-earth-doped NaYF4/ Au@CdS composite photo-catalyst and preparation method thereof |
| CN106268884B (en) * | 2016-08-16 | 2019-04-05 | 福州大学 | A kind of rear-earth-doped NaYF4/ Au@CdS composite photo-catalyst and preparation method thereof |
| CN106540731A (en) * | 2016-09-29 | 2017-03-29 | 沈阳化工大学 | Plasma and the enhanced multiband responsive photocatalyst preparation method of upper conversion |
| CN106540731B (en) * | 2016-09-29 | 2018-12-18 | 沈阳化工大学 | Plasma and the multiband responsive photocatalyst preparation method of upper conversion enhancing |
| CN108620100A (en) * | 2017-03-23 | 2018-10-09 | 中国科学院城市环境研究所 | A kind of high magnetic near infrared light composite catalyst and preparation method thereof |
| CN108620098B (en) * | 2017-03-23 | 2021-04-02 | 中国科学院城市环境研究所 | Preparation and protection method of magnetic near-infrared light composite photocatalyst |
| CN108620098A (en) * | 2017-03-23 | 2018-10-09 | 中国科学院城市环境研究所 | A kind of magnetism near infrared light composite photo-catalyst prepares and its guard method |
| CN108620100B (en) * | 2017-03-23 | 2020-12-18 | 中国科学院城市环境研究所 | Efficient magnetic near-infrared light composite catalyst and preparation method thereof |
| CN107008464A (en) * | 2017-04-12 | 2017-08-04 | 河海大学 | A kind of visible light-responded NaYF4:The preparation method and application of La, Ce@TiO2 composites |
| CN107008464B (en) * | 2017-04-12 | 2019-04-30 | 河海大学 | A kind of visible light-responded NaYF4:La,Ce@TiO2The preparation method and application of composite material |
| CN108273530A (en) * | 2018-01-23 | 2018-07-13 | 莆田学院 | A kind of high magnetic near infrared light composite nano-catalyst and preparation method thereof |
| CN108273530B (en) * | 2018-01-23 | 2020-10-30 | 莆田学院 | High-efficiency magnetic near-infrared light composite nano catalyst and preparation method thereof |
| CN108579772B (en) * | 2018-04-25 | 2020-08-18 | 江南大学 | Method for photocatalytic degradation of deoxynivalenol by composite nano material |
| CN108579772A (en) * | 2018-04-25 | 2018-09-28 | 江南大学 | A kind of method of composite nano materials photocatalytic degradation deoxynivalenol |
| CN109603920B (en) * | 2018-12-18 | 2020-04-07 | 同济大学 | Visible light excited cellulose-TiO2Composite photocatalyst |
| CN109603920A (en) * | 2018-12-18 | 2019-04-12 | 同济大学 | Cellulose-the TiO of excited by visible light2Composite photo-catalyst |
| CN111282572A (en) * | 2020-03-26 | 2020-06-16 | 辽宁大学 | Composite material with near-infrared light catalysis effect and preparation method and application thereof |
| CN111282572B (en) * | 2020-03-26 | 2022-01-14 | 辽宁大学 | Composite material with near-infrared light catalysis effect and preparation method and application thereof |
| CN111495396A (en) * | 2020-06-04 | 2020-08-07 | 江西理工大学 | Ultrasonic/microwave-assisted preparation of NaYF4:Yb3+,Tb3+/TiO2Method for preparing composite photocatalytic material |
| CN112892577A (en) * | 2021-01-29 | 2021-06-04 | 浙江大学 | Photo-thermal synergetic catalytic material capable of utilizing full-spectrum absorption of near-infrared light and preparation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103316703B (en) | 2015-07-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103316703B (en) | High-efficiency near-infrared light compound photocatalyst and preparation method thereof | |
| CN103212392B (en) | Method for preparing TiO2/kieselguhr composite photocatalytic material by using sol-gel method | |
| CN104549500B (en) | A kind of nonmetal liquid phase doping prepares B doping g-C3n4the method of photocatalyst | |
| CN104588065A (en) | Rare-earth composite g-C3N4 graphene photocatalyst and preparation method thereof | |
| CN102205247B (en) | Composite oxide photocatalyst LiCuNb3-xTaxO9 with visible light response and preparation method thereof | |
| CN102489293B (en) | Preparation method of tin dioxide/bismuth tungstate composite photocatalyst | |
| CN101791565A (en) | TiO2@ graphite phase carbon nitride heterojunction composite photocatalyst and preparation method thereof | |
| CN102974373A (en) | Visible-light photocatalytic material and preparation method thereof | |
| CN102500390B (en) | Preparation method of iron oxide/bismuth tungstate composite photocatalyst | |
| CN101422725A (en) | Preparation method and use of visible light responsive nitrogen-doped titanium dioxide nano-tube | |
| CN103831107B (en) | A kind of preparation method of di-iron trioxide nanometer sheet parcel carbon nano-fiber catalyst | |
| CN103920513B (en) | Ti 3+: TiO 2/ TiF 3composite semiconductor light-catalyst and preparation method thereof | |
| CN105664995A (en) | Multi-element co-doped nano titanium dioxide photocatalytic material | |
| CN104383950A (en) | Bi2O3-BiOI heterojunction visible-light response photocatalyst and preparation method thereof | |
| CN101885603B (en) | Ceramic particle with far infrared and photocatalysis functions and manufacturing method thereof | |
| CN102205246A (en) | Visible light-responsive composite oxide photocatalyst LiCuNb1-xTaxO4 and preparation method thereof | |
| CN102764649A (en) | Metal-silver-supported titanium dioxide photocatalyst and preparation method thereof | |
| CN102211019B (en) | Visible light-responsive composite oxide photochemical catalyst Ba1-xSrxLi2Ti6O14 and preparation method thereof | |
| CN103521212A (en) | Photocatalyst Sm2LiVO6 with visible light response and preparation method thereof | |
| CN103521210A (en) | Photocatalyst Bi3Sb3Zn2O14 with visible light response | |
| CN102600828B (en) | Visible light responded composite oxide photocatalyst LiBiTiO4 and its preparation method | |
| CN102794188A (en) | PtC14/Bi2WO6 photocatalyst, and preparation and application thereof | |
| CN102527409A (en) | Tungsten-nitrogen binary co-doped nanometer TiO2 photocatalyst and preparation method thereof | |
| CN101757905B (en) | Visible light responding composite oxide photocatalyst Li6Ti5Nb2-xTaxO18 and preparation method | |
| CN107519852A (en) | A kind of method that normal temperature prepares efficient nano titanium dioxide optical catalyst |
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 |