CN102125828A - Up-conversion light-emitting material modified photocatalyst and preparation method thereof - Google Patents

Up-conversion light-emitting material modified photocatalyst and preparation method thereof Download PDF

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CN102125828A
CN102125828A CN2010105867912A CN201010586791A CN102125828A CN 102125828 A CN102125828 A CN 102125828A CN 2010105867912 A CN2010105867912 A CN 2010105867912A CN 201010586791 A CN201010586791 A CN 201010586791A CN 102125828 A CN102125828 A CN 102125828A
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luminescent material
conversion luminescent
light
tio
conversion
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CN102125828B (en
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樊君
刘恩周
胡晓云
侯文倩
张倩
杨宇豪
叶岩溪
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Northwest University
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Northwest University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention discloses an up-conversion light-emitting material modified photocatalyst and a preparation method thereof. The up-conversion light-emitting material modified photocatalyst is prepared by compounding an up-conversion light-emitting material and nano-TiO2, wherein the TiO2 is uniformly adsorbed on the surface of the up-conversion light-emitting material and in the pore passages of the up-conversion light-emitting material; the up-conversion light-emitting material is a porous micron bar, the length of the porous micron bar is 10-20mu m, the length-diameter ratio of the porous micron bar is 2-4, and the pore passages on the porous micron bar are mutually communicated; and the porous micron bar can absorb visible light of 500-540nm and 560-610nm, absorb near-infrared light of 840-880nm and emit ultraviolet light of 290-380nm. In the invention, the ultraviolet light which is emitted after the up-conversion light-emitting material absorbs visible light and near-infrared light is used for exciting the nano-TiO2, thereby realizing the photocatalysis of the visible light and near-infrared light, indirectly expanding the spectral response range of the nano-TiO2, and improving the utilization ratio of the photocatalytic reaction to the visible light and near-infrared light.

Description

Photochemical catalyst of a kind of up-conversion luminescent material modification and preparation method thereof
Technical field
The invention belongs to fields such as photoelectric functional material, catalysis material, relate to a kind of nano-TiO of novel up-conversion luminescent material modification 2Photochemical catalyst and preparation and in the application of solar energy aspect utilizing.
Background technology
Energy shortage, environmental pollution and a large amount of CO 2The greenhouse effects that discharging causes have become the main problem that world today's development faces, development new forms of energy and regenerative resource, control CO 2Discharging, realization CO 2Recycling, slow down the common recognition that greenhouse effects have become various circles of society.Current, in the technical method of numerous researchs and solution, be considered to one of green technology that has application prospect in conjunction with photocatalysis technology with solar energy.Utilize new energy technologies such as abundant solar energy generates electricity, solar energy catalyzing manufacturing of hydrogen to solve energy problem; Utilize solar energy photocatalytic technology reduction CO 2, can not only be with CO 2Be converted into energy chemical substance, as CH 3OH, CH 4Deng, and can slow down greenhouse effects.Above-mentioned solar energy photocatalytic technology has been subjected to widely to be paid close attention to, and the key of implementing this process is the exploitation of high-performance optical catalyst material.
TiO 2Being the catalysis material of extensive use in the photocatalysis technology, having that heat endurance and chemical stability are good, specific area is big, nontoxic, advantages such as cost is low, long service life, is a kind of photocatalyst material of function admirable.Yet because TiO 2Energy gap is 3.12eV, can only absorbing wavelength less than the ultraviolet light of 387nm, this makes the utilization rate of solar energy have only about 4%, causes phototranstormation efficiency low, industrial applications is restricted greatly.In order to expand TiO 2The photoresponse scope, Chinese scholars is to TiO 2Carried out a large amount of study on the modification, for example metal ion mixing, noble metal loading, semiconductor are compound, dye sensitization and nonmetallic ion-doped etc., though these methods can make TiO 2Photoresponse zone produce red shift, reduce TiO 2Energy gap, but the oxidation-reduction potential that reduces to reduce light induced electron and hole of energy gap causes photocatalysis performance to reduce.
Up-conversion luminescent material is that a kind of energy absorbs a plurality of energy photons and launches the material of high-energy photons, and promptly light absorbing wavelength is greater than wavelength of transmitted light.If with up-conversion luminescent material and TiO 2Compound, visible or infrared light is converted to ultraviolet light excites TiO again 2, do not reducing TiO 2Under the prerequisite of energy gap, can improve TiO 2To the utilization rate of visible light and infrared light, will further widen TiO 2At solar cell material, photocatalytic hydrogen production by water decomposition, CO 2The application of aspects such as the synthetic and environmental protection of recycling, Green Chemistry.
Because the 4f energy level of rare earth element has transition energy level widely, up-conversion luminescent material commonly used both at home and abroad at present mostly is rear-earth-doped material greatly, for fear of dependence to rare earth resources, seeking non-terres rares, to have a up-conversion luminescent material of higher quantum efficiency and emission ultraviolet light significant, but up to the present do not find the relevant report of non-terres rares up-conversion luminescent material.
Summary of the invention
The objective of the invention is to, photochemical catalyst of a kind of up-conversion luminescent material modification and preparation method thereof is provided, the photochemical catalyst of the up-conversion luminescent material modification that makes has visible light and near infrared light catalytic activity.
In order to realize above-mentioned task, the present invention takes following technical solution:
A kind of photochemical catalyst of up-conversion luminescent material modification is characterized in that, the photochemical catalyst of this up-conversion luminescent material modification that makes is by up-conversion luminescent material and nano-TiO 2Be composited TiO 2Evenly be adsorbed in the surface and duct of up-conversion luminescent material.
Described up-conversion luminescent material is the porous micron bar, length 10-20 μ m, and draw ratio is 2-4, the duct on the porous micron bar is interconnected.This porous micron bar can absorb the visible light of 500nm ~ 540nm and 560nm ~ 610nm, and the near infrared light of 840nm ~ 880nm, the ultraviolet light of emission 290nm ~ 380nm.
The preparation method of the photochemical catalyst of described up-conversion luminescent material modification is with up-conversion luminescent material and nano-TiO 2Be scattered in the water, after the ultrasonic processing, make TiO 2Evenly be adsorbed in the surface and duct of up-conversion luminescent material, after the drying, be warming up to 500 ℃, be incubated 3h, obtain the nano-TiO of up-conversion luminescent material modification with 5 ℃/min 2Photochemical catalyst.
Wherein, the preparation method of up-conversion luminescent material is: borate glass and barium fluoride are dissolved in hydrofluoric acid, continue to stir 10h after, carry out hydro-thermal reaction, centrifugal, dry, annealing, grinding and obtain.
The weight ratio of borate glass and barium fluoride is (0.1 ~ 5): 1; Hydrothermal reaction condition: 12-48h, 120-200 ℃; Annealing conditions: be warming up to 500 ℃ with 5 ℃/min, insulation 3h.The up-conversion luminescent material that makes is that the porous micron is bar-shaped, the about 10-20 μ of excellent length m, and draw ratio is approximately 2-4, and the duct on the porous micron bar is interconnected, and helps and nano-TiO 2Compound.Up-conversion luminescent material mainly absorbs 500 nm-540nm, 560nm-610nm visible light, and the near infrared light of 840nm-880nm, the strongest absworption peak is at 520nm, 583nm and 860nm place, the ultraviolet light of emission 290nm ~ 380nm, the strongest emission peak is at 304nm, 324nm and 342nm place, and its emission light life-span is about 18ms.
The photochemical catalyst of up-conversion luminescent material modification of the present invention brings technique effect as follows:
1, up-conversion luminescent material and nano-TiO 2In conjunction with after, can make visible light and near infrared light be converted to ultraviolet light, excite TiO then 2Produce photocatalytic activity, expanded nano-TiO indirectly 2Spectral response range;
2, up-conversion luminescent material and nano-TiO 2In conjunction with after, do not reduce TiO 2Energy gap, electronics and hole that optical excitation produces have kept higher redox ability, the photocatalysis efficiency height;
3, up-conversion luminescent material does not contain rare earth ion, has reduced the dependence to rare earth resources, and its preparation method is simple, and cost is low, and the hydrofluoric acid in its preparation process can be recycled after centrifugal, pollutes little;
4, up-conversion luminescent material not only can absorb visible light, and can absorb near infrared light, can be used for solar energy photovoltaic material, photocatalytic hydrogen production by water decomposition, photo catalytic reduction CO 2, Green Chemistry is synthetic and the aspects such as waste water and gas processing of environmental protection.
Description of drawings
Fig. 1 is the three-dimensional light spectrogram of up-conversion luminescent material;
Fig. 2 is the emission spectrum figure of up-conversion luminescent material under the 583nm optical excitation;
Fig. 3 is the exciting light spectrogram of up-conversion luminescent material under the monitoring of 324nm light.
Fig. 4 is the sem photograph of up-conversion luminescent material;
Fig. 5 is the nano-TiO of up-conversion luminescent material modification 2The sem photograph of photochemical catalyst.
The present invention is described in further detail below in conjunction with embodiment.
The specific embodiment
Embodiment 1: the preparation of up-conversion luminescence conversion materials
With 4.5g borate glass and 3gBaF 2Put into the polytetrafluoroethylene (PTFE) retort, add 30mLHF, room temperature continues to stir 10h, subsequently solution is poured into 100mL hydro-thermal synthesis tank, puts into air dry oven, 180 ℃ of insulation 24h, naturally cooling back 6000rmp/min is centrifugal, with 40 ℃ of dry 24h of centrifugal gained white precipitate, desciccate is warming up to 500 ℃ with 5 ℃/min, the insulation 3h, grind after the cooling up-conversion luminescent material.Collect centrifugal gained HF solution simultaneously, recycle.
The up-conversion luminescent material three-dimensional light spectrogram that present embodiment makes as shown in Figure 1, as seen, up-conversion luminescent material has the emission of tangible light in 290nm ~ 380nm, at 500nm ~ 540nm, 560nm ~ 610nm and 840nm ~ 880nm tangible light absorption is arranged among the figure.Emission spectrum figure under the 583nm optical excitation as shown in Figure 2, as seen from the figure, the emission wavelength of this up-conversion luminescent material is between 290nm ~ 380nm, the strongest emission peak is at 304nm and 324nm place.
The exciting light spectrogram of up-conversion luminescent material under 324nm light monitoring as shown in Figure 3, as seen from the figure, the absorbing wavelength of up-conversion luminescent material is between the 560nm-610nm, the strongest absworption peak is at the 583nm place.Its sem photograph as shown in Figure 4.
Embodiment 2: the nano-TiO of up-conversion luminescence conversion materials modification 2 The preparation of photochemical catalyst
With 4g up-conversion luminescence conversion materials and 1g nano-TiO 2(Degussa P25) is scattered in the 50mL distilled water, and ultrasonic processing 5min makes TiO 2Evenly be adsorbed in the surface and duct of up-conversion luminescent material, after its 40 ℃ of dryings, be warming up to 500 ℃, be incubated 3h, obtain the nano-TiO of up-conversion luminescence conversion materials modification with 5 ℃/min 2Photochemical catalyst.
The nano-TiO of up-conversion luminescent material modification 2The sem photograph of photochemical catalyst as shown in Figure 5.
Embodiment 3: go up converting photocatalysis agent photo catalytic reduction CO 2 Performance
Nano-TiO with the up-conversion luminescent material modification of embodiment 2 preparation 2Photocatalyst applications is in photo catalytic reduction CO 2, be reflected in the quartzy photo catalysis reactor of homemade air tight cycle and carry out catalyst concn 0.5g/L, 50 ℃ of reaction temperatures, CO 2Circular flow 20mL/s, reaction time 10h, light source are 500W xenon lamp (wavelength is greater than 400nm), methanol yield 276 μ mol/g-cat in the reactant liquor, and pure nano-TiO 2Not having methyl alcohol under the same conditions generates.

Claims (4)

1. the photochemical catalyst of a up-conversion luminescent material modification is characterized in that, the photochemical catalyst of this up-conversion luminescent material modification that makes is by up-conversion luminescent material and nano-TiO 2Be composited TiO 2Evenly be adsorbed in the surface and duct of up-conversion luminescent material.
2. the photochemical catalyst of up-conversion luminescent material modification as claimed in claim 1 is characterized in that, described up-conversion luminescent material is the porous micron bar, length 10-20 μ m, and draw ratio is 2-4, the duct on the porous micron bar is interconnected.
3. the photochemical catalyst of up-conversion luminescent material modification as claimed in claim 1 or 2, it is characterized in that, described up-conversion luminescent material absorbs the visible light of 500-540nm and 560-610nm, and the near infrared light of 840-880nm, the ultraviolet light of emission 290-380nm.
4. the preparation method of the photochemical catalyst of the described up-conversion luminescent material modification of claim 1 is characterized in that, this method is with up-conversion luminescent material and nano-TiO 2Be scattered in the water, ultrasonic processing makes TiO 2Evenly be adsorbed in the surface and duct of up-conversion luminescent material, after the drying, be warming up to 500 ℃, be incubated 3h, promptly obtain the TiO of up-conversion luminescent material modification with 5 ℃/min 2Photochemical catalyst;
The preparation method of described up-conversion luminescent material is, borate glass and barium fluoride are dissolved in hydrofluoric acid by weight 0.1 ~ 5:1, after continuing to stir 10h, carries out hydro-thermal reaction, hydrothermal reaction condition: 12h ~ 48h, 120 ℃ ~ 200 ℃ of temperature; Centrifugal, be warming up to 500 ℃ with 5 ℃/min, insulation 3h, grind promptly the cooling back.
CN201010586791A 2010-12-14 2010-12-14 Up-conversion light-emitting material modified photocatalyst and preparation method thereof Expired - Fee Related CN102125828B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102311734A (en) * 2011-09-23 2012-01-11 辽宁大学 Upconversion UV (ultraviolet) luminescent material of broadband spectral adsorption and application thereof
CN109692695A (en) * 2018-12-27 2019-04-30 东北大学 A kind of near infrared light response type nano composite titania material and preparation method thereof
CN113351247A (en) * 2021-06-25 2021-09-07 哈尔滨理工大学 NaYF4Preparation of/TpPa-1 composite material and hydrogen production by photolysis of water

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003210998A (en) * 2002-01-25 2003-07-29 Japan Science & Technology Corp Photocatalyst system
CN1506155A (en) * 2002-12-06 2004-06-23 中国科学院化学研究所 Photocatalytic method to titania with LED as light source
CN101642702A (en) * 2009-09-09 2010-02-10 吉林大学 Red light or infrared light catalytic material comprising semiconductor material and up-conversion material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003210998A (en) * 2002-01-25 2003-07-29 Japan Science & Technology Corp Photocatalyst system
CN1506155A (en) * 2002-12-06 2004-06-23 中国科学院化学研究所 Photocatalytic method to titania with LED as light source
CN101642702A (en) * 2009-09-09 2010-02-10 吉林大学 Red light or infrared light catalytic material comprising semiconductor material and up-conversion material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
《环境科学》 20060630 王君等 上转换发光剂掺杂纳米TiO2的制备及可见光降解乙基紫的研究 第1.3，2.1节 1-3 第27卷, 第6期 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102311734A (en) * 2011-09-23 2012-01-11 辽宁大学 Upconversion UV (ultraviolet) luminescent material of broadband spectral adsorption and application thereof
CN102311734B (en) * 2011-09-23 2013-09-04 辽宁大学 Upconversion UV (ultraviolet) luminescent material of broadband spectral adsorption and application thereof
CN109692695A (en) * 2018-12-27 2019-04-30 东北大学 A kind of near infrared light response type nano composite titania material and preparation method thereof
CN109692695B (en) * 2018-12-27 2022-02-01 东北大学 Near-infrared light response type nano titanium dioxide composite material and preparation method thereof
CN113351247A (en) * 2021-06-25 2021-09-07 哈尔滨理工大学 NaYF4Preparation of/TpPa-1 composite material and hydrogen production by photolysis of water

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