CN105694887A - Preparation method of Ho<3+>-Yb<3+>-F<-> codoped TiO2 upconversion nanopowder and application of preparation method - Google Patents
Preparation method of Ho<3+>-Yb<3+>-F<-> codoped TiO2 upconversion nanopowder and application of preparation method Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000011858 nanopowder Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 80
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- WDVGLADRSBQDDY-UHFFFAOYSA-N holmium(3+);trinitrate Chemical compound [Ho+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WDVGLADRSBQDDY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims description 36
- 238000007254 oxidation reaction Methods 0.000 claims description 36
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 36
- 150000002910 rare earth metals Chemical class 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 27
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 23
- 229910052689 Holmium Inorganic materials 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 18
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 18
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 12
- 229960004756 ethanol Drugs 0.000 claims description 12
- 239000012528 membrane Substances 0.000 claims description 12
- 238000007650 screen-printing Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000000975 dye Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 125000004429 atom Chemical group 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000001856 Ethyl cellulose Substances 0.000 claims description 6
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000012327 Ruthenium complex Substances 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- 230000001476 alcoholic effect Effects 0.000 claims description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 229920001249 ethyl cellulose Polymers 0.000 claims description 6
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000010409 thin film Substances 0.000 claims description 6
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 239000003995 emulsifying agent Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 238000007496 glass forming Methods 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 229940116411 terpineol Drugs 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 238000003303 reheating Methods 0.000 claims description 2
- 238000001228 spectrum Methods 0.000 abstract description 7
- -1 polytetrafluoroethylene Polymers 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000002329 infrared spectrum Methods 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract 2
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract 2
- 238000005119 centrifugation Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 abstract 1
- 238000001132 ultrasonic dispersion Methods 0.000 abstract 1
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005049 combustion synthesis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
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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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B01J35/39—
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a preparation method of Ho<3+>-Yb<3+>-F<-> codoped TiO2 upconversion nanopowder. The method comprises the following steps that 1, a holmium nitrate and ytterbium nitrate solution with the purity ranging from 90 wt% to 98 wt% is prepared; 2, hydrosol is prepared; 3, a reaction precursor solution is prepared; 4, the reaction precursor solution is transferred to a polytetrafluoroethylene lining of a high-pressure reaction kettle with the volume of 200 ml, the kettle is sealed, and the high-pressure reaction kettle is put into a high-temperature drying oven for a reaction for 22-26 h at the temperature ranging from 190 DEG C to 210 DEG C; 5, after the reaction is completed, supernate in the polytetrafluoroethylene lining is removed, ultrasonic dispersion with ethyl alcohol and centrifugation are conducted three times, redundant water and nitric acid are removed, and a centrifugal product is obtained; the centrifugal product is put into a drying oven to be dried at 50-70 DEG C, grinding is conducted, and the Ho<3+>-Yb<3+>-F<-> codoped TiO2 upconversion nanopowder is obtained. The prepared Ho<3+>-Yb<3+>-F<-> codoped TiO2 upconversion nanopowder can absorb infrared spectrum in solar spectrum to emit visible light so as to achieve the upconversion effect, and the photoelectric conversion efficiency of a TiO2 sensitized solar cell and the photocatalytic efficiency of TiO2 can be improved by means of the effect.
Description
Technical field
The present invention relates to the evaluation and exploration technology field of the synthesis of inorganic material and new forms of energy, be specifically related to a kind of Ho3+-Yb3+-F-Codope TiO2The preparation method of upper conversion nano powder and application thereof。
Background technology
Titanium dioxide (Ti02) it is a kind of important wide bandgap semiconductor materials, nature exists with anatase, rutile and three kinds of different structures of brockite, there is the advantages, particularly TiO such as stable chemical nature, excellent corrosion resistance and weatherability, higher catalysis is active, nontoxic2Its big specific surface area of nano material substantially increases its surface activity, makes it in solar energy photoelectric conversion, photolysis water hydrogen manufacturing, and the aspect such as pollutant in photochromic and photocatalytic degradation air and water has broad application prospects。Such as, with TiO2Receive significant attention as the DSSC of light anode and the research of quantum dot sensitized battery and obtained very big progress。But, TiO2As wide bandgap semiconductor materials, sunlight is at TiO2On quasiconductor, its incident photon has two kinds of loss mechanisms originating from semiconductor intrinsic characteristic: can not by semiconductor absorber lower than the photon of quasiconductor band gap；High-energy photon scatters and disappears with the form of heat higher than the part energy of quasiconductor band gap, and this is two principal elements of restriction absorbing incident light efficiency。And the solar energy of 50% is in the near infrared region of wavelength 700-2500nm in solar spectrum。Therefore to expand TiO2The spectral response range of nano material, the task of top priority is to improve TiO2The photocatalysis efficiency of nano material and the photoelectric transformation efficiency of solaode。
Summary of the invention
In order to overcome shortcoming and the deficiency of prior art, the primary and foremost purpose of the present invention is in that to provide a kind of Ho3+-Yb3+-F-Codope TiO2The preparation method of upper conversion nano powder, this preparation method the Ho prepared3+-Yb3+-F-Codope TiO2Upper conversion nano powder can absorb the infrared spectrum in solar spectrum and launch visible ray and realize upconversion mechanism, utilizes this effect can improve TiO2The photoelectric transformation efficiency of sensitization solar cell and TiO2Photocatalysis efficiency。
It is a further object of the present invention to provide above-mentioned Ho3+-Yb3+-F-Codope TiO2The Ho that the preparation method of upper conversion nano powder obtains3+-Yb3+-F-Codope TiO2The purposes of upper conversion nano powder。
The present invention is achieved through the following technical solutions:
A kind of Ho3+-Yb3+-F-Codope TiO2The preparation method of upper conversion nano powder, comprises the steps:
A) at temperature is 70-90 DEG C, rare-earth oxidation holmium and rare-earth oxidation ytterbium are dissolved in excessive nitric acid, rare-earth oxidation holmium and rare-earth oxidation ytterbium are completely dissolved；After rare-earth oxidation holmium and rare-earth oxidation ytterbium are completely dissolved, reheating and evaporate unnecessary nitric acid, now solution is in neutrality, obtains holmium nitrate and Ytterbium(III) nitrate. solution that purity is 90-98wt%；
B) nitric acid and Fluohydric acid. are joined in 100ml deionized water, be stirring evenly and then adding into 25ml butyl titanate and continue stirring 20-40min, be heated to 90-100 DEG C of stirring 1-3h, obtain the hydrosol；
C) purity step a) obtained is the holmium nitrate of 90-98wt% and Ytterbium(III) nitrate. solution joins in the hydrosol that step b) obtains, and stirs 20-40min, obtains reaction precursor liquid；
D) reaction precursor liquid is transferred in the polytetrafluoroethyllining lining of the autoclave that volume is 200ml, seals still；Autoclave is placed in high temperature drying case, reacts 20-24h at 190-210 DEG C；
E) after having reacted, remove the supernatant in polytetrafluoroethyllining lining, disperse with EtOH Sonicate, centrifugal, repeat 3 times, remove unnecessary water and nitric acid, obtain centrifugal product；Centrifugal product being placed 50-70 DEG C of drying in drying baker, grinds, anneal 20-40min at temperature is 430-470 DEG C in air, obtains Ho3+-Yb3+-F-Codope TiO2Upper conversion nano powder。
Above-mentioned Ho3+-Yb3+-F-Codope TiO2The Ho that the preparation method of upper conversion nano powder prepares3+-Yb3+-F-Codope TiO2The sign of upper conversion nano powder: the X-ray diffraction such as Fig. 1-5 (XRD) figure, scanning electron microscope (SEM) figure, transmission electron microscope (TEM) figure, x-ray photoelectron power spectrum (XPS) figure and fluorescence spectrum figure can be adopted to characterize the Ho prepared3+-Yb3+-F-Codope TiO2The pattern of upper conversion nano powder, structure, composition and luminescent properties。
Wherein, the mass ratio of rare-earth oxidation holmium described in step a) and rare-earth oxidation ytterbium is 0.28-1.4:0.29-2.19。
Wherein, the volume ratio of nitric acid described in step b) and Fluohydric acid. is 2.5:0.4-1。
Wherein, in step c), regulate Ho atom in reaction precursor liquid, Yb atom and the F atom atomic percent relative to Ti atom by regulating the addition of Fluohydric acid., holmium nitrate and Ytterbium(III) nitrate. solution；In described reaction precursor liquid, Ho atom, Yb atom and F atom are relative to atomic percent respectively Ho/Ti:2-10%, Yb/Ti:2-15%, F/Ti=12-31% of Ti atom。
The invention also discloses a kind of above-mentioned Ho3+-Yb3+-F-Codope TiO2The Ho that the preparation method of upper conversion nano powder obtains3+-Yb3+-F-Codope TiO2Upper conversion nano power applications is in preparing DSSC。
Wherein, the preparation method of described DSSC, comprise the steps:
1) cleaning of FTO electro-conductive glass: be sequentially placed in acetone, dehydrated alcohol and deionized water by FTO electro-conductive glass each ultrasonic cleaning 8-12min, then dries；
2) preparation of silk screen printing slurry: 0.8-1.0g ethyl cellulose is joined in 8.0-8.2g ethanol, make the alcoholic solution that ethyl cellulose mass fraction is 8.9-11.1wt%, 9.4-9.8g terpineol and 9.0-9.4g dehydrated alcohol is added again gradually in this alcoholic solution, mix homogeneously, obtains mixed solution；By the above-mentioned Ho prepared3+-Yb3+-F-Codope TiO2Upper conversion nano powder 2.0-2.4g adds in this mixed solution；Magnetic agitation 16-24min, re-using ultrasonic power is 130-180W, supersonic frequency is 30-50KHZ ultrasonic disperse 16-24min, it is alternately repeated magnetic agitation and ultrasonic disperse 3-5 time, 40-60 DEG C of rotary evaporation is till without ethanol evaporation, it is subsequently adding the acetylacetone,2,4-pentanedione of 0.4-0.8ml and the OP emulsifying agent of 0.4-0.8ml, stirs, obtain silk screen printing slurry；
3) Ho3+-Yb3+-F-Codope TiO2The preparation of upper conversion nano porous membrane light anode: adopt screen printing technique, by step 2) in the silk screen printing slurry for preparing, be printed onto on FTO electro-conductive glass forming size is the Ho of 6mm*6mm3+-Yb3+-F-Codope TiO2Upper conversion nano porous membrane；This thin film being put into 430-470 DEG C of sintering 20-40min in Muffle furnace, then cools to 75-85 DEG C of taking-up, being immediately placed in concentration is 4.8-5.2 × 10-4The ethanol solution of the ruthenium complex N719 dyestuff of mol/L soaks 22-26h, washes away the dyestuff of remained on surface after taking-up with ethanol, dry, obtain Ho3+-Yb3+-F-Codope TiO2Upper conversion nano porous membrane light anode, keeps in Dark Place；
4) assembling of DSSC: by Ho3+-Yb3+-F-Codope TiO2Upper conversion nano porous membrane light anode be coated with the FTO glass of Pt thin film to electrode, KI/I2Solution is electrolyte, is assembled into DSSC。
Wherein, the structural formula of the dyestuff of ruthenium complex N719 described in step 3) be (n-2Bu4N)2-cis-Ru(L1)2(NCS)2。
Wherein, KI/I described in step 4)2The solute of solution is 0.5mol/LKI+0.05mol/LI2, solvent is percent by volume is 20wt% isopropanol and percent by volume is 80wt% acetonitrile。
The present invention compared with prior art, has the advantages that
1) present invention adopts deionized water, butyl titanate and nitric acid as reactant, using Fluohydric acid., Ytterbium(III) nitrate. and holmium nitrate as adulterant, adopts sol-gel self-combustion synthesis to prepare Ho3+-Yb3+-F?Codope TiO2Upper conversion nano powder；And by regulating the addition of Fluohydric acid., Ytterbium(III) nitrate. and holmium nitrate in reaction precursor liquid, it is possible to regulate preparation Ho3+-Yb3+-F?Codope TiO2Foreign ion Ho in upper conversion nano powder3+、Yb3+And F?Atomic percent, thus changing the luminous intensity at up-conversion luminescence peak。
2) Ho that the present invention prepares3+-Yb3+-F?Codope TiO2Upper conversion nano powder, and as wide bandgap semiconductor materials, can only absorb the pure TiO of ultraviolet light2Compare, it is possible to absorb the infrared spectrum in solar spectrum and launch visible ray, it is achieved upconversion mechanism。
3) Ho that the present invention prepares3+-Yb3+-F?Codope TiO2Upper conversion nano powder can be applied to prepare DSSC, it is possible to infrared spectrum is converted to the visible ray that can be absorbed by dyestuff, expands the absorption region of solar spectral, such that it is able to improve the photoelectric transformation efficiency of DSSC。
4) Ho that the present invention prepares3+-Yb3+-F?Codope TiO2Upper conversion nano powder can be used in the pollutant in photolysis water hydrogen manufacturing and photocatalytic degradation air and water, can improve light-catalysed efficiency。
Accompanying drawing explanation
The Ho that Fig. 1 the inventive method prepares3+-Yb3+-F-Codope TiO2X-ray diffraction (XRD) figure of upper conversion nano powder。
The Ho that Fig. 2 the inventive method prepares3+-Yb3+-F-Codope TiO2Scanning electron microscope (SEM) figure of upper conversion nano powder。
The Ho that Fig. 3 the inventive method prepares3+-Yb3+-F-Codope TiO2Transmission electron microscope (TEM) figure of upper conversion nano powder。
The Ho that Fig. 4 the inventive method prepares3+-Yb3+-F-Codope TiO2X-ray photoelectron power spectrum (XPS) figure of upper conversion nano powder。
The Ho that Fig. 5 the inventive method prepares3+-Yb3+-F-Codope TiO2Upper conversion nano powder fluorescence spectrum figure under 980nm laser excitation。
Detailed description of the invention
Further illustrating the present invention below by detailed description of the invention, following example are the present invention preferably embodiment, but embodiments of the present invention are not by the restriction of following embodiment。
Above-mentioned Ho3+-Yb3+-F-Codope TiO2The Ho that the preparation method of upper conversion nano powder prepares3+-Yb3+-F-Codope TiO2The sign of upper conversion nano powder: the X-ray diffraction such as Fig. 1-5 (XRD) figure, scanning electron microscope (SEM) figure, transmission electron microscope (TEM) figure, x-ray photoelectron power spectrum (XPS) figure and fluorescence spectrum figure can be adopted to characterize the Ho prepared3+-Yb3+-F-Codope TiO2The structure of upper conversion nano powder, pattern, composition and luminescent properties。XRD figure according to Fig. 1 is it can be seen that Ho3+-Yb3+-F-Codope TiO2Upper conversion nano powder is made up of the mixed phase of rutile and two kinds of structures of anatase；
The TEM figure of the SEM figure and Fig. 3 according to Fig. 2 can obtain Ho3+-Yb3+-F-Codope TiO2Upper conversion nano powder distribution ratio is more uniform, and Average Particle Diameters is about 20nm；
XPS figure according to Fig. 4 is it can be seen that Ho3+-Yb3+-F-Codope TiO2Ho in upper conversion nano powder3+、Yb3+And F-It is incorporated into TiO2In, the full spectrogram of XPS all has obvious peak；
Fluorescence spectrum figure according to Fig. 5 it can be seen that under the excitation of 980nm, Ho3+-Yb3+-F-Codope TiO2Upper conversion nano powder launches wavelength respectively at three glow peaks of 544nm, 650nm and 750nm, it is achieved that being converted to visible ray on infrared light。
Embodiments of the invention and comparative example adopt following raw material, but are not limited only to these raw materials:
Rare-earth oxidation holmium: Aladdin, 12055-62-8；
Rare-earth oxidation ytterbium: Aladdin, 1314-37-0；
Nitric acid: Guangzhou Chemical Reagent Factory, analytical pure；
Fluohydric acid.: Tianjin is big chemical reagent forever, analytical pure。
Embodiment 1:Ho
3+
-Yb
3+
-F
-
Codope TiO
2
The preparation of upper conversion nano powder
A) it is at 80 DEG C, 0.28g rare-earth oxidation holmium and 1.24g rare-earth oxidation ytterbium are dissolved in excessive nitric acid in temperature, rare-earth oxidation holmium and rare-earth oxidation ytterbium are completely dissolved；After rare-earth oxidation holmium and rare-earth oxidation ytterbium are completely dissolved, reheat and evaporate unnecessary nitric acid, obtain holmium nitrate and Ytterbium(III) nitrate. solution that purity is 95wt%；
B) 2.5ml nitric acid and 0.4ml Fluohydric acid. are joined in 100ml deionized water, be stirring evenly and then adding into 25ml butyl titanate and continue stirring 30min, be heated to 95 DEG C of stirring 2h, obtain the hydrosol；
C) purity step a) obtained is the holmium nitrate of 95wt% and Ytterbium(III) nitrate. solution joins in the hydrosol that step b) obtains, and stirs 30min, obtains reaction precursor liquid；
D) reaction precursor liquid is transferred in the polytetrafluoroethyllining lining of the autoclave that volume is 200ml, seals still；Autoclave is placed in high temperature drying case, reacts 24h at 200 DEG C；
E) after having reacted, remove the supernatant in polytetrafluoroethyllining lining, disperse with EtOH Sonicate, centrifugal, repeat 3 times, remove unnecessary water and nitric acid, obtain centrifugal product；Centrifugal product is placed 60 DEG C of drying in drying baker, grinds, be the 30min that anneals in air at 450 DEG C in temperature, obtain Ho3+-Yb3+-F-Codope TiO2Upper conversion nano powder；The Ho prepared3+-Yb3+-F-Codope TiO2The pattern of upper conversion nano powder, structure, composition and luminescent properties analysis are as Figure 1-5。
Embodiment 2:Ho
3+
-Yb
3+
-F
-
Codope TiO
2
The preparation of upper conversion nano powder
A) it is at 80 DEG C, 0.84g rare-earth oxidation holmium and 0.29g rare-earth oxidation ytterbium are dissolved in excessive nitric acid in temperature, rare-earth oxidation holmium and rare-earth oxidation ytterbium are completely dissolved；After rare-earth oxidation holmium and rare-earth oxidation ytterbium are completely dissolved, reheat and evaporate unnecessary nitric acid, obtain holmium nitrate and Ytterbium(III) nitrate. solution that purity is 96wt%；
B) 2.5ml nitric acid and 0.7ml Fluohydric acid. are joined in 100ml deionized water, be stirring evenly and then adding into 25ml butyl titanate and continue stirring 30min, be heated to 95 DEG C of stirring 2h, obtain the hydrosol；The other the same as in Example 1。
Embodiment 3:Ho
3+
-Yb
3+
-F
-
Codope TiO
2
The preparation of upper conversion nano powder
A) it is at 80 DEG C, 1.4g rare-earth oxidation holmium and 2.19g rare-earth oxidation ytterbium are dissolved in excessive nitric acid in temperature, rare-earth oxidation holmium and rare-earth oxidation ytterbium are completely dissolved；After rare-earth oxidation holmium and rare-earth oxidation ytterbium are completely dissolved, reheat and evaporate unnecessary nitric acid, obtain holmium nitrate and Ytterbium(III) nitrate. solution that purity is 98wt%；
B) 2.5ml nitric acid and 1ml Fluohydric acid. are joined in 100ml deionized water, be stirring evenly and then adding into 25ml butyl titanate and continue stirring 30min, be heated to 95 DEG C of stirring 2h, obtain the hydrosol；The other the same as in Example 1。
Embodiment 4: the Ho that embodiment 1 prepares
3+
-Yb
3+
-F
-
Codope TiO
2
Upper conversion nano power applications is in preparing DSSC
The preparation method of described DSSC, comprises the steps:
1) cleaning of FTO electro-conductive glass: be sequentially placed in acetone, dehydrated alcohol and deionized water by FTO electro-conductive glass each ultrasonic cleaning 10min, then dries；
2) preparation of silk screen printing slurry: 0.9g ethyl cellulose is joined in 8.1g ethanol, make the alcoholic solution that ethyl cellulose mass fraction is 10wt%, in this alcoholic solution, add 9.6g terpineol and 9.2g dehydrated alcohol, mix homogeneously more gradually, obtain mixed solution；The Ho that embodiment 1 is prepared3+-Yb3+-F-Codope TiO2Upper conversion nano powder 2.2g adds in this mixed solution；Magnetic agitation 20min, re-using ultrasonic power is 150W, supersonic frequency is 40KHZ ultrasonic disperse 20min, it is alternately repeated magnetic agitation and ultrasonic disperse 3-5 time, 50 DEG C of rotary evaporations are till without ethanol evaporation, it is subsequently adding the acetylacetone,2,4-pentanedione of 0.6ml and the OP emulsifying agent of 0.6ml, stirs, obtain silk screen printing slurry；
3) Ho3+-Yb3+-F-Codope TiO2The preparation of upper conversion nano porous membrane light anode: adopt screen printing technique, by step 2) in the silk screen printing slurry for preparing, be printed onto on FTO electro-conductive glass forming size is the Ho of 6mm*6mm3+-Yb3+-F-Codope TiO2Upper conversion nano porous membrane；This thin film being put into 450 DEG C of sintering 30min in Muffle furnace, then cools to 75-85 DEG C of taking-up, being immediately placed in concentration is 5.0 × 10-4The ethanol solution of the ruthenium complex N719 dyestuff of mol/L soaks 24h, washes away the dyestuff of remained on surface after taking-up with ethanol, dry, obtain Ho3+-Yb3+-F-Codope TiO2Upper conversion nano porous membrane light anode, keeps in Dark Place；Wherein, the structural formula of described ruthenium complex N719 dyestuff be (n-2Bu4N)2-cis-Ru(L1)2(NCS)2；
4) assembling of DSSC: by Ho3+-Yb3+-F-Codope TiO2Upper conversion nano porous membrane light anode be coated with the FTO glass of Pt thin film to electrode, KI/I2Solution is electrolyte, is assembled into DSSC；Wherein, described KI/I2The solute of solution is 0.5mol/LKI+0.05mol/LI2, solvent is percent by volume is 20wt% isopropanol and percent by volume is 80wt% acetonitrile。
Claims (8)
1. a Ho3+-Yb3+-F-Codope TiO2The preparation method of upper conversion nano powder, it is characterised in that comprise the steps:
A) at temperature is 70-90 DEG C, rare-earth oxidation holmium and rare-earth oxidation ytterbium are dissolved in excessive nitric acid, rare-earth oxidation holmium and rare-earth oxidation ytterbium are completely dissolved；After rare-earth oxidation holmium and rare-earth oxidation ytterbium are completely dissolved, reheating and evaporate unnecessary nitric acid, now solution is in neutrality, obtains holmium nitrate and Ytterbium(III) nitrate. solution that purity is 90-98wt%；
B) nitric acid and Fluohydric acid. are joined in 100ml deionized water, be stirring evenly and then adding into 25ml butyl titanate and continue stirring 20-40min, be heated to 90-100 DEG C of stirring 1-3h, obtain the hydrosol；
C) purity step a) obtained is the holmium nitrate of 90-98wt% and Ytterbium(III) nitrate. solution joins in the hydrosol that step b) obtains, and stirs 20-40min, obtains reaction precursor liquid；
D) reaction precursor liquid is transferred in the polytetrafluoroethyllining lining of the autoclave that volume is 200ml, seals still；Autoclave is placed in high temperature drying case, reacts 20-24h at 190-210 DEG C；
E) after having reacted, remove the supernatant in polytetrafluoroethyllining lining, disperse with EtOH Sonicate, centrifugal, repeat 3 times, remove unnecessary water and nitric acid, obtain centrifugal product；Centrifugal product being placed 50-70 DEG C of drying in drying baker, grinds, anneal 20-40min at temperature is 430-470 DEG C in air, obtains Ho3+-Yb3+-F-Codope TiO2Upper conversion nano powder。
2. Ho according to claim 13+-Yb3+-F-Codope TiO2The preparation method of upper conversion nano powder, it is characterised in that the mass ratio of rare-earth oxidation holmium described in step a) and rare-earth oxidation ytterbium is 0.28-1.4:0.29-2.19。
3. Ho according to claim 13+-Yb3+-F-Codope TiO2The preparation method of upper conversion nano powder, it is characterised in that the volume ratio of nitric acid described in step b) and Fluohydric acid. is 2.5:0.4-1。
4. Ho according to claim 13+-Yb3+-F-Codope TiO2The preparation method of upper conversion nano powder, it is characterised in that in reaction precursor liquid described in step c), Ho atom, Yb atom and F atom are relative to atomic percent respectively Ho/Ti:2-10%, Yb/Ti:2-15%, F/Ti=12-31% of Ti atom。
5. the Ho as described in any one of claim 1-43+-Yb3+-F-Codope TiO2The Ho that the preparation method of upper conversion nano powder obtains3+-Yb3+-F-Codope TiO2Upper conversion nano power applications is in preparing DSSC。
6. Ho according to claim 53+-Yb3+-F-Codope TiO2Upper conversion nano power applications is in preparing DSSC, it is characterised in that the preparation method of described DSSC, comprises the steps:
1) cleaning of FTO electro-conductive glass: be sequentially placed in acetone, dehydrated alcohol and deionized water by FTO electro-conductive glass each ultrasonic cleaning 8-12min, then dries；
2) preparation of silk screen printing slurry: 0.8-1.0g ethyl cellulose is joined in 8.0-8.2g ethanol, make the alcoholic solution that ethyl cellulose mass fraction is 8.9-11.1wt%, 9.4-9.8g terpineol and 9.0-9.4g dehydrated alcohol is added again gradually in this alcoholic solution, mix homogeneously, obtains mixed solution；The Ho that claim 1-4 is prepared3+-Yb3+-F-Codope TiO2Upper conversion nano powder 2.0-2.4g adds in this mixed solution；Magnetic agitation 16-24min, re-using ultrasonic power is 130-180W, supersonic frequency is that 30-50KHZ carries out ultrasonic disperse 16-24min, it is alternately repeated magnetic agitation and ultrasonic disperse 3-5 time, 40-60 DEG C of rotary evaporation is till without ethanol evaporation, it is subsequently adding the acetylacetone,2,4-pentanedione of 0.4-0.8ml and the OP emulsifying agent of 0.4-0.8ml, stirs, obtain silk screen printing slurry；
3) Ho3+-Yb3+-F-Codope TiO2The preparation of upper conversion nano porous membrane light anode: adopt screen printing technique, by step 2) in the silk screen printing slurry for preparing, be printed onto on FTO electro-conductive glass forming size is the Ho of 6mm*6mm3+-Yb3+-F-Codope TiO2Upper conversion nano porous membrane；This thin film being put into 430-470 DEG C of sintering 20-40min in Muffle furnace, then cools to 75-85 DEG C of taking-up, being immediately placed in concentration is 4.8-5.2 × 10-4The ethanol solution of the ruthenium complex N719 dyestuff of mol/L soaks 22-26h, washes away the dyestuff of remained on surface after taking-up with ethanol, dry, obtain Ho3+-Yb3+-F-Codope TiO2Upper conversion nano porous membrane light anode, keeps in Dark Place；
4) assembling of DSSC: by Ho3+-Yb3+-F-Codope TiO2Upper conversion nano porous membrane light anode be coated with the FTO glass of Pt thin film to electrode, KI/I2Solution is electrolyte, is assembled into DSSC。
7. Ho according to claim 53+-Yb3+-F-Codope TiO2Upper conversion nano power applications is in preparing DSSC, it is characterised in that the structural formula of the dyestuff of ruthenium complex N719 described in step 3) be (n-2Bu4N)2-cis-Ru(L1)2(NCS)2。
8. Ho according to claim 53+-Yb3+-F-Codope TiO2Upper conversion nano power applications is in preparing DSSC, it is characterised in that KI/I described in step 4)2The solute of solution is 0.5mol/LKI+0.05mol/LI2, solvent is percent by volume is 20wt% isopropanol and percent by volume is 80wt% acetonitrile。
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