CN110420652A - A kind of NaYF4:Yb/Er@MoS2Core-shell structure micron crystalline substance and preparation method thereof - Google Patents
A kind of NaYF4:Yb/Er@MoS2Core-shell structure micron crystalline substance and preparation method thereof Download PDFInfo
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- 239000000126 substance Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 77
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 77
- 239000011258 core-shell material Substances 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 9
- 229910004619 Na2MoO4 Inorganic materials 0.000 claims abstract description 4
- 238000005253 cladding Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 4
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 229910015667 MoO4 Inorganic materials 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 8
- 238000004140 cleaning Methods 0.000 abstract description 7
- 239000004065 semiconductor Substances 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 56
- 229910052691 Erbium Inorganic materials 0.000 description 55
- 235000019441 ethanol Nutrition 0.000 description 14
- 229910002651 NO3 Inorganic materials 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- 229910052761 rare earth metal Inorganic materials 0.000 description 9
- -1 rare earth nitrate Chemical class 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 239000001509 sodium citrate Substances 0.000 description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 6
- 230000003595 spectral effect Effects 0.000 description 6
- 239000011734 sodium Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229940053652 fluorinse Drugs 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 3
- 229940038773 trisodium citrate Drugs 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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Abstract
A kind of NaYF4:Yb/Er@MoS2Core-shell structure micron crystalline substance and preparation method thereof, the present invention relates to upper conversion@two-dimensional semiconductor materials and preparation method thereof.NaYF of the invention4:Yb/Er@MoS2Core-shell structure micron crystalline substance is with Yb3+、Er3+Codope NaYF4Micron is brilliant for kernel and in core outer cladding MoS2It constitutes.Preparation method；By Na2MoO4·2H2O、SC(NH2)2、H2C2O4It is added to the water and shell stoste is made；Again by Yb3+、Er3+Codope NaYF4Micron crystalline substance, which is added in shell stoste, to react, then is transferred in reaction kettle and carries out hydro-thermal reaction, and cleaning, drying obtain NaYF4:Yb/Er@MoS2Core-shell structure micron is brilliant.The core-shell structure micron crystal structure is stablized.It can be used for photocatalysis field.
Description
Technical field
The present invention relates to upper conversion@two-dimensional semiconductor materials and preparation method thereof.
Background technique
With the rapid development of economy, environmental pollution and problem of energy crisis receive more and more attention.People are exerting
Power finds clean reproducible energy, to achieve the purpose that protect environment energy saving, solar energy, wind energy, biomass energy, Hydrogen Energy etc.
All it is renewable energy, and water decomposition can be provided to a great potential for the Photocatalitic Technique of Semiconductor of hydrogen for mankind's new energy
Direction.Influence photocatalytic activity because being known as: the separation of semiconductor band gap width and energy band present position, photo-generated carrier is imitated
Rate, spectral response range of catalysis material etc..Most-often used catalysis material TiO2Its band gap width is 3.2ev, is swashed
Hair wavelength is located at 387nm, is located at ultraviolet region, determines that the ultraviolet light that it is only capable of being absorbed and utilized in ultraviolet light or sunlight carries out
Photocatalyzed Hydrogen Production significantly limits its light-catalysed efficiency.Up-conversion have near infrared light is transformed into it is ultraviolet and can
Light-exposed characteristic combines the low energy of two or more low energy near-infrared photons, by the electronics being excited " promotion "
To expected high level, thus the spectral response range of Photocatalyzed Hydrogen Production class catalyst can be widened near infrared region.
The combination of current semiconductor material and up-conversion luminescent material is generally simple physical mixed, physical mixed
The performance of sample depends on mixed uniformity coefficient, and in addition the energy transmission efficiency between the two of physical mixed kind substance is poor, leads
Cause product low to the utilization rate of sunlight.
Summary of the invention
The present invention is to solve the sunlights of the semiconductor of existing physical mixing processes preparation and upper conversion composite material
The low technical problem of utilization rate, and a kind of NaYF is provided4:Yb/Er@MoS2Core-shell structure micron crystalline substance and preparation method thereof.
NaYF of the invention4:Yb/Er@MoS2Core-shell structure micron crystalline substance is with Yb3+、Er3+Codope NaYF4Micron crystalline substance be
Kernel and in core outer cladding MoS2It constitutes, uses NaYF4:Yb3+/Er3+@MoS2It indicates.
Above-mentioned NaYF4:Yb/Er@MoS2The preparation method of core-shell structure micron crystalline substance, sequentially includes the following steps:
One, by Na2MoO4·2H2O、SC(NH2)2、H2C2O4It is added to the water, is heated to temperature and is 20~50 DEG C and stirs 20
~30min obtains shell stoste；
Two, by Yb3+、Er3+Codope NaYF4Micron is brilliant to be added in the shell stoste that step 1 obtains, and is stirred to react 0.6
After~0.8h, reaction solution is transferred in the reaction kettle with polytetrafluoroethyllining lining, is sealed；
Three, reaction kettle is put into heating furnace, is warming up to 160~200 DEG C of 24~48h of holding, be cooled to room temperature centrifugation point
From, the solid formation ethanol washing isolated is clean, and it is dry, obtain NaYF4:Yb/Er@MoS2Core-shell structure micron is brilliant.
NaYF of the invention4:Yb/Er@MoS2Core-shell structure micron crystalline substance is a kind of stable NaYF4:Yb3+/Er3+@MoS2It is different
Matter core-shell structure, this stable structure is by MoS2Semiconductor is even closer in conjunction with up-conversion luminescent material, so as to more
Add and efficiently utilizes infrared photon energy.It is a kind of pale powder.
It is coated on Yb3+、Er3+Codope NaYF4Nanometer MoS outside micron crystalline substance2S-Mo-S in edge lattice is coordinated meeting
Unsaturated Mo and S atom are generated, MoS is caused2Edge generates preferable photocatalytic activity site.Upper conversion micron crystalline substance and MoS2
In conjunction with the stable core-shell structure of formation, the brilliant application of upper conversion micron is so that the NaYF4:Yb/Er@MoS2Core-shell structure micron
Crystalline substance can more efficiently utilize infrared energy, and the utilization of sunlight is extended near infrared region, keeps energy supply more abundant, together
When shell core rock-steady structure in turn ensure by it is upper conversion micron crystalline substance conversion energy can continually be conveyed to MoS2, to mention
High photocatalysis efficiency.
The present invention is by nanoscale MoS2By chemical bond or other make micro-nano active force ordered fabrication to Yb3+、Er3+It is double-doped
Miscellaneous NaYF4The brilliant surface of micron, other than improving the transmitting of fluorescence resonance energy, additionally it is possible to be effectively prevented conversion micron nucleus
Contaminated inactivation.
The present invention overcomes NaYF4:Yb3+/Er3+@MoS2This core-shell structure is not easy growth shaping, is difficult to improve sunlight
The technical issues of utilization rate, realizes the preparation of core-shell structure, and stable structure.
Detailed description of the invention
Fig. 1 is in embodiment 1 through the obtained NaYF in step 14: 20%Yb3+/ 2%Er3+3000 times of micron crystalline substance is swept
Retouch electromicroscopic photograph；
Fig. 2 is in embodiment 1 through the obtained NaYF in step 14: 20%Yb3+/ 2%Er3+10000 times of micron crystalline substance is swept
Retouch electromicroscopic photograph；
Fig. 3 is the NaYF that embodiment 1 obtains4: 20%Yb3+/ 2%Er3+@MoS2The scanning electron microscope of core-shell structure micron crystalline substance is shone
Piece；
Fig. 4 is the NaYF that embodiment 1 obtains4: 20%Yb3+/ 2%Er3+@MoS2The element of core-shell structure micron crystalline substance
Mapping figure；
Fig. 5 is the NaYF that embodiment 1 obtains4: 20%Yb3+/ 2%Er3+@MoS2The EDS energy spectrum diagram of core-shell structure micron crystalline substance；
Fig. 6 is the NaYF that embodiment 1 obtains4: 20%Yb3+/ 2%Er3+@MoS2The XRD spectra of core-shell structure micron crystalline substance；
Fig. 7 is the NaYF prepared in embodiment 1 through step 14: 20%Yb3+/ 2%Er3+、NaYF4: 20%Yb3+/ 2%Er3 +With MoS2The sample and NaYF of direct physical mixed4: 20%Yb3+/ 2%Er3+@MoS2The up-conversion fluorescence of core-shell structure micron crystalline substance
Spectrogram；
Fig. 8 is NaYF prepared by embodiment 24: 20%Yb3+/ 2%Er3+@MoS2The transmission electron microscope of core-shell structure micron crystalline substance shines
Piece；
Fig. 9 is NaYF prepared by embodiment 24: 20%Yb3+/ 2%Er3+@MoS2The Up-conversion emission of core-shell structure micron crystalline substance
Spectrogram；
Figure 10 is NaYF prepared by embodiment 34: 10%Yb3+/ 1%Er3+@MoS2The EDS power spectrum of core-shell structure micron crystalline substance
Figure；
Figure 11 is NaYF prepared by embodiment 34: 10%Yb3+/ 1%Er3+@MoS2The upper conversion of core-shell structure micron crystalline substance is sent out
Penetrate spectrogram.
Specific embodiment
Specific embodiment 1: the NaYF of present embodiment4:Yb/Er@MoS2Core-shell structure micron crystalline substance is with Yb3+、Er3+
Codope NaYF4Micron is brilliant for kernel and in core outer cladding MoS2It constitutes, uses NaYF4:Yb3+/Er3+@MoS2It indicates.
Specific embodiment 2: the present embodiment is different from the first embodiment in that with Yb3+、Er3+Codope NaYF4
In micron crystalline substance, Yb3+The atomic percent of doping is 10%~30%；Er3+The atomic percent of doping is 1%~3%；It is other
It is same as the specific embodiment one.
Specific embodiment 3: the present embodiment is different from the first and the second embodiment in that with Yb3+、Er3+Codope
NaYF4In micron crystalline substance, NaYF4:Yb3+/Er3+For hexagonal phase, micron crystalline substance is having a size of 2~3 μm；It is other with specific embodiment one or
Two is identical.
Specific embodiment 4: NaYF described in specific embodiment one4:Yb/Er@MoS2The system of core-shell structure micron crystalline substance
Preparation Method sequentially includes the following steps:
One, by Na2MoO4·2H2O、SC(NH2)2、H2C2O4It is added to the water, is heated to temperature and is 20~50 DEG C and stirs 20
~30min obtains shell stoste；
Two, by Yb3+、Er3+Codope NaYF4Micron is brilliant to be added in the shell stoste that step 1 obtains, and is stirred to react 0.6
After~0.8h, reaction solution is transferred in the reaction kettle with polytetrafluoroethyllining lining, is sealed；
Three, reaction kettle is put into heating furnace, is warming up to 160~200 DEG C of 24~48h of holding, be cooled to room temperature centrifugation point
From, the solid formation ethanol washing isolated is clean, and it is dry, obtain NaYF4:Yb/Er@MoS2Core-shell structure micron is brilliant.
Specific embodiment 5: present embodiment and Na in step 1 unlike specific embodiment four2MoO4·
2H2O、SC(NH2)2With H2C2O4Molar ratio be 1:(3~5): (0.3~1.5)；It is other identical as specific embodiment four.
Specific embodiment 6: present embodiment Na in step 1 unlike specific embodiment four or five2MoO4·
2H2The ratio between amount and the volume of water of the substance of O are 1mmol:(10~15) mL；It is other identical as specific embodiment four or five.
Specific embodiment 7: dry in step 3 unlike one of present embodiment and specific embodiment four to six
Temperature when dry is 60-80 DEG C, and drying time is 2~6h；It is other identical as one of specific embodiment four to six.
Specific embodiment 8: unlike one of present embodiment and specific embodiment four to seven described in step 2
Yb3+、Er3+Codope NaYF4Micron crystalline substance is synthesized with hydro-thermal method, and synthesis step is as follows:
(1) 0.0459~0.1377g Er is weighed2O3, 0.2364~0.7092g Yb2O3, 0.9560~1.3839g
Y2O3, it is respectively placed in 50ml cleaning beaker, suitable distilled water is added, is heated on Electric stove, nitric acid solution is added dropwise,
And stirred using glass bar, stop that nitric acid solution is added dropwise after solution in beaker is gradually clarified, continues to heat and stir, evaporate
After extra acid, it is cooled to room temperature, then is settled in 100ml volumetric flask, three kinds of rare earth nitrate solutions are obtained；
(2) 30ml Y (NO is measured respectively3)3Solution, 16ml Yb (NO3)3Solution, 8ml Er (NO3)3Solution holds in 100ml
In measuring bottle, adds 42ml distilled water to dilute, obtain mixed rare earth nitrates solution；
(3) 0.6299g NaF is weighed in 50ml cleaning centrifuge tube, and ultrasonic dissolution is spare after 30ml distilled water is added；
(4) it weighs 8.8230g trisodium citrate to be put into 100ml beaker, it is standby to be transferred to dissolution constant volume in 100ml volumetric flask
With；
(5) 4ml sodium citrate solution and 6ml mixed rare earth nitrates solution are added in the clean beaker for being placed with magneton,
20min is stirred on magnetic stirring apparatus, adds the configured Fluorinse of 28.8ml, is continued to stir 30min, will be reacted molten
Liquid is fitted into polytetrafluoroethyllining lining, and is put into reaction kettle, and hydro-thermal reaction for 24 hours, be used in combination by centrifuge separation under the conditions of 180 DEG C
Ethyl alcohol carries out 3 washings, obtains NaYF4: (10~30) Yb3+/ (1~3) Er3+；
It is other identical as one of specific embodiment four to six.
Beneficial effects of the present invention are verified with the following examples:
Embodiment 1: the NaYF of the present embodiment4:Yb/Er@MoS2The preparation method of core-shell structure micron crystalline substance, according to the following steps
It carries out:
One, hydro-thermal method synthesizes Yb3+、Er3+Codope NaYF4Micron crystalline substance NaYF4: 20%Yb3+/ 2%Er3+: specific step
It is as follows:
(1) 0.0918g Er is weighed2O3、0.4728g Yb2O3、1.1291g Y2O3, it is respectively placed in 50ml cleaning beaker,
Suitable distilled water is added, is heated on Electric stove, nitric acid solution is added dropwise, and stir using glass bar, to molten in beaker
Liquid stops that nitric acid solution is added dropwise after gradually clarifying, and continues to heat and stir, and after evaporating extra acid, is cooled to room temperature, then fixed
Hold into 100ml volumetric flask, obtains three kinds of rare earth nitrate solutions；
(2) 30ml Y (NO is measured respectively3)3Solution, 16ml Yb (NO3)3Solution, 8ml Er (NO3)3100ml is added in solution
In volumetric flask, adds 42ml distilled water to dilute, obtain mixed rare earth nitrates solution；
(3) it weighs 0.6299g NaF to be added in 50ml cleaning centrifuge tube, ultrasonic dissolution is spare after 30ml distilled water is added；
(4) it weighs 8.8230g trisodium citrate to be put into 100ml beaker, it is standby to be transferred to dissolution constant volume in 100ml volumetric flask
With；
(5) 4ml sodium citrate solution and 6ml mixed rare earth nitrates solution are added in the clean beaker for being placed with magneton,
20min is stirred on magnetic stirring apparatus, adds the configured Fluorinse of 28.8ml, is continued to stir 30min, will be reacted molten
Liquid is fitted into polytetrafluoroethyllining lining, and is put into reaction kettle, and hydro-thermal reaction for 24 hours, be used in combination by centrifuge separation under the conditions of 180 DEG C
Ethyl alcohol carries out 3 washings, obtains Yb3+、Er3+Codope NaYF4Micron is brilliant, is denoted as NaYF4: 20%Yb3+/ 2%Er3+；
Two, 0.72g Na is weighed2MoO4·2H2O、0.96g SC(NH2)2、0.22g H2C2O430mL deionized water is added
In, it is placed on magnetic stirring apparatus, being heated to temperature is 30 DEG C, and stirs 20min, obtains shell stoste；
Three, the 0.205g NaYF for preparing step 14: 20%Yb3+/ 2%Er3+Micron is brilliant to be added to what step 2 obtained
In shell stoste, after reaction 0.8h is stirred at room temperature, it is 50mL with the anti-of polytetrafluoroethyllining lining that reaction solution, which is transferred to volume,
It answers in kettle, seals；
Four, reaction kettle is put into air dry oven, is warming up to 180 DEG C of holding 30h, after reaction, certainly by reaction kettle
It is so down to room temperature, supernatant liquor is removed, the centrifuge separation of 10ml ethyl alcohol is added in bottom solid, the solid formation isolated is washed with ethyl alcohol
It washs 3 times, is added in the sample after washing in 5ml ethyl alcohol, be put into 60 DEG C of baking oven dry 2h, obtain NaYF4: 20%Yb3+/
2%Er3+@MoS2Core-shell structure micron is brilliant.
Obtained NaYF in the present embodiment step 14: 20%Yb3+/ 2%Er3+Brilliant 3000 times of the scanning electron microscope of micron is shone
Piece is as shown in Figure 1, NaYF4: 20%Yb3+/ 2%Er3+Brilliant 10000 times of the stereoscan photograph of micron is as shown in Figure 2.From Fig. 1 and
Fig. 2 can be seen that the NaYF being prepared4: 20%Yb3+/ 2%Er3+Brilliant micron is hexagonal plate, and surface is clean, free from admixture,
Crystallization degree with higher.
The NaYF that the present embodiment obtains4: 20%Yb3+/ 2%Er3+@MoS2Core-shell structure micron crystalline substance is a kind of greyish white toner
End, its scanning electron microscope (SEM) photograph is as shown in figure 3, from figure 3, it can be seen that core-shell structure NaYF4: 20%Yb3+/ 2%Er3+@MoS2It is micro-
The rough surface of meter Jing, illustrates MoS2Deposit to nucleating surface, hexagonal phase NaYF4: 20%Yb3+/ 2%Er3+@MoS2The brilliant ruler of micron
Very little about 2.4 μm.
The NaYF that the present embodiment obtains4: 20%Yb3+/ 2%Er3+@MoS2The element mapping of core-shell structure micron crystalline substance schemes
As shown in figure 4, including Mo, S, F, Y, Na, Yb and Er element, from fig. 4, it can be seen that there is Mo and S on hexagonal plate surface
Signal, also confirm that MoS2It is deposited on NaYF4: 20%Yb3+/ 2%Er3+The brilliant surface of micron.Wherein the elemental signals of Na, Y, F are non-
Chang Qiang, and be in hexagon shape, it fits like a glove with scanning electron microscope result.Also occur Yb in figure and the signal of Er is equally uniform
Dispersion, illustrate Yb and Er Uniform Doped in NaYF4In lattice.
The NaYF that the present embodiment obtains4: 20%Yb3+/ 2%Er3+@MoS2The EDS power spectrum of the element of core-shell structure micron crystalline substance
As shown in figure 5, from fig. 5, it can be seen that there are Na, Y, F, Yb, Er, Mo and S signal peaks, with element in core-shell structure particle
Mapping result is mutually confirmed, it was demonstrated that successful growth goes out a kind of stable NaYF4: 20%Yb3+/ 2%Er3+@MoS2Nucleocapsid knot
Structure.
The NaYF that the present embodiment obtains4: 20%Yb3+/ 2%Er3+@MoS2XRD spectra such as Fig. 6 institute of core-shell structure micron crystalline substance
Show, from fig. 6, it can be seen that occurring very strong diffraction maximum and NaYF at 16 °, 31 °, 34 °, 39 °, 43 °, 53 °, 71 °, 78 °4
Standard spectrogram (JCPDS:16-0344) goodness of fit it is all very high, illustrate NaYF4: 20%Yb3+/ 2%Er3+Nucleus has very
High degree of crystallization.The diffraction maximum gone out simultaneously at 15 ° and 33 ° is standard MoS2It is corresponding, it was demonstrated that form stable NaYF4: 20%
Yb3+/ 2%Er3+@MoS2Core-shell structure.
The NaYF that will be prepared through step 14: 20%Yb3+/ 2%Er3+, NaYF4: 20%Yb3+/ 2%Er3+With MoS2Direct object
Manage the NaYF that mixed sample and the present embodiment obtain4: 20%Yb3+/ 2%Er3+@MoS2Core-shell structure micron crystalline substance carries out conversion
Fluorescence spectrum test, testing light source use 1W/cm2980nm laser, obtained spectrogram is as shown in fig. 7, NaYF4: 20%Yb3 +/ 2%Er3+The curve of spectrum as shown in curve a, can be seen that NaYF from curve a4: 20%Yb3+/ 2%Er3+Upper conversion it is glimmering
Light includes that 3 strong transmitting spectral peak is located at 525nm, 540nm and 660nm, corresponds respectively to Er3+Ion2H11/2→4I15/2
、4S3/2→4I15/2With4F9/2→4I15/2Transition.
NaYF4: 20%Yb3+/ 2%Er3+With MoS2The curve of spectrum of the sample of direct physical mixed is as shown in b, from curve b
In as can be seen that green emitted light only have 20% by MoS2It absorbs.
Coat MoS2After shell, obtained NaYF4: 20%Yb3+/ 2%Er3+@MoS2The spectrum of core-shell structure micron crystalline substance is bent
Line as shown by c, can be seen that NaYF from curve c4:Yb/Er@MoS2The emission peak positions of core-shell structure micron crystalline substance there is no
Variation, and fluorescent emission intensity is substantially change.NaYF4:Yb3+,Er3+@MoS2Core-shell structure particle is to 525nm and 540nm
Green emitted light has stronger absorption transformation, and there are about 60% photon energies by MoS for green emitted luminous intensity2Shell is inhaled
It receives, leads to spectral intensity sharp fall, to know the NaYF of core-shell structure4:Yb/Er@MoS2Core-shell structure micron crystalline substance has
Superior light conversion properties energy.
Embodiment 2: the NaYF of the present embodiment4: 20%Yb3+/ 2%Er3+@MoS2The preparation method of core-shell structure micron crystalline substance,
It sequentially includes the following steps:
One, using method same as Example 1, hydro-thermal method synthesizes Yb3+、Er3+Codope NaYF4Micron crystalline substance NaYF4:
20%Yb3+/ 2%Er3+；
Two, 0.48g Na is weighed2MoO4·2H2O、0.68g SC(NH2)2、0.14g H2C2O430mL deionized water is added
In, it is placed on magnetic stirring apparatus, being heated to temperature is 30 DEG C, and stirs 30min, obtains shell stoste；
Three, the 0.205g NaYF for preparing step 14: 20%Yb3+/ 2%Er3+Micron is brilliant to be added to what step 2 obtained
In shell stoste, after reaction 0.6h is stirred at room temperature, it is 50mL with the anti-of polytetrafluoroethyllining lining that reaction solution, which is transferred to volume,
It answers in kettle, seals；
Four, reaction kettle is put into air dry oven, is warming up to 200 DEG C and keeps for 24 hours, after reaction, certainly by reaction kettle
It is so down to room temperature, supernatant liquor is removed, the centrifuge separation of 10ml ethyl alcohol is added in bottom solid, the solid formation isolated is washed with ethyl alcohol
It washs 3 times, is added in the sample after washing in 10ml ethyl alcohol, be put into 80 DEG C of baking oven dry 2h, obtain NaYF4: 20%Yb3 +/ 2%Er3+@MoS2Core-shell structure micron is brilliant.
NaYF manufactured in the present embodiment4: 20%Yb3+/ 2%Er3+@MoS2The transmission electron microscope photo of core-shell structure micron crystalline substance is such as
Shown in Fig. 8, from figure 8, it is seen that micron crystalline substance is in hexagon shape, it is hexagonal phase NaYF4: 20%Yb3+/ 2%Er3+Surface deposition
MoS2, the rough surface of micron crystalline substance.
NaYF manufactured in the present embodiment4: 20%Yb3+/ 2%Er3+@MoS2The Up-conversion emission spectrum of core-shell structure micron crystalline substance
Figure is as shown in figure 9, from fig. 9, it can be seen that prepared NaYF4: 20%Yb3+/ 2%Er3+@MoS2Sample is in 980nm laser light
3 up-conversion fluorescences are generated under source excitation and emit spectral peak, the green light of respectively 525nm and 540nm, and the feux rouges of 660nm needs to infuse
Meaning, the intensity that peak occurs for green light is 107, is matched with 1 result of embodiment, illustrating that the patented method can be prepared will be infrared
Light is transformed into visible region and is MoS2The high performance material that shell is absorbed and utilized, can apply to photocatalysis field.
Embodiment 3: the NaYF of the present embodiment4: 10%Yb3+/ 1%Er3+@MoS2The preparation method of core-shell structure micron crystalline substance,
It sequentially includes the following steps:
One, hydro-thermal method synthesizes Yb3+、Er3+Codope NaYF4Micron crystalline substance NaYF4:10Yb3+/1Er3+, preparation method is such as
Under:
(1) 0.0459g Er is weighed2O3、0.2364g Yb2O3、1.2884g Y2O3, it is respectively placed in 50ml cleaning beaker,
Suitable distilled water is added, is heated on Electric stove, nitric acid solution is added dropwise, and stir using glass bar, in beaker
Solution stops that nitric acid solution is added dropwise after gradually clarifying, and continues to heat and stir, after evaporating extra acid, is cooled to room temperature, then
It is settled in 100ml volumetric flask, obtains three kinds of rare earth nitrate solutions；
(2) 30ml Y (NO is measured respectively3)3Solution, 16ml Yb (NO3)3Solution, 8ml Er (NO3)3Solution holds in 100ml
In measuring bottle, adds 42ml distilled water to dilute, obtain mixed rare earth nitrates solution；
(3) 0.6299g NaF is weighed in 50ml cleaning centrifuge tube, and ultrasonic dissolution is spare after 30ml distilled water is added；
(4) it weighs 8.8230g trisodium citrate to be put into 100ml beaker, it is standby to be transferred to dissolution constant volume in 100ml volumetric flask
With；
(5) 4ml sodium citrate solution and 6ml mixed rare earth nitrates solution are added in the clean beaker for being placed with magneton,
20min is stirred on magnetic stirring apparatus, adds the configured Fluorinse of 28.8ml, is continued to stir 30min, will be reacted molten
Liquid is fitted into polytetrafluoroethyllining lining, and is put into reaction kettle, and hydro-thermal reaction for 24 hours, be used in combination by centrifuge separation under the conditions of 180 DEG C
Ethyl alcohol carries out 3 washings, obtains Yb3+、Er3+Codope NaYF4Micron is brilliant, is denoted as NaYF4:10Yb3+/1Er3+；
Two, 1.21g Na is weighed2MoO4·2H2O, 1.14g SC (NH2)2, 0.27g H2C2O430mL deionized water is added
In, it is placed on magnetic stirring apparatus, being heated to temperature is 30 DEG C, and stirs 30min, obtains shell stoste；
Three, the 0.205g NaYF for preparing step 14: 10%Yb3+/ 1%Er3+Micron is brilliant to be added to what step 2 obtained
In shell stoste, after reaction 0.7h is stirred at room temperature, it is 50mL with the anti-of polytetrafluoroethyllining lining that reaction solution, which is transferred to volume,
It answers in kettle, seals；
Four, reaction kettle is put into air dry oven, is warming up to 190 DEG C and keeps for 24 hours, after reaction, certainly by reaction kettle
It is so down to room temperature, supernatant liquor is removed, the centrifuge separation of 10ml ethyl alcohol is added in bottom solid, the solid formation isolated is washed with ethyl alcohol
It washs 3 times, is added in the sample after washing in 10ml ethyl alcohol, be put into 70 DEG C of baking oven dry 2h, obtain NaYF4: 10%Yb3 +/ 1%Er3+@MoS2Core-shell structure micron is brilliant.
NaYF manufactured in the present embodiment4: 10%Yb3+/ 1%Er3+@MoS2The EDS energy spectrum diagram of core-shell structure micron crystalline substance is as schemed
Shown in 10, from fig. 10 it can be seen that there are Na, Y, F, Yb, Er, Mo and S signal peaks in core-shell structure particle.
NaYF manufactured in the present embodiment4: 10%Yb3+/ 1%Er3+@MoS2The Up-conversion emission spectrum of core-shell structure micron crystalline substance
Figure is as shown in figure 11, it can be seen from figure 11 that prepared NaYF4: 10%Yb3+/ 1%Er3+@MoS2Sample is in 980nm laser
3 up-conversion fluorescences transmitting spectral peaks of generation under light source activation, the green light of respectively 525nm and 540nm, the feux rouges of 660nm, and
The intensity that peak occurs for green light is about 100, and intensity is slightly weaker than sample prepared by example 1, this is because only adulterating in core
10%Yb3+And 1%Er3+Ion causes nucleus to shine and is weaker than NaYF in itself4: 20%Yb3+/ 2%Er3+Nucleus, but from upper conversion
From the point of view of the emission peak positions and intensity of fluorescence, the same material for confirming this method preparation can convert infrared light to visible green
It and is MoS2Shell is absorbed and utilized, and has the great potential applied in photocatalysis field.
Claims (7)
1. a kind of NaYF4:Yb/Er@MoS2Core-shell structure micron is brilliant, it is characterised in that this micron of crystalline substance is with Yb3+、Er3+Codope
NaYF4Micron is brilliant for kernel and in core outer cladding MoS2It constitutes.
2. a kind of NaYF according to claim 14:Yb/Er@MoS2Core-shell structure micron is brilliant, it is characterised in that with Yb3+、
Er3+Codope NaYF4In micron crystalline substance, Yb3+The atomic percent of doping is 10%~30%；Er3+The atomic percent of doping is
1%~3%.
3. a kind of NaYF according to claim 1 or 24:Yb/Er@MoS2Core-shell structure micron is brilliant, it is characterised in that with Yb3 +、Er3+Codope NaYF4In micron crystalline substance, NaYF4:Yb3+/Er3+For hexagonal phase, micron crystalline substance is having a size of 2~3 μm.
4. preparing a kind of NaYF described in claim 14:Yb/Er@MoS2The method of core-shell structure micron crystalline substance, it is characterised in that should
Method sequentially includes the following steps:
One, by Na2MoO4·2H2O、SC(NH2)2、H2C2O4Be added to the water, be heated to temperature be 20~50 DEG C and stir 20~
30min obtains shell stoste；
Two, by Yb3+、Er3+Codope NaYF4Micron is brilliant to be added in the shell stoste that step 1 obtains, it is stirred to react 0.6~
After 0.8h, reaction solution is transferred in the reaction kettle with polytetrafluoroethyllining lining, is sealed；
Three, reaction kettle is put into heating furnace, is warming up to 160~200 DEG C of 24~48h of holding, is cooled to room temperature centrifuge separation, point
The solid formation ethanol washing separated out is clean, dry, obtains NaYF4:Yb/Er@MoS2Core-shell structure micron is brilliant.
5. a kind of NaYF according to claim 44:Yb/Er@MoS2The preparation method of core-shell structure micron crystalline substance, feature exist
The Na in step 12MoO4·2H2O、SC(NH2)2With H2C2O4Molar ratio be 1:(3~5): (0.3~1.5).
6. a kind of NaYF according to claim 4 or 54:Yb/Er@MoS2The preparation method of core-shell structure micron crystalline substance, it is special
Sign is Na in step 12MoO4·2H2The ratio between amount and the volume of water of the substance of O are 1mmol:(10~15) mL.
7. a kind of NaYF according to claim 4 or 54:Yb/Er@MoS2The preparation method of core-shell structure micron crystalline substance, it is special
Levying the temperature when drying being in step 3 is 60-80 DEG C, and drying time is 2~6h.
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| CN110846024A (en) * | 2019-11-19 | 2020-02-28 | 常州工程职业技术学院 | Near-infrared multiband photoelectric response up-conversion @ MoS2Composite material and use thereof |
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