CN104371725B - NaYF4:Yb/Er-MoS2The preparation method of conjugate - Google Patents
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Abstract
NaYF4:Yb/Er-MoS2The preparation method of conjugate, comprises the following steps: (1) is by MoS2Mix with organic solvent, seal, vibration, obtain MoS2-organic solvent aaerosol solution; (2) by MoS2-organic solvent aaerosol solution seals, centrifugal, takes out the longitudinal middle level solution after being centrifuged, obtains MoS2Receive micro-fragment solution; (3) at MoS2Receive and micro-fragment solution adds NaYF4: Yb/Er, seal, vibration, obtain NaYF4:Yb/Er-MoS2Conjugate aaerosol solution. The present invention is simple, with low cost, it is simple to high-volume commercial production, the NaYF prepared4:Yb/Er-MoS2Conjugate is better than MoS at visible waveband optical limiting property2, it is better than NaYF near infrared band optical limiting property4: Yb/Er rare earth nanometer particle, can be used for lasing safety.
Description
Technical field
The present invention relates to a kind of rare earth and MoS2The preparation method of conjugate, is specifically related to a kind of NaYF4:Yb/Er-MoS2Receive the preparation method of micro-fragment conjugate.
Background technology
In present stage, optics uses and has had spread near infrared band, iraser technology is ripe and militarily uses extensively, such as range finder using laser, laser target designator, laser radar, laser guidance and blinding laser weapons etc., all can temporarily blinding human eye or interference, destruction equipment photoelectric sensor, constitute a serious threat. So, the material that near-infrared laser is carried out optical Limiting by research and manufacture is necessary, and the optical limitation protection eyes of available material and device are from laser hazard.
At infrared band, upper conversion rare earth nano material such as NaYF4: Yb/Er has very strong linear absorption and non-linear absorption, i.e. optical Limiting, but owing to having numerous transition patterns in the 4f shell of its ion, if be excited in infrared light district, the wavelength visible ray less than exciting light can be launched, so can be restricted in some application, and it is only small in visible waveband linear absorption; At visible waveband, Graphene and MoS2There is good linear absorption and non-linear absorption etc. two-dimensional material, i.e. optical Limiting, but absorb only small in near-infrared low light intensity lower linear. Accordingly, it would be desirable to a kind of material having good nonlinear optical limiting characteristic at visible and near infrared band.
At present, WeiWei, TingchaoHe et al. has successfully prepared graphene oxide and rare earth NaYF4: Yb/Er nano composite material, it is notable at the optical limiting property of infrared band, but little at visible waveband graphene oxide and its composite optical Limiting difference. MoS2The wavelength selectivity optical limitation research of solution (Wang Yuanqian, He Jun etc. Acta Physica Sinica, 2014,63 (14): 144204) in describe MoS2Nano micro-material also has optical limiting property, but is not directed to MoS2The preparation of composite, although the MoS of preparation2Nano micro-material has certain light amplification characteristic under little light intensity, but is not appropriate in lasing safety.
Summary of the invention
The technical problem to be solved is to provide a kind of excellent at visible waveband and near infrared band optical limiting property, can be used for the NaYF of lasing safety4:Yb/Er-MoS2The preparation method of conjugate.
The technical solution adopted for the present invention to solve the technical problems is as follows: NaYF4:Yb/Er-MoS2The preparation method of conjugate, comprises the following steps:
(1) by MoS2Mixing with organic solvent, seal, vibrate 1.5～2.5h, obtains MoS2-organic solvent aaerosol solution;
(2) by step (1) gained MoS2-organic solvent aaerosol solution seals, centrifugal, pipettes centrifugal rear longitudinal middle level solution, obtains the MoS that width is 10～15 μm2Receive micro-fragment solution;
(3) in the MoS that step (2) gained width is 10～15 μm2Receive and micro-fragment solution adds rare earth NaYF4: Yb/Er, seal, vibrate 1.5～2.5h, obtains NaYF4:Yb/Er-MoS2Conjugate aaerosol solution.
Further, in step (1), every liter of organic solvent adds MoS2Amount be 2～3g.
Further, in step (1), described organic solvent is ethanol, oxolane, N-Methyl pyrrolidone or DMF.
Further, in step (2), the amount of pipetting of described longitudinal middle level solution is the 25～35% of the liquor capacity that suspends after being centrifuged.
Further, in step (3), in the MoS that step (2) gained every liter width is 10～15 μm2Receive and micro-fragment solution adds NaYF4: the amount of Yb/Er is 2～3g.
Further, in step (1) and (3), the frequency of described vibration is 36～40kHz, and the temperature of vibration is 30～50 DEG C.
Further, in step (2), described centrifugal rotating speed is 1400～1600r/min, and the centrifugal time is 40～50min.
Further, by NaYF described in step (3)4:Yb/Er-MoS2Conjugate aaerosol solution is at 70～80 DEG C, and under rotating speed 2500～3500r/min, rejection film is dried, and obtains NaYF4:Yb/Er-MoS2Conjugate thin film.
The solution prepared by step (1) and (2) is MoS2Receive micro-fragment aaerosol solution, can remove, by centrifugal, the MoS that width is bigger2Fragment so that the longitudinal middle level solution MoS pipetted2The width of micro-fragment received is 10～15 μm, by the MoS that this step is prepared2Light is anti-reflection, and Limiting effect is best, directly affects NaYF4:Yb/Er-MoS2The optical Limiting effect of conjugate; In step (3), organic solvent can disperse MoS2With rare earth NaYF4: Yb/Er, form aaerosol solution, then pass through vibration and make the energy generation transition of two kinds of materials, thus realizing combining, because 1) vibrating can be easier to the MoS reunited respectively2Shake is scattered, and solution is sufficiently mixed with rare earth (rare earth is easy to reunite); 2) when supersonic oscillations, there will be tiny bubble in solution, breaking of bubble can produce High Temperature High Pressure, strengthens aaerosol solution Brownian movement, makes NaYF4: Yb/Er and MoS2It is easier to the combination that reacts.
Preparation method of the present invention has the advantage that
(1) present approach provides a kind of NaYF4:Yb/Er-MoS2The preparation method of conjugate, has filled up the deficiency of this preparation method in prior art, to research rare earth NaYF further4: Yb/Er and MoS2The characteristic that micro-fragment of receiving combines lays the foundation;
(2) MoS prepared according to the inventive method2Fragment z is nanoscale on direction, can embody nano-meter characteristic, and all the other directions are micro-meter scales, it is possible to prevent the damage to human body;
(3) NaYF prepared according to the inventive method4:Yb/Er-MoS2Micro-fragment bonding state of receiving is fine, and NaYF4:Yb/Er-MoS2Receive and do not reunite between micro-fragment, good dispersion;
(4) NaYF prepared according to the inventive method4:Yb/Er-MoS2Conjugate, the optical limiting property under 530nm visible light wave range is better than MoS2, and before light intensity reaches optical Limiting threshold values, it does not have the effect that light is anti-reflection occurs, can be used for lasing safety;And optical limiting property is better than NaYF under the near infrared band of 780nm4: Yb/Er;
(5) NaYF obtained by oscillating reactions4:Yb/Er-MoS2Conjugate is far superior to the product obtained by natural dissolving method on bonding state and optical Limiting effect.
Accompanying drawing explanation
Fig. 1 is embodiment 1MoS2Receive micro-fragment microscope figure;
Fig. 2 is embodiment 1MoS2Atomic force microscope figure;
Fig. 3 is embodiment 1N, NaYF prepared by dinethylformamide4:Yb/Er-MoS2Conjugate bonding state SEM schemes;
Fig. 4 is NaYF prepared by embodiment 2 oxolane4:Yb/Er-MoS2Conjugate bonding state SEM schemes;
Fig. 5 is NaYF prepared by embodiment 3 ethanol4:Yb/Er-MoS2Conjugate bonding state SEM schemes;
Fig. 6 is NaYF prepared by embodiment 4N-methyl pyrrolidone4:Yb/Er-MoS2Conjugate bonding state SEM schemes;
Fig. 7 is NaYF prepared by reference examples N,N-dimethylformamide4:Yb/Er-MoS2Conjugate bonding state SEM schemes;
Fig. 8 is embodiment 1NaYF4:Yb/Er-MoS2Conjugate (Che) and MoS2Pump-probe life diagram;
Fig. 9 is embodiment 1NaYF4:Yb/Er-MoS2Conjugate (Che), the NaYF that naturally prepared by dissolving4:Yb/Er-MoS2And NaYF (phy)4: Yb/Er(RE) fluorescence lifetime figure;
Figure 10 is embodiment 1NaYF4:Yb/Er-MoS2Conjugate (Che), the NaYF that naturally prepared by dissolving4:Yb/Er-MoS2And MoS (phy)2Under 530nm visible light wave range, normalized transmittance is with the change curve of light intensity;
Figure 11 is embodiment 1NaYF4:Yb/Er-MoS2Conjugate (Che) and NaYF4: Yb/Er(RE) under 780nm near infrared band normalized transmittance with the change curve of light intensity.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the invention will be further described.
Embodiment 1
(1) by commercially available for 0.1498g MoS2Powder and 60mLN, dinethylformamide mixes, and seals, and in ultrasonic cleaner, frequency 40kHz, under temperature 45 C, vibrate 2h, forms homogeneous solution, obtains MoS2-N,N-dimethylformamide solution suspension solution; (2) 60mLMoS is taken2-DMF aaerosol solution seals, and is centrifuged 45min when 1500r/min, takes out centrifugal rear longitudinal middle level solution 20mL, obtains the MoS that width is 10～15 μm2Receive micro-fragment solution; (3) at the MoS that 20mL width is 10～15 μm2Receive and micro-fragment solution adds the commercially available rare earth NaYF of 0.0494g4: Yb/Er, seal, in ultrasonic cleaner, frequency 40kHz, under temperature 45 C, vibrate 2h, obtains NaYF4:Yb/Er-MoS2Conjugate aaerosol solution.
To the MoS prepared by the present embodiment2Fragment shooting optical microscope photograph (referring to Fig. 1) and atomic force microscopy (referring to Fig. 2) can be seen that MoS2Fragment width is 10～15 μm, and thickness is 150～310nm, and the MoS through discrete preparation of vibrating is described2Fragment is a kind of two-dimensional material, namely only at the material that one, z direction dimension is nanoscale. Material safe to the human body on conventional yardstick, on nanoscale may not safety because the material of nanoscale can be directly entered human body cell, and according to MoS prepared by the inventive method2Fragment z is nanoscale on direction, can embody nano-meter characteristic, and all the other directions are micro-meter scales, is prevented from again the damage to human body.
Take out 5mLNaYF4:Yb/Er-MoS2Conjugate aaerosol solution, drips on microscope slide, 75 DEG C, and under 3000r/min rotating speed, rejection film is dried, and obtains NaYF4:Yb/Er-MoS2Conjugate thin film, examines under a microscope rare earth NaYF4: Yb/Er and MoS2Receive micro-fragment bonding state, referring to Fig. 3.
As can be seen from Figure 3, roomy bright fragment is single MoS2Receiving micro-fragment, being faint in color in reunion shape is NaYF4: Yb/Er granule, NaYF4: Yb/Er granule is pasted on MoS2Receive micro-fragment surrounding, it can be seen that NaYF4:Yb/Er-MoS2Micro-fragment bonding state of receiving is fine, and NaYF4:Yb/Er-MoS2Receive and do not reunite between micro-fragment, good dispersion.
By Fig. 8 pump-probe life diagram it can be seen that the NaYF for preparing of the present embodiment4:Yb/Er-MoS2The pump-probe life-span t=163fs that conjugate is measured is more than MoS2Life-span t=105fs, be because NaYF4: Yb/Er has portion of energy to transfer to MoS2On, illustrate that this nano composite material occurs in that the phenomenon that energy shifts, it was demonstrated that NaYF4:Yb/Er-MoS2Already in connection with; By Fig. 9 fluorescence lifetime figure it can be seen that the NaYF for preparing of the present embodiment4:Yb/Er-MoS2Conjugate fluorescence lifetime t=0.740ns is less than NaYF4: Yb/Er life-span t=0.875ns, due to MoS in the present embodiment2Thickness is 150～310nm, this thickness MoS2There is no fluorescence (MoS2Unstressed configuration, the fluorescence lifetime of rare earth is very long, MoS2Itself is without influence on the rare earth life-span, only when they combine and there occurs that energy transfer just there will be the shortening of fluorescence lifetime), it is possible to judge whether the energy of rare earth shifts by testing fluorescence, thus proving rare earth and MoS2Combination, this nano material known occurs in that energy transfer phenomenon accordingly, and the portion of energy of rare earth has transferred to MoS2Cause that fluorescence lifetime shortens, it was demonstrated that NaYF4:Yb/Er-MoS2Already in connection with.
As shown in Figure 10, the NaYF that prepared by the present embodiment4:Yb/Er-MoS2Conjugate optical Limiting threshold values (being optical Limiting during normalized transmittance < 100%) under 530nm visible light wave range is 2.89E10G/cm2It is less than pure MoS2Optical Limiting threshold values 4.43E10G/cm2, illustrate that its optical limiting property is better than MoS at 530nm place2, and before light intensity reaches optical Limiting threshold values, it does not have the effect that light is anti-reflection occurs, so can be used for lasing safety.
As shown in Figure 11, the NaYF that prepared by the present embodiment4:Yb/Er-MoS2Conjugate optical Limiting threshold values under the near infrared band of 780nm is 2.02E10G/cm2Less than NaYF4: Yb/Er optical Limiting threshold values 2.94E10G/cm2, illustrate that optical limiting property is better than NaYF at 780nm place4:Yb/Er。
Embodiment 2
(1) by commercially available for 0.1236g MoS2Powder mixes with 60mL oxolane, seals, and in ultrasonic cleaner, frequency 36kHz, at temperature 30 DEG C, vibrate 2.5h, forms homogeneous solution, obtains MoS2-oxolane aaerosol solution; (2) 60mLMoS is taken2-oxolane aaerosol solution seals, and is centrifuged 50min when 1400r/min, takes out centrifugal rear longitudinal middle level solution 15mL, obtains the MoS that width is 10～15 μm2Receive micro-fragment solution; (3) at the MoS that 15mL width is 10～15 μm2Receive and micro-fragment solution adds the commercially available rare earth NaYF of 0.0437g4: Yb/Er, seal, in ultrasonic cleaner, frequency 36kHz, at temperature 30 DEG C, vibrate 1.5h, obtains NaYF4:Yb/Er-MoS2Conjugate aaerosol solution.
Take out 5mLNaYF4:Yb/Er-MoS2Conjugate aaerosol solution, drips on microscope slide, 70 DEG C, and under 2500r/min rotating speed, rejection film is dried, and obtains NaYF4:Yb/Er-MoS2Conjugate thin film, examines under a microscope rare earth NaYF4: Yb/Er and MoS2Receive micro-fragment bonding state, referring to Fig. 4.
As shown in Figure 4, roomy bright fragment is single MoS2Receiving micro-fragment, being faint in color in reunion shape is NaYF4: Yb/Er granule, NaYF4: Yb/Er granule is pasted on MoS2Receive micro-fragment surrounding, it can be seen that NaYF4:Yb/Er-MoS2Micro-fragment bonding state of receiving is fine.
Embodiment 3
(1) by commercially available for 0.1652g MoS2Powder mixes with 60mL ethanol, seals, and in ultrasonic cleaner, frequency 38kHz, at temperature 40 DEG C, vibrate 1.5h, forms homogeneous solution, obtains MoS2-ethanol floats solution; (2) 60mLMoS is taken2-ethanol suspension solution seals, and is centrifuged 40min when 1600r/min, takes out centrifugal rear longitudinal middle level solution 21mL, obtains the MoS that width is 10～15 μm2Receive micro-fragment solution;(3) at the MoS that 21mL width is 10～15 μm2Receive and micro-fragment solution adds the commercially available rare earth NaYF of 0.0431g4: Yb/Er, seal, in ultrasonic cleaner, frequency 38kHz, at temperature 40 DEG C, vibrate 2.5h, obtains NaYF4:Yb/Er-MoS2Conjugate aaerosol solution.
Take out 5mLNaYF4:Yb/Er-MoS2Conjugate aaerosol solution, drips on microscope slide, 80 DEG C, and under 3500r/min rotating speed, rejection film is dried, and obtains NaYF4:Yb/Er-MoS2Conjugate thin film, examines under a microscope rare earth NaYF4: Yb/Er and MoS2Receive micro-fragment bonding state, referring to Fig. 5.
As shown in Figure 5, roomy bright fragment is single MoS2Receiving micro-fragment, being faint in color in reunion shape is NaYF4: Yb/Er granule, NaYF4: Yb/Er granule is pasted on MoS2Receive micro-fragment surrounding, it can be seen that NaYF4:Yb/Er-MoS2Micro-fragment bonding state of receiving is fine.
Embodiment 4
(1) by commercially available for 0.1781g MoS2Powder mixes with 60mLN-methyl pyrrolidone, seals, and in ultrasonic cleaner, frequency 39kHz, under temperature 50 C, vibrate 2h, forms homogeneous solution, obtains MoS2-N-Methyl pyrrolidone aaerosol solution; (2) 60mLMoS is taken2-N-Methyl pyrrolidone aaerosol solution seals, and is centrifuged 48min when 1450r/min, takes out centrifugal rear longitudinal middle level solution 18mL, obtains the MoS that width is 10～15 μm2Receive micro-fragment solution; (3) at the MoS that 18mL width is 10～15 μm2Receive and micro-fragment solution adds the commercially available rare earth NaYF of 0.0534g4: Yb/Er, seal, in ultrasonic cleaner, frequency 39kHz, under temperature 50 C, vibrate 1.8h, obtains NaYF4:Yb/Er-MoS2Conjugate aaerosol solution.
Take out 5mLNaYF4:Yb/Er-MoS2Conjugate aaerosol solution, drips on microscope slide, 78 DEG C, and under 2900r/min rotating speed, rejection film is dried, and obtains NaYF4:Yb/Er-MoS2Conjugate thin film, examines under a microscope rare earth NaYF4: Yb/Er and MoS2Receive micro-fragment bonding state, referring to Fig. 6.
It will be appreciated from fig. 6 that roomy bright fragment is single MoS2Receiving micro-fragment, being faint in color in reunion shape is NaYF4: Yb/Er granule. NaYF4: Yb/Er granule is pasted on MoS2Receive micro-fragment surrounding, it can be seen that NaYF4:Yb/Er-MoS2Micro-fragment bonding state of receiving is fine.
Reference examples
(1) by 0.1498 commercially available MoS2Powder and 60mLN, dinethylformamide mixes, and seals, and in ultrasonic cleaner, frequency 40kHz, under temperature 45 C, vibrate 2h, forms homogeneous solution, obtains MoS2-N,N-dimethylformamide aaerosol solution; (2) 60mLMoS is taken2-DMF aaerosol solution seals, and is centrifuged 45min when 1500r/min, takes out centrifugal rear longitudinal middle level solution 20mL, obtains the MoS that width is 10～15 μm2Receive micro-fragment solution; (3) at the MoS that 20mL width is 10～15 μm2Receive and micro-fragment solution adds the commercially available rare earth NaYF of 0.0494g4: Yb/Er, allow it naturally dissolve, obtain NaYF4:Yb/Er-MoS2Conjugate aaerosol solution.
Take out 5mLNaYF4:Yb/Er-MoS2Conjugate aaerosol solution, drips on microscope slide, 75 DEG C, and under 3000r/min rotating speed, rejection film is dried, and obtains NaYF4:Yb/Er-MoS2Conjugate thin film, examines under a microscope rare earth NaYF4: Yb/Er and MoS2Receive micro-fragment bonding state, referring to Fig. 7.
As shown in Figure 7, rare earth NaYF4: Yb/Er and MoS2Micro-fragment bonding state of receiving dissolves bonding state comparative effectiveness with vibration and is not as, although have rare earth NaYF4: Yb/Er can be combined in MoS2Receive micro-fragment surrounding, but most rare earth NaYF4: Yb/Er is difficult to stick to MoS2On, it is free in MoS2Receive micro-fragment periphery or reunite in the solution, it does not have be attached to MoS2Receive micro-fragment up.
Naturally the NaYF of preparation is dissolved as shown in Figure 94:Yb/Er-MoS2The fluorescence lifetime of conjugate entirety and NaYF4: Yb/Er fluorescence lifetime basically identical (in figure, curve phy and RE essentially coincides), it is seen that in fluorescence lifetime test, mainly NaYF4: Yb/Er has played effect, the MoS of doping2The rare-earth fluorescent life-span is not affected, it was demonstrated that its bonding state is very poor or is not bound with at all.
As shown in Figure 10, the NaYF of preparation is naturally dissolved4:Yb/Er-MoS2Conjugate is optical Limiting threshold values 6E10G/cm under 530nm visible light wave range2It is far longer than pure MoS2(4.43E10G/cm2) or the NaYF for preparing of oscillating reactions4:Yb/Er-MoS2Conjugate (2.89E10G/cm2), so naturally dissolving the NaYF prepared4:Yb/Er-MoS2Its optical Limiting poor effect of conjugate.
Claims (5)
1.NaYF4:Yb/Er-MoS2The preparation method of conjugate, it is characterised in that: comprise the following steps:
(1) by MoS2Mix with organic solvent, every liter of organic solvent adds MoS2Amount be 2～3g, seal, vibrate 1.5～2.5h, obtain MoS2-organic solvent aaerosol solution;
(2) by step (1) gained MoS2-organic solvent aaerosol solution seals, centrifugal, pipettes longitudinal middle level solution of suspension liquor capacity 25～35% after being centrifuged, obtains the MoS that width is 10～15 μm2Receive micro-fragment solution;
(3) in the MoS that step (2) gained every liter width is 10～15 μm2Receive and micro-fragment solution adds rare earth NaYF4: Yb/Er2～3g, seal, vibrate 1.5～2.5h, obtains NaYF4:Yb/Er-MoS2Conjugate aaerosol solution.
2. NaYF according to claim 14:Yb/Er-MoS2The preparation method of conjugate, it is characterised in that: in step (1), described organic solvent is ethanol, oxolane, N-Methyl pyrrolidone or DMF.
3. NaYF according to claim 1 or claim 24:Yb/Er-MoS2The preparation method of conjugate, it is characterised in that: in step (1) and (3), the frequency of described vibration is 36～40kHz, and the temperature of vibration is 30～50 DEG C.
4. NaYF according to claim 1 or claim 24:Yb/Er-MoS2The preparation method of conjugate, it is characterised in that: in step (2), described centrifugal rotating speed is 1400～1600r/min, and the centrifugal time is 40～50min.
5. NaYF according to claim 1 or claim 24:Yb/Er-MoS2The preparation method of conjugate, it is characterised in that: by NaYF described in step (3)4:Yb/Er-MoS2Conjugate aaerosol solution is at 70～80 DEG C, and under rotating speed 2500～3500r/min, rejection film is dried, and obtains NaYF4:Yb/Er-MoS2Conjugate thin film.
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