CN109928426A - A kind of nanocrystalline Rb of novel rubidium bismuth chlorine perovskite7Bi3Cl16And preparation method thereof - Google Patents
A kind of nanocrystalline Rb of novel rubidium bismuth chlorine perovskite7Bi3Cl16And preparation method thereof Download PDFInfo
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Abstract
This application discloses a kind of crystal structures and preparation method thereof of novel rubidium bismuth chlorine perovskite nanocrystalline material.The chemical formula of the crystalline material is Rb7Bi3Cl16, belong to trigonal system, space group P-31c, cell parameter is α=β=90 °, γ=120 °, Z=2.The preparation method of the nanocrystalline material predominantly uses polar solvent dissolution bismuth chloride and rubidium chloride, using straight chain organic amine and organic carboxyl acid as surfactant, then using weak polar solvent as dispersing agent dispersion.It is resulting it is nanocrystalline there is good fluorescent characteristic, excitation wavelength 365nm, launch wavelength 437nm, fluorescence quantum yield reaches as high as 28.43%.Also there is good thermal stability, water stability and photostability simultaneously.The nanocrystalline material has wide practical use in photoelectric field, such as LED, bio-imaging, fluorescence detection etc..
Description
Technical field
This application involves the structures and preparation method of a kind of novel rubidium bismuth chlorine perovskite nanocrystalline material.
Background technique
Perovskite is nanocrystalline, and with its high quantum yield, energy band is adjustable, and excitation purity is high, prepares easy and at low cost etc. excellent
Point becomes popular one of photoelectric material of new generation, has broad application prospects in fields such as display, medicine.However, current
Perovskite it is nanocrystalline mainly based on lead-based perovskite, e.g., CsPbX3, (CH3NH3)PbX3(X=Cl, Br, I) etc., exists
Lead toxicity it is relatively strong and lead-based perovskite meets water, light, hot problem of easy degradation, seriously constrain that perovskite is nanocrystalline to answer
With popularization.For this purpose, scholars propose the strategy of metal replacement, i.e., using with ns similar with lead2Other poison of electronic configuration
The smaller metal of property is replaced, such as Sn, Ge, Bi, Sb.
Wherein, tin based perovskites and germanium based perovskite, since Sn and Ge is easily oxidized to tetravalence by divalent, stability is bad,
Fluorescence quantum yield is low, and such unleaded perovskite also needs further to study improvement；And bismuthino perovskite is nanocrystalline, such as:
(CH3NH3)3Bi2X9And Cs3Bi2X9It is nanocrystalline etc., have better thermal stability, water stability and long-time stability, toxicity compared with
Weak, the advantages that fluorescence property is good is that the unleaded perovskite of current most researching value is one of nanocrystalline, LED, biology at
The photoelectric fields such as picture, fluorescence detection have broad application prospects.
The application is innovatively using the organic amine of long-chain and organic carboxyl acid as surfactant, and polar solvent is as molten
Agent, weak polar solvent synthesize a kind of novel nanocrystalline Rb of rubidium bismuth chlorine perovskite as dispersing agent7Bi3Cl16.Its preparation side
Method is simple, and unique structure, fluorescence property is good, and stability greatly improves.It is about by the quantum yield being calculated
28.43%, it is a kind of novel photoelectric nanocrystalline material with application value.
Summary of the invention
According to the one aspect of the application, provide a kind of novel perovskite nanocrystalline material, the nanocrystalline material have compared with
Good blue-fluorescence, excitation wavelength 365nm, launch wavelength 437nm, the fluorescence quantum yield being calculated are 28.43%.
In addition, the crystalline material has good thermal stability, water stability and photostability.Therefore, the nanocrystalline material is in photoelectricity
Display field has wide practical use.
The perovskite nanocrystalline material, which is characterized in that chemical formula Rb7Bi3Cl16, nanocrystalline material is in class ball
Shape nano particle, average grain diameter are 1.85 ± 0.8nm, as shown in Figure 1.
The nanocrystalline Rb of perovskite7Bi3Cl16Crystal structure it is as shown in Figure 2.It is characterized in that, belong to trigonal system,
Space group is P-31c, and cell parameter is α=β=
90 °, γ=120 °, Z=2；Octahedron [the BiCl that each Bi atom and adjacent six Cl Atomic coordinates are formed6]3-Or side is shared
Dimer [Bi2Cl10]4-, it is octahedra to be alternately stacked with dimer, discrete sandwich structure is formed, and Rb ion is then point
Cloth is in octahedra or dimer gap, with balancing charge.
According to the another aspect of the application, the preparation method of the nanocrystalline material is provided, which is characterized in that using length
For the organic amine and organic carboxyl acid of chain as surfactant, polar solvent will with the ratio of 1:10 in isothermal reaction as solvent
Reaction solution is dispersed in weak polar solvent, after centrifugation removes big particulate matter, obtains stable nanocrystalline colloid solution.
Preferably, in the initial reactant, the mixed proportion of bismuth chloride and rubidium chloride is BiCl3: RbCl=1:1.5
~2.5, it is configured to the solution that reactant concentration is 0.015~0.05mol/L.
Preferably, in the reactant, the concentration of surfactant is every 1mL reaction solution, the addition of straight chain organic amine
40~100 μ L are measured, the additional amount of straight chain organic carboxyl acid is 4~10 μ L.
Preferably, the optional n,N-Dimethylformamide of the polar solvent (DMF), dimethyl sulfoxide (DMSO), γ-
At least one of butyrolactone (GBL).
Preferably, the isothermal reaction temperature is 60~100 DEG C.
Preferably, the isothermal reaction time is 1~4 hour.
Preferably, the organic amine is optionally from least one of octylame, lauryl amine, oleyl amine.
Preferably, the organic carboxyl acid is optionally from least one of oleic acid, lauric acid.
Preferably, the weak polar solvent is optionally from least one in dehydrated alcohol, isopropanol, methylene chloride, toluene
Kind.
The beneficial effect that the present invention can generate includes at least:
(1) this application provides a kind of Modern Nanocrystalline Material, which has preferable blue-fluorescence, excitation wave
A length of 365nm, launch wavelength 437nm, the fluorescence quantum yield being calculated be 28.43%, have good thermal stability,
Water stability and photostability.Therefore, which is widely used in fields such as photoelectric display, bio-imaging, fluorescence detections
Prospect.
(2) this application provides the preparation method of above-mentioned nano material, using the synthetic method of mild condition, 60~
Under 100 DEG C of constant temperature, the method that reprecipitation is assisted by ligand, can high yield obtain high-purity sample.Method is simple,
Mild condition, the nanocrystalline pattern and partial size synthesized are more uniform.
Detailed description of the invention
Fig. 1 is the nanocrystalline Rb of the perovskite7Bi3Cl16Pattern schematic diagram.
Fig. 2 is the grain size distribution of sample 1#.
Fig. 3 is the crystal unit cell structure chart of sample 1#.
Fig. 4 is the X ray diffracting spectrum of sample 1#；Wherein gray line is according to Rb7Bi3Cl16Single crystal X-ray diffraction parses
Crystal structure, the X ray diffracting spectrum being fitted；Black line is the figure that the X x ray diffraction of sample 1# powder is tested
Spectrum；The impurity peaks that the diffraction maximum of grey chromosphere instruction is sample 1#.
Fig. 5 is the fluorescence pattern of sample 1#.
Fig. 6 is the thermogravimetric map of sample 1#.
Fig. 7 is the water stability empirical curve of sample 1#.
Fig. 8 is the Photostability experiments curve of sample 1#.
Specific embodiment
Below with reference to embodiment, the application is further described.It should be understood that these embodiments be merely to illustrate the application without
For limiting scope of the present application.In the following examples, the experimental methods for specific conditions are not specified, usually according to normal condition or
According to the normal condition proposed by manufacturer.
1 sample preparation of embodiment
Novel rubidium bismuth chlorine perovskite nanocrystalline material Rb is prepared as one7Bi3Cl16Preferred embodiment, side
Method is as follows: by raw material RbCl, BiCl3, polar solvent, straight chain organic amine and straight chain organic carboxyl acid mix be placed according to a certain percentage
Ultrasound is carried out in sample bottle, then carries out isothermal reaction, and reaction temperature is 60~100 DEG C, and the reaction time is 1~4 hour, is then set
At room temperature slowly, weak polar solvent dispersion is added by 1:10 in reaction solution, clear can be obtained in centrifugation removal bulky grain
Rb7Bi3Cl16Nanocrystalline colloid solution.The reaction ratio and condition of experiment and the relationship of sample number into spectrum are as shown in table 1.
The relationship of table 1 sample synthesis condition and sample number into spectrum
The pattern of 2 sample of implementation column and granularmetric analysis
Pattern and granularmetric analysis, institute are carried out using sample 1 of the Japanese JEM-2100 transmission electron microscope to dilution processing
Obtain result such as Fig. 1 and Fig. 2.Sample 1# nanocrystalline is in near-spherical nano particle, and average grain diameter is 1.85 ± 0.8nm, and partial size meets
Normal distribution.
The preparation of 3 Sample crystals of embodiment and structure elucidation
For checking R b7Bi3Cl16Nanocrystalline component and structure have synthesized Rb using hydro-thermal method7Bi3Cl16Monocrystalline, specific method
It is as follows: RbCl and BiCl3According to the ratio mixed dissolution of 1:2.33 in concentrated hydrochloric acid, 160 DEG C hydro-thermal reaction 24 hours, then slowly
Crystallisation by cooling obtains transparent bulk crystals.And using single crystal X-ray diffraction to Rb7Bi3Cl16Monocrystalline carries out structure elucidation.
Wherein single crystal X-ray diffraction is in German Bruker company Rigaku Mercury CCD type X-ray single crystal diffractometer
Upper progress.Data collection temperature is 293K, and diffraction light sources are graphite monochromatised Mo-K alpha ray Scanning side
Formula is ω -2 θ；Data carry out absorption correction processing using Multi-Scan method.Structure elucidation uses SHELXTL-2016 program
Packet is completed；The position that heavy atom is determined with direct method obtains remaining atomic coordinates with poor Fourier synthetic method；With based on F2It is complete
The coordinate and anisotropy thermal parameter of all atoms of Matrix least square method refine.(crystal structure is as shown in Figure 3)
In addition, the powder x-ray diffraction of sample carries out on the x-ray powder diffraction instrument of German Bruker company D8 type,
Test condition is fixed target monochromatic source Cu-K α, and wavelength isScanning range is 3-50 °, and scanning step is
0.02°。
By powder x-ray diffraction the results show that the XRD spectrum and Rb of sample 1#~20#7Bi3Cl16The XRD of monocrystalline fitting
Map is almost the same, and peak position is essentially identical, and each sample peak intensity slightly has difference.
Using sample 1# as Typical Representative, as the gray line in Fig. 4 represents the crystal knot parsed according to its single crystal X-ray diffraction
Structure, the X ray diffracting spectrum being fitted, and the black line representative sample 1# in Fig. 4 pulverizes, last X-ray diffraction is tested
The map arrived, peak position and peak intensity are almost the same.Illustrate that gained sample has very high-purity.
The experiment of 4 fluorometric investigation of embodiment and result
Sample 1# fluorometric investigation experiment it is specific as follows: using Cary Eclipse spectrofluorimeter (Varian,
America) and QM/TM 3360 (PTI, America), fluorescence detection is carried out to sample 1#, excitation wavelength 365nm emits
Wavelength is 437nm.Using quinine sulfate as standard, the relative fluorescence quantum yield being calculated is 28.43%.Test result table
Bright Rb7Bi3Cl16It is nanocrystalline that there is good blue-fluorescence, such as Fig. 5.
5 heat stability testing of embodiment
The heat stability testing of sample 1# is enterprising in Mettler Toledo Inc., Switzerland TGA/1100SF type thermogravimetric analyzer
Row.Take Rb7Bi3Cl16Crystal powder takes about 5mg to be added in crucible, 30~800 DEG C of temperature range of debugging scanning, scanning speed
Degree is 10 DEG C/min.As a result as shown in fig. 6, as seen from the figure this it is nanocrystalline start to decompose at 400 DEG C or so, explanation
Rb7Bi3Cl16There is good thermal stability before 400 DEG C.
The test of 6 water stability of embodiment
After taking the sample 1# colloidal solution of 4mL to mix with 2mL deionized water, the fluorescence intensity of real-time measurement sample 1#, warp
Test in about 24 hours is crossed, the result shows that sample 1# is still able to maintain about 80% fluorescence intensity, there is preferable water stability.
7 light stability test of embodiment
Illumination experiment is carried out to the sample 1# colloidal solution of 4mL at distance 10cm using the ultraviolet lamp of 5W, and is remembered in real time
Its fluorescence intensity is recorded, after tested, the fluorescence intensity of sample 1# shows under the illumination condition of 12 hours and first increases becoming of dropping afterwards
Gesture, and nearly 95% fluorescence intensity is still able to maintain after illumination 12 hours, show that sample 1# has good photostability.
The above is only several embodiments of the present invention, not any type of limitation is done to the present invention, although this hair
It is bright to be disclosed as above with preferred embodiment, however be not intended to limit the invention, any person skilled in the art, it is not taking off
In the range of technical solution of the present invention, a little variation or modification are made using the technology contents of the disclosure above and is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (9)
1. a kind of novel rubidium bismuth chlorine perovskite nano crystal material, which is characterized in that chemical formula Rb7Bi3Cl16, crystal knot
Structure belongs to trigonal system, space group P-31c, and cell parameter is
α=β=90 °, γ=120 °, Z=2；Its nanocrystalline material is in near-spherical nano particle, and average grain diameter is 1.85 ± 0.8nm, phase
It is 13.41~28.43% to fluorescence quantum yield.
2. the method for preparing nanocrystalline material described in claim 1, which is characterized in that by anhydrous bismuth chloride and rubidium chloride by reaction
Ratio is dissolved in polar solvent, and ultrasound 30 minutes adds corresponding long-chain organic carboxyl acid and long-chain organic amine as surface
Activating agent obtains precursor solution after isothermal reaction.Weak polar solvent is added in the ratio of 1:10 in the precursor solution prepared
It is diluted, dilute solution stirs 10 minutes, then carries out 9000rpm and be centrifuged 8 minutes, and resulting clear solution is rubidium bismuth chlorination
Object perovskite nanocrystal colloidal solution.
3. according to the method described in claim 2, it is characterized in that, in the initial solution, bismuth chloride and rubidium chloride rub
You are than being BiCl3: RbCl=1:1.5~2.5.
4. according to the method described in claim 2, it is characterized in that, isothermal reaction temperature be 60~100 DEG C, the isothermal reaction time
It is 1~4 hour.
5. according to the method described in claim 2, it is characterized in that, selected polar solvent is optionally from N, N- dimethyl formyl
At least one of amine (DMF), dimethyl sulfoxide (DMSO), gamma-butyrolacton (GBL), be configured to concentration be 0.03~
The reaction solution of 0.05mol/L.
6. according to the method described in claim 2, it is characterized in that, selected long-chain organic carboxyl acid is optionally from oleic acid, laurel
At least one of acid, every 1mL reaction solution, 40~100 μ L of additional amount.
7. according to the method described in claim 2, it is characterized in that, selected long-chain organic amine is optionally from octylame, lauryl amine, oleyl amine
At least one of, every its additional amount of 1mL reaction dissolvent is 4~10 μ L.
8. according to the method described in claim 2, it is characterized in that, the weak polar solvent optionally from dehydrated alcohol, isopropanol,
At least one of methylene chloride, toluene.
9. light emitting diode, bio-imaging, fluorescence detection application, which is characterized in that contain crystal described in claim 1
Material or the crystalline material being prepared according to any one of claim 2-8 the method.
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| CN111088034A (en) * | 2019-12-26 | 2020-05-01 | 江南大学 | Lead-free bismuth-based perovskite @ SiO2Core-shell material and preparation method and application thereof |
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Application publication date: 20190625 |