CN113862712B - Preparation method of lead-containing or bismuth-containing perovskite nanocrystals - Google Patents
Preparation method of lead-containing or bismuth-containing perovskite nanocrystals Download PDFInfo
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- 239000002159 nanocrystal Substances 0.000 title claims abstract description 26
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 15
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 28
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- 239000007787 solid Substances 0.000 claims abstract description 16
- 239000003446 ligand Substances 0.000 claims abstract description 14
- ISWNAMNOYHCTSB-UHFFFAOYSA-N methanamine;hydrobromide Chemical compound [Br-].[NH3+]C ISWNAMNOYHCTSB-UHFFFAOYSA-N 0.000 claims abstract description 7
- LLWRXQXPJMPHLR-UHFFFAOYSA-N methylazanium;iodide Chemical compound [I-].[NH3+]C LLWRXQXPJMPHLR-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 239000000243 solution Substances 0.000 claims description 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 22
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- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 14
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- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 8
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000005642 Oleic acid Substances 0.000 claims description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 8
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- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 claims description 7
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 6
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 6
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- 238000003760 magnetic stirring Methods 0.000 claims description 6
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- 244000137852 Petrea volubilis Species 0.000 claims description 5
- 229960002446 octanoic acid Drugs 0.000 claims description 5
- QAZGSZIABORBEG-UHFFFAOYSA-N octanoic acid;toluene Chemical compound CC1=CC=CC=C1.CCCCCCCC(O)=O QAZGSZIABORBEG-UHFFFAOYSA-N 0.000 claims description 5
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 4
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- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
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- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
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- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
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- 229910052802 copper Inorganic materials 0.000 description 2
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
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- 238000000101 transmission high energy electron diffraction Methods 0.000 description 2
- IGRCWJPBLWGNPX-UHFFFAOYSA-N 3-(2-chlorophenyl)-n-(4-chlorophenyl)-n,5-dimethyl-1,2-oxazole-4-carboxamide Chemical compound C=1C=C(Cl)C=CC=1N(C)C(=O)C1=C(C)ON=C1C1=CC=CC=C1Cl IGRCWJPBLWGNPX-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- ZSBXGIUJOOQZMP-JLNYLFASSA-N Matrine Chemical compound C1CC[C@H]2CN3C(=O)CCC[C@@H]3[C@@H]3[C@H]2N1CCC3 ZSBXGIUJOOQZMP-JLNYLFASSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- KURZCZMGELAPSV-UHFFFAOYSA-N [Br].[I] Chemical compound [Br].[I] KURZCZMGELAPSV-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/11—Halogen containing compounds
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/09—Nitrogen containing compounds
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
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- Metallurgy (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
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Abstract
The invention discloses a preparation method of lead-containing or bismuth-containing perovskite nanocrystals, which adopts an electrochemical method and comprises (1) synthesizing methyl ammonium bromide and methyl ammonium iodide; (2) Synthesis of MA 3 Bi 2 Br 9 Nanocrystalline or synthetic CH 3 NH 3 PbBr 3 A nanocrystalline; (3) Synthesis of MA 3 Bi 2 I 9 Nanocrystalline or synthetic CH 3 NH 3 PbI 3 And (3) nanocrystalline. The invention adopts an electrochemical method to prepare the lead-containing or bismuth-containing perovskite nanocrystals for the first time, thereby greatly reducing the total solvent and solid loss. Secondly, both the high temperature hot injection and the ligand-assisted precipitation processes need to be performed under inert atmosphere from the required atmosphere, whereas the electrochemistry can be performed under air conditions, which saves working costs. In addition, the heat injection method is carried out in a higher temperature environment (120-180 ℃), is complex, and further increases the synthesis cost and expense. The electrochemical process of the present invention has the beneficial effect of being simple and cost effective in preparing high quality perovskite.
Description
Technical Field
The invention relates to the technical field of perovskite nanocrystals, in particular to a preparation method of lead-containing or bismuth-containing perovskite nanocrystals.
Background
In recent years, metal halide Perovskite Nanocrystals (PNCs) have become a hotspot and an important point of research in the photoelectric field, attract a wide range of attention of numerous material scientists, and have made considerable progress and development due to their high photoluminescence quantum yield, strong anisotropic absorption or emission, higher exciton binding energy and widely adjustable band gap, long carrier diffusion length, high charge carrier mobility, suitable defect tolerance, and ease of processing in solution. The metal halide perovskite quantum dots have good application value in a series of devices such as light emitting diodes, lasers, photodetectors, solar cells and the like.
Although there are various methods of synthesizing metal halide perovskites, the high temperature hot injection and low temperature ligand-assisted precipitation are the dominant methods. However, the two methods still have a few problems in practical application, such as (1) low yield, and multiple separation steps are needed to obtain relatively high-purity nanocrystals; (2) The energy consumption is high or the photoluminescence quantum yield is low. Whereas electrochemical synthesis (FIGS. 1 and 2) has a sustainable and renewable reaction process, electrochemical synthesis has a number of prominent advantages: (1) Sustainable and easily controllable reaction process in the reaction direction; (2) Can be carried out at normal temperature and normal pressure, greatly reduces the requirements on reaction equipment, and is simple and convenient to operate; (3) Less side reaction and less waste discharge, and no environmental pollution; (4) solvent and energy consumption can be greatly reduced. We successfully prepared MAPbX by electrochemical method 3 And MA 3 Pb 2 X 9 (x=br, I) two perovskite nanocrystals (fig. 2-4).
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of perovskite nanocrystals containing lead or bismuth by adopting an electrochemical method.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a preparation method of bismuth-containing perovskite nanocrystals comprises the following steps:
(1) Synthesis of methyl ammonium bromide and methyl ammonium iodide: dropwise adding hydrobromic acid or hydroiodic acid into aqueous solution of methylamine in magnetic stirring and ice bath, and stirring; then rotary evaporating at 50deg.C in rotary evaporator, dissolving the product with ethanol after reaction, reverse precipitating with diethyl ether, cleaning, vacuum drying, and storing in a dryer;
(2) Synthesis of MA 3 Bi 2 Br 9 Nanocrystalline: accurately weigh CH 3 NH 3 Br (MABr) in a sample bottle, adding n-butanol (BuOH) and Oleic Acid (OA), heating and stirring at 75 ℃, and then slowly cooling at room temperature; electrolyzing the solution in a glass bottle with a bismuth electrode as an anode and a carbon rod as a cathode under the condition of 100mA constant current, centrifuging the electrolyzed reaction solution in a plugged centrifuge tube, discarding supernatant, washing with chloroform to obtain a solid sample, and dissolving the obtained solid sample in an organic solvent or further washing and drying;
(3) Synthesis of MA 3 Bi 2 I 9 Nanocrystalline: accurately weigh CH 3 NH 3 I (MAI) in a sample bottle, buOH and Chloroform (CH) were added 3 Cl), heating and stirring at 90 ℃, and then slowly cooling at room temperature; weighing sodium oleate in a sample bottle, adding caprylic acid, heating and fully dissolving to obtain clear sodium oleate-caprylic acid ligand solution; taking the mixture containing CH 3 NH 3 Adding n-butanol again into the solution and ligand solution of I in a glass vial, and electrolyzing with bismuth electrode as anode and carbon rod as cathode under the condition of 100mA constant current; centrifuging the electrolyzed reaction solution in a plugged centrifuge tube, discarding supernatant, and washing with chloroform to obtain a solid sample; the resulting solid sample is dissolved in an organic solvent or further washed and dried.
A preparation method of lead-containing perovskite nanocrystals comprises the following steps:
(1) Synthesis of methyl ammonium bromide and methyl ammonium iodide: dropwise adding hydrobromic acid or hydroiodic acid into aqueous solution of methylamine in magnetic stirring and ice bath, and stirring; then rotary evaporating at 50deg.C in rotary evaporator, dissolving the product with ethanol after reaction, reverse precipitating with diethyl ether, cleaning, vacuum drying, and storing in a dryer;
(2) Synthesis of CH 3 NH 3 PbBr 3 Nanocrystalline: (1) dissolving MABr in BuOH to form MABr-BuOH precursor solution in a sample bottle; heating the solution in air at 80 ℃, and naturally cooling to room temperature; then, tetraoctyl ammonium bromide (TOABr) is dissolved in a mixed solvent of OA and toluene and put into a sample bottle to form TOABr-OA-toluene precursor solution; TOABr is also dissolved in a mixed solvent of oleylamine (OAm) and toluene and placed into a sample bottle to form a TOABr-OAm-toluene precursor solution; (2) carrying out electrolysis, manually polishing a lead electrode by using fine sand paper before each electrolysis experiment, and cleaning by using ethanol or acetone; adding MABr-BuOH, TOABr-OA-toluene and TOABr-OAm-toluene, and carrying out constant-current electrolysis at room temperature; after the reaction is finished, centrifuging the electrolyte to obtain a product; discarding the supernatant, and adding an organic solvent into the obtained product to disperse to obtain a colloid solution;
(3) Synthesis of CH 3 NH 3 PbI 3 Nanocrystalline: (1) dissolving MAI in BuOH to form MAI-BuOH precursor solution in a sample bottle; heating the solution in air at 80 ℃, and naturally cooling to room temperature; mixing n-octanoic acid and toluene in a sample bottle to form an octanoic acid-toluene precursor solution; mixing OAm and toluene in a sample bottle to form OAm-toluene precursor solution; (2) carrying out electrolysis, manually polishing a lead electrode by using fine sand paper before each electrolysis experiment, and cleaning by using ethanol or acetone; adding a mixed solvent of MAI-BuOH, octanoic acid-toluene and OAm-toluene, and carrying out constant-current electrolysis at room temperature; after the reaction is finished, centrifuging the electrolyte to obtain a product; the supernatant is discarded, and the obtained product is added into an organic solvent for dispersion to obtain a colloidal solution.
Compared with the prior art, the invention has the following beneficial effects: the existing high-temperature injection method and ligand-assisted precipitation method are large in total solvent and solid loss. Aiming at the problem, the invention adopts an electrochemical method to prepare the perovskite nano crystal containing lead or bismuth for the first time, thereby greatly reducing the total solvent and solid loss. Secondly, both the high temperature hot injection and the ligand-assisted precipitation processes need to be performed under inert atmosphere from the required atmosphere, whereas the electrochemistry can be performed under air conditions, which saves working costs. In addition, the heat injection method is carried out in a higher temperature environment (120-180 ℃), is complex, and further increases the synthesis cost and expense. The electrochemical process of the present invention has the beneficial effect of being simple and cost effective in preparing high quality perovskite.
Drawings
FIG. 1 is a schematic diagram of an electrochemical synthesis process;
FIG. 2 is a schematic diagram of an electrochemical synthesis apparatus;
FIG. 3 shows electrochemical synthesis of MAPbX 3 Nanocrystals and characterization of their materials (x=br, I) (a) MAPbBr 3 And MAPbI 3 The solution was irradiated with room temperature light and ultraviolet light (lambda) ex =365 nm). (b) Absorption spectrum (UV) and fluorescence spectrum (PL) of the solution. (c) MAPbBr 3 And MAPbI 3 Powder X-ray diffraction pattern (XRD). (d, e) purified MAPbBr 3 And MAPbI 3 Electron diffraction patterns (TEM) and (f) infrared spectra (FT-IR);
FIG. 4 is MAPbX 3 A size distribution profile of nanocrystals;
FIG. 5 is a schematic diagram of a mixed perovskite MAPb (Br) x I 1-x ) 3 Is described. (a) Mixed halide PNC solutions with ultraviolet illumination (lambda) ex =365 nm). (b) Bromine-iodine ratio (Br/I) in pre-designed precursor solution and actual ratio of product nanocrystals. (c, d) mixing the absorption spectrum and PL spectrum of the halide perovskite nanocrystals with (d) XRD spectrum;
FIG. 6 is an electrochemically synthesized MA 3 Pb 2 X 9 Nanocrystals and material characterization thereof (x=br, I). (a) MA (MA) 3 Bi 2 X 9 Absorption spectrum and image of nanocrystalline powder; (b) a powder XRD pattern and a crystalline powder; reference value MA 3 Bi 2 Br 9 :ICSD#110575；MA 3 Bi 2 I 9 :CCDC# 1433118。(c,d)MA 3 Bi 2 Br 9 And MA 3 Bi 2 I 9 TEM and SAED (inset) images.
Detailed Description
Example 1:
the preparation method of the lead-containing perovskite nanocrystals comprises the following steps:
(1) Synthesis of methyl ammonium bromide and methyl ammonium iodide: 10mL hydrobromic acid (HBr, 48% in water) or 15mL hydroiodic acid (HI, 47.0% in water) were added dropwise to 10.82mL methylamine (CH) with magnetic stirring and ice bath 3 NH 2 MA,40% aqueous solution) was stirred for 2h. Then spin-evaporated in a rotary evaporator at a temperature of 50 ℃ for 30 minutes. After the reaction, the product was dissolved in ethanol, reverse precipitated with diethyl ether, washed, dried in vacuum at 30℃for 4 hours, and stored in a desiccator.
(2) Synthesis of CH 3 NH 3 PbBr 3 Nanocrystalline: (1) first, 11.2mg of CH 3 NH 3 Br (MABr, 0.1 mmol) was dissolved in 2mL n-butanol (BuOH) to form a MABr-BuOH precursor solution in a 20mL sample bottle. The solution was heated in air at 80 ℃ for 1 hour and then naturally cooled to room temperature. 54.7mg of tetraoctylammonium bromide (TOABr, 0.1 mmol) is then dissolved in a mixed solvent (containing 5mL oleic acid OA and 5mL toluene) and placed in a 20mL sample bottle to form a TOABr-OA-toluene precursor solution. Then, 54.7mg TOABr (0.1 mmol) was dissolved in a mixed solvent (including 5mL oleylamine OAm and 5mL toluene) and placed in a 20mL sample bottle to form a TOABr-OAm-toluene precursor solution. (2) The electrolysis step is thatElectroSyn 2.0 cell. The lead electrodes were hand polished with fine sand paper and rinsed with a small amount of ethanol prior to each electrolysis experiment. MABr-BuOH: TOABr-OA-toluene: TOABr-OAm-toluene (30:30:1 v/v,3.0 mL) was added. The electrolysis was carried out at room temperature for 5min with constant current of 5mA. After the reaction was completed, the electrolyte was centrifuged at 8000rpm for 2min by a centrifuge to obtain a product. The supernatant was discarded, and the obtained product was dispersed in chloroform as an organic solvent to obtain a colloidal solution.
(3) Synthesis of CH 3 NH 3 PbI 3 Nanocrystalline: (1) first, 15.8mg of CH 3 NH 3 I (MAI, 0.1 mmol) was dissolved in 2mL BuOH to form MAI-BuOH precursor solution in a 20mL sample bottle. The solution was heated in air at 80℃for 1 hour and then self-heatedAnd then cooled to room temperature. Then 5mL of n-octanoic acid (OcA) and 5mL of toluene were mixed in a 20mL sample bottle to form an octanoic acid-toluene precursor solution. 5mL of OAm and 5mL of toluene were then mixed in a 20mL sample bottle to form a OAm-toluene precursor solution. (2) Electrolytic processElectroSyn 2.0 cell. The lead electrodes were hand polished with fine grit paper and rinsed with a small amount of ethanol prior to each electrolysis experiment. MAI-BuOH OcA-toluene OAm-toluene (10:10:1 v/v,2.1 mL) was added. The electrolysis was carried out at room temperature for 10min with constant current of 5mA. After the reaction was completed, the electrolyte was centrifuged at 8000rpm for 2min by a centrifuge to obtain a product. The supernatant is discarded, and the obtained product is added with toluene as an organic solvent for dispersion to obtain a colloidal solution.
(4) Characterization of perovskite nanocrystalline properties: (1) ultraviolet-visible absorption spectroscopy (UV) test: and analyzing the absorption characteristic of the perovskite nanocrystalline sample in the visible light region. The test range is 300-850nm, and the step length is 0.5nm. Firstly, toluene is used as a blank reference sample to test a baseline, 3-5 drops of sample solution are added into toluene, and the mixture is uniformly mixed and then tested. (2) Fluorescence emission (PL) detection: and testing the luminescence property of the perovskite nanocrystalline, and setting the wavelength of an excitation light source to be 365nm. Sample solutions diluted in toluene were placed in a cuvette for testing. (3) X-ray powder diffraction phase analysis (XRD): the samples were made into films for phase analysis and crystal structure characterization. Using Cu K alpha 1 A source (λ= 0.15506 nm), a scanning rate of 2 °/min, and a scanning range (2θ) of 3 ° -55 °. (4) Fourier transform attenuated total reflection infrared (ATR-FTIR): the vacuum dried sample was placed in an infrared spectrometer to analyze the interaction of the nanoparticle surface with the ligand. (5) Transmission Electron Microscope (TEM) topography analysis: transmission electron microscopy images were obtained on a JEOL JEM-2010HR microscope at an accelerating voltage of 200 kV. The diluted nanocrystalline suspension droplets were cast onto a transmission electron microscope grid (200 mesh, carbon coated copper grid) to prepare samples.
CH 3 NH 3 PbBr 3 The absorption band edge and PL emission peak of PNCs are located at 505nm and 515 nm, full width at half maximum (FWHM) was 21nm. The obtained product is characterized by adopting powder X-ray diffraction (XRD) and Transmission Electron Microscopy (TEM), and the perovskite nanocrystalline size distribution obtained by analyzing the crystal structure and the size distribution (figure 4) is relatively uniform. Notably, the XRD spectrum of the sample (FIG. 3) can be indexed as pure tetragonal CH 3 NH 3 PbBr 3 。 CH 3 NH 3 PbBr 3 TEM images of PNCs (FIG. 3) confirm CH 3 NH 3 PbBr 3 PNCs are cubic phases. MAPbI 3 PNCs have PL emission peaks at 758nm and half-width values of 42nm. In addition, the XRD spectrum of the sample (FIG. 3) can be determined as pure tetragonal MAPbI 3 。
Example 2:
mixed halogenated perovskite MAPb (Br) was also synthesized according to the method of example 1 x I 1-x ) 3 . It can be seen that as the ratio of Br/I in the precursor solution decreases, the fluorescence of the resulting solution changes from green to red (fig. 5 a). Notably, the Br/I ratios of the mixed halide perovskite nanocrystals were all higher than the corresponding mixed precursor solutions (fig. 5 b), indicating that iodide ions were more likely to enter the lattice during nucleation. The X-ray diffraction data (XRD) for each mixed halide sample indicated that there was only one set of cubic phase diffraction patterns (fig. 5 c), indicating that the I and Br ions were well mixed in the perovskite nanocrystalline lattice. MAPb (Br) estimated according to Vegard's law x I 1-x ) 3 The corresponding x values are between 0.17 and 0.98, indicating that the electrochemical method successfully achieves tuning of the halide composition in the visible region between 540nm and 730 nm.
Example 3:
the preparation method of the bismuth-containing perovskite nanocrystals comprises the following steps:
(1) Synthesis of methyl ammonium bromide and methyl ammonium iodide: 10mL hydrobromic acid (HBr, 48% in water) or 15mL hydroiodic acid (HI, 47.0% in water) were added dropwise to 10.82mL methylamine (CH) with magnetic stirring and ice bath 3 NH 2 MA,40% aqueous solution) was stirred for 2h. Then spin-evaporated in a rotary evaporator at a temperature of 50 ℃ for 30 minutes. After the reaction is finished, the product is dissolved by ethanol, and is reversely precipitated by diethyl ether, washed and really treated at 30 DEG CAir-drying for 4 hours, and storing in a dryer.
(2) Synthesis of MA 3 Bi 2 Br 9 Nanocrystalline: accurately weigh 11.2mg CH 3 NH 3 Br in a 20mL sample bottle, 3mL BuOH and 100. Mu.L OA were added and stirred at 75℃for 60min. Then cooled slowly at room temperature. 3mL of the solution is taken in a 5mL glass vial, a bismuth electrode is taken as an anode, a carbon rod is taken as a cathode, and electrolysis is carried out for 20min under the condition of 100mA constant current. And centrifuging the reaction solution after the electrolysis in a plugged centrifuge tube at 12000rpm for 1min, discarding the supernatant, and washing the solid sample obtained by 2-3 times with chloroform. The resulting solid sample was further washed and dried.
(3) Synthesis of MA 3 Bi 2 I 9 Nanocrystalline: accurately weigh 31.6mg CH 3 NH 3 In a 20mL sample bottle, 4mL BuOH and 16mL chloroform were added and stirred at 90℃for 20min. Then cooled slowly at room temperature. 100mg of sodium oleate (NaOA) is weighed into a sample bottle, 2mL of octanoic acid is added, and the mixture is heated for 30min to be fully dissolved, so that a clear NaOA-OcA ligand solution is obtained. Taking 3mL of the mixture containing CH 3 NH 3 In a 5mL glass vial, 400 μl of n-butanol was again added to the solution I and 600 μl of the ligand solution, and the solution was electrolyzed for 30min under a constant current of 100mA with bismuth electrode as anode and carbon rod as cathode. And centrifuging the reaction solution after the electrolysis in a plugged centrifuge tube at 12000rpm for 1min, discarding the supernatant, and washing the solid sample obtained by 2-3 times with chloroform. The resulting solid sample was further washed and dried.
(4) Characterization of perovskite nanocrystalline properties: (1) ultraviolet-visible absorption spectroscopy (UV) test: and analyzing the absorption characteristic of the perovskite nanocrystalline sample in the visible light region. The test range is 300-850nm, and the step length is 0.5nm. Firstly, toluene is used as a blank reference sample to test a baseline, 3-5 drops of sample solution are added into toluene, and the mixture is uniformly mixed and then tested. (2) Fluorescence emission (PL) detection: and testing the luminescence property of the perovskite nanocrystalline, and setting the wavelength of an excitation light source to be 365nm. Sample solutions diluted in toluene were placed in a cuvette for testing. (3) X-ray powder diffraction phase analysis (XRD): the samples were made into films for phase analysis and crystal structure characterization. Using Cu K alpha 1 Source (lambda=0.15506 nm), the scanning rate is 2 DEG/min, and the scanning range (2 theta) is 3 DEG to 55 deg. (4) Fourier transform attenuated total reflection infrared (ATR-FTIR): the vacuum dried sample was placed in an infrared spectrometer to analyze the interaction of the nanoparticle surface with the ligand. (5) Transmission Electron Microscope (TEM) topography analysis: transmission electron microscopy images were obtained on a JEOL JEM-2010HR microscope at an accelerating voltage of 200 kV. The diluted nanocrystalline suspension droplets were cast onto a transmission electron microscope grid (200 mesh, carbon coated copper grid) to prepare samples.
Example 4:
MA was also obtained according to the procedure of example 3 3 Bi 2 Br 9 And MA 3 Bi 2 I 9 UV, PL, XRD, TEM, electron selective diffraction (SAED) data (fig. 6). For MA 3 Bi 2 Br 9 The sample was confirmed to be the target product by comparison with the standard spectrum, and had crystal planes (100), (101), (002), (110), (102) and the like (fig. 6 b). As shown in FIG. 6c, by further structural morphology analysis, it was observed that the size distribution of the nanocrystals was below 50nm, MA 3 Bi 2 Br 9 The nanocrystals are in a cubic-like shape, with dimensions of about 20nm to 50nm. For MA 3 Bi 2 I 9 The sample was confirmed to be the target product by comparison with the standard spectrum, and had crystal planes (002), (010), (011), (012), (004) and the like (fig. 6 b). As shown in FIGS. 6c and d, further structural morphology analysis, nanocrystalline sizes below 30nm, MA were observed 3 Bi 2 I 9 The nanocrystals are also cube-like in shape, with dimensions of about 20nm to 30nm.
Example 5: comparison of different preparation methods
The material costs we embody by different methods (table 1) are higher for both the high temperature hot injection method and the ligand assisted precipitation method than for the electrochemical method in terms of total solvent and solid losses. From the aspect of the required atmosphere, the high-temperature hot injection method and the ligand auxiliary precipitation method are both required to be carried out under inert atmosphere, and the electrochemistry can be carried out under air condition, so that the working cost is saved to a certain extent. In addition, the heat injection method is carried out in a higher temperature environment (120-180 ℃), is complex, and further increases the synthesis cost and expense. The electrochemical process according to the invention therefore has the development advantage of being simple and cost-effective in the preparation of high quality perovskite.
TABLE 1 comparison of the amounts of the three materials
Claims (2)
1. The preparation method of the bismuth-containing perovskite nanocrystal is characterized by comprising the following steps:
(1) Synthesis of methyl ammonium bromide and methyl ammonium iodide: dropwise adding hydrobromic acid or hydroiodic acid into aqueous solution of methylamine in magnetic stirring and ice bath, and stirring; then rotary evaporating at 50deg.C in rotary evaporator, dissolving the product with ethanol after reaction, reverse precipitating with diethyl ether, cleaning, vacuum drying, and storing in a dryer;
(2) Synthesis of MA 3 Bi 2 Br 9 Nanocrystalline: accurately weigh 11.2mg CH 3 NH 3 Br in a sample bottle, 3mL of BuOH and 100 μl of oleic acid were added, heated and stirred at 75deg.C, and then cooled slowly at room temperature; electrolyzing the solution in a glass bottle with a bismuth electrode as an anode and a carbon rod as a cathode under the condition of constant current of 100mA, centrifuging the electrolyzed reaction solution in a plugged centrifuge tube, discarding supernatant, washing with chloroform to obtain a solid sample, and dissolving the obtained solid sample in an organic solvent or further washing and drying;
(3) Synthesis of MA 3 Bi 2 I 9 Nanocrystalline: accurately weigh 31.6mg CH 3 NH 3 I, adding 4mL of BuOH and 16mL chloroform into a sample bottle, heating and stirring at 90 ℃, and then slowly cooling at room temperature; weighing 100mg sodium oleate in a sample bottle, adding 2mL caprylic acid, heating to fully dissolve to obtain clear sodium oleate-caprylic acid ligand solution; taking 3mL and containing CH 3 NH 3 The solution of I and 600. Mu.L of ligand solution were placed in a glass vial and 400. Mu.L of n-butanol was again added as bismuthThe electrode is an anode, and the carbon rod is a cathode for electrolysis under the condition of 100mA constant current; centrifuging the electrolyzed reaction solution in a plugged centrifuge tube, discarding supernatant, and washing with chloroform to obtain a solid sample; the resulting solid sample is dissolved in an organic solvent or further washed and dried.
2. A preparation method of lead-containing perovskite nanocrystals is characterized by comprising the following steps:
(1) Synthesis of methyl ammonium bromide and methyl ammonium iodide: dropwise adding hydrobromic acid or hydroiodic acid into aqueous solution of methylamine in magnetic stirring and ice bath, and stirring; then rotary evaporating at 50deg.C in rotary evaporator, dissolving the product with ethanol after reaction, reverse precipitating with diethyl ether, cleaning, vacuum drying, and storing in a dryer;
(2) Synthesis of CH 3 NH 3 PbBr 3 Nanocrystalline: (1) will 11.2mg CH 3 NH 3 Br is dissolved in 2mL n-butanol, and MABr-BuOH precursor solution is formed in a sample bottle; heating the solution in air at 80 ℃, and naturally cooling to room temperature; then 54.7mg tetraoctyl ammonium bromide is dissolved in toluene containing 5mL oleic acid and 5mL toluene and placed in a sample bottle to form a TOABr-oleic acid-toluene precursor solution; then, 54.7mg of TOABr was dissolved in a sample bottle comprising 5mL oleylamine and 5mL toluene to form a TOABr-oleylamine-toluene precursor solution; (2) carrying out electrolysis, manually polishing a lead electrode by using fine sand paper before each electrolysis experiment, and cleaning by using ethanol or acetone; adding MABr-BuOH, TOABr-OA-toluene and TOABr-oleylamine-toluene in a volume ratio of 30:30:1, and carrying out constant-current electrolysis at room temperature by electrolysis with current of 5 mA; after the reaction is finished, centrifuging the electrolyte to obtain a product; discarding the supernatant, and adding an organic solvent into the obtained product to disperse to obtain a colloid solution;
(3) Synthesis of CH 3 NH 3 PbI 3 Nanocrystalline: (1) will 15.8mg CH 3 NH 3 I is dissolved in 2mL BuOH to form MAI-BuOH precursor solution in a sample bottle; heating the solution in air at 80 ℃, and naturally cooling to room temperature; then 5mL n-octanoic acid and 5mL toluene were mixed in the sampleForming an octanoic acid-toluene precursor solution in a bottle; mixing 5mL oleylamine and 5mL toluene in a sample bottle to form an oleylamine-toluene precursor solution; (2) carrying out electrolysis, manually polishing a lead electrode by using fine sand paper before each electrolysis experiment, and cleaning by using ethanol or acetone; adding MAI-BuOH, octanoic acid-toluene and oleylamine-toluene mixed solvent in a volume ratio of 10:10:1, and carrying out constant-current electrolysis at room temperature, wherein the current is 5 mA; after the reaction is finished, centrifuging the electrolyte to obtain a product; the supernatant is discarded, and the obtained product is added into an organic solvent for dispersion to obtain a colloidal solution.
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