CN115194174A - Morphology-controllable high-quality bismuth metal nanocrystalline and preparation method thereof - Google Patents
Morphology-controllable high-quality bismuth metal nanocrystalline and preparation method thereof Download PDFInfo
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- CN115194174A CN115194174A CN202210635190.9A CN202210635190A CN115194174A CN 115194174 A CN115194174 A CN 115194174A CN 202210635190 A CN202210635190 A CN 202210635190A CN 115194174 A CN115194174 A CN 115194174A
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 50
- 239000002243 precursor Substances 0.000 claims abstract description 37
- 239000002159 nanocrystal Substances 0.000 claims abstract description 35
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims abstract description 21
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 17
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims abstract description 17
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- FQNHWXHRAUXLFU-UHFFFAOYSA-N carbon monoxide;tungsten Chemical group [W].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] FQNHWXHRAUXLFU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims abstract description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical group [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 56
- 239000013078 crystal Substances 0.000 abstract description 9
- 230000001276 controlling effect Effects 0.000 abstract description 6
- 238000002347 injection Methods 0.000 abstract description 3
- 239000007924 injection Substances 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000002077 nanosphere Substances 0.000 description 16
- 238000002441 X-ray diffraction Methods 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 239000002073 nanorod Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000001000 micrograph Methods 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 238000005273 aeration Methods 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 6
- 238000010791 quenching Methods 0.000 description 6
- 230000000171 quenching effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- -1 salt bismuth chloride Chemical class 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- 201000011510 cancer Diseases 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
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- 238000003745 diagnosis Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
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- 238000000635 electron micrograph Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
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- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002074 nanoribbon Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
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- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0553—Complex form nanoparticles, e.g. prism, pyramid, octahedron
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- B22F1/065—Spherical particles
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Abstract
The invention discloses a morphology-controllable high-quality bismuth metal nanocrystalline and a preparation method thereof, and the morphology-controllable high-quality bismuth metal nanocrystalline comprises the following steps of S1: mixing bismuth chloride with oleylamine and trioctylphosphine to prepare a precursor solution of bismuth; s2, adding an octadecene solvent into tungsten carbonyl to obtain a solution, and heating the solution; s3: controlling the temperature when the precursor solution of the bismuth obtained in the step S1 is added into the solution obtained in the step S2, and then cooling to room temperature after the crystal is grown; s4: adding an organic solvent, and centrifuging to obtain the high-quality bismuth metal nanocrystalline with controllable morphology; wherein, the steps S1 to S4 are all carried out in the inert gas atmosphere. The invention realizes the shape control of the bismuth nanocrystal by regulating the injection temperature of the precursor solution of bismuth and adding a specific surfactant.
Description
Technical Field
The invention belongs to the field of nanotechnology, and relates to a preparation method of high-quality bismuth metal nanocrystals with controllable morphology.
Background
Efficient, controllable synthesis of metal Nanocrystals (NCs) is a fundamental stone of nanotechnology and is widely used in various practical applications, such as catalysis, photonics, electronics, information storage, optical sensing, energy storage, and the like. Over the past few decades, it has been demonstrated that adjusting the composition, size, shape, and surface structure of metal nanocrystals can tailor their physical and chemical properties to produce novel or enhanced properties for specific applications. Notably, the exposed crystal faces of metal nanocrystals can affect their catalytic activity and selectivity. The shape-controlled synthesis and application of precious metal nanocrystals such as Au, ag, pt, pd, etc. and their nanoalloys have been widely developed, and as promising substitutes, non-precious metal nanocrystals rich on earth have the excellent characteristics of non-toxicity and low cost, and are more suitable for industrial applications (catalysis, batteries, etc.). However, for most cases, the controlled synthesis of high quality non-noble metal nanocrystals remains challenging.
Non-noble metal bismuth (Bi) is an interesting metal, chemically stable, abundant and non-toxic. It has a layered rhombohedral atomic arrangement with large lattice spacing, which makes the metallic bismuth nanocrystals have excellent performance in catalysis, batteries and clinical diagnosis. Scientists have now prepared spherical nanoparticles, nanoribbons and nanowires of Bi, which are coupled to CO 2 Or N 2 Have interesting catalytic properties. However, metal bismuth nanocrystals have multiple morphologies, often a single morphology cannot be obtained during synthesis, and fine morphological control of metal bismuth nanocrystals is not currently possible.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a high-quality bismuth metal nanocrystalline with controllable morphology.
The method is realized by the following technical scheme:
a preparation method of high-quality bismuth metal nanocrystalline with controllable morphology comprises the following steps:
s1: mixing bismuth chloride with oleylamine and trioctylphosphine to prepare a precursor solution of bismuth;
s2, adding an octadecene solvent into tungsten carbonyl to obtain a solution, and heating the solution;
s3: controlling the temperature when the precursor solution of bismuth in the step S1 is added into the solution in the step S2, adding the precursor solution of bismuth in the step S1 into the solution in the step S2, then preserving heat, and cooling to room temperature after preserving heat;
s4: adding an organic solvent, and centrifuging to obtain the high-quality bismuth metal nanocrystalline with controllable morphology;
wherein, the steps S1 to S4 are all carried out in the inert gas atmosphere.
Further, the temperature of the bismuth precursor solution in the step S1 when being added into the solution in the step S2 is controlled to be 210-230 ℃. The temperature of the precursor solution of bismuth when being added into the solution in the step S2 is controlled to be 210-230 ℃, so that the nucleation rate of bismuth atoms can be accelerated, each surface of the bismuth nanocrystal has approximate surface energy, all crystal surfaces are stable, and the spherical shape is preferable because the bismuth nanocrystal has the lowest specific surface area, so that the overall surface energy can be reduced, and further the isotropic bismuth nanosphere can be obtained.
Further, the precursor solution of bismuth in the step S1 further includes a surfactant; in step S3, the temperature of the bismuth precursor solution in the step S1 when the bismuth precursor solution is added into the solution in the step S2 is controlled to be 150-170 ℃. The higher the injection temperature is, the more inclined the nanocrystals are to form spherical or spheroidal nanocrystals, while under the low temperature condition, the surface energy of each crystal face of the nanocrystals is different, so the temperature of the bismuth precursor solution added into the solution in the step S2 is controlled to be 150-170 ℃, and a surfactant is added into the bismuth precursor solution, the surfactant can be adsorbed on the specific crystal face of the nanocrystals, the surface energy of the crystal face is reduced, and the nanocrystals with specific morphology and uniformity, such as triangular plates or rods, are obtained.
Further, the surfactant is cetyltrimethylammonium chloride or cetyltrimethylammonium bromide. The long-chain alkyl in the surfactant mainly has the effect of helping the metal salt bismuth chloride to be dissolved, and the halogen ions in the surfactant are adsorbed on different specific surfaces of the nano seed crystal, so that the surface energy of the surface is reduced, and the growth speed of a crystal face is influenced. The formation of unique shapes is determined by different chemisorption preferences of halogen ions on bismuth metal nanocrystals, and is a key factor for adjusting the morphology of the bismuth metal nanocrystals, so that the bismuth nanocrystals grow into specific non-spherical morphologies, for example, the morphology of the bismuth nanocrystals can be controlled to tend to form one-dimensional nanorods or two-dimensional triangular nanosheets.
Specifically, in step S4, the organic solvent is a combination of n-hexane and ethanol. The n-hexane plays a dispersing role, the ethanol plays a precipitating role, and the n-hexane and the ethanol together help the nano metal to clean redundant ligands in the centrifugal process.
Further, in step S1, the mass-to-volume ratio of bismuth chloride to oleylamine and trioctylphosphine is 54mg: (1-3) mL: (1-5) mL.
Further, the mass ratio of the bismuth chloride to the tungsten carbonyl is 54: (10-50).
Further, the mass ratio of the bismuth chloride to the surfactant is 54: (20-120).
Specifically, in step S4, the centrifugal speed is 4000-5000rpm.
Specifically, the inert gas may be argon or nitrogen.
Further, the heat preservation time in the step S3 is 5-10min.
Further, in step S3, keeping the temperature at 210-230 ℃ for 5-10min, and waiting for the crystal to finish growing.
The invention also provides a high-quality bismuth metal nanocrystalline with controllable morphology, which is prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the morphology of the bismuth metal nanocrystalline is regulated and controlled by controlling the injection temperature of the bismuth precursor solution and introducing the specific surfactant into the bismuth precursor solution, and the high-quality bismuth metal nanocrystalline with uniform morphology is obtained. For example, the shape of the bismuth metal nanocrystalline can be controlled to grow towards the direction of the nanospheres by controlling the temperature of the bismuth precursor solution at 210-230 ℃ during adding; adding a specific surfactant into the bismuth precursor solution, controlling the temperature of the bismuth precursor solution at 150-170 ℃, and controlling the morphology of the bismuth metal nanocrystalline to grow in the rod-like and triangular sheet-like directions.
2. The preparation method of the morphology-controllable high-quality bismuth metal nanocrystalline provided by the invention also has the advantages of short preparation time and low cost, and the prepared product can be stably dispersed in n-hexane solution.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic flow chart of a preparation method of morphology-controllable high-quality bismuth metal nanocrystals provided by the present invention;
FIG. 2 is an electron microscope image of a bismuth metal nanosphere prepared in example 1 of the present invention;
FIG. 3 is an electron microscope image of the bismuth metal nanoprism prepared in example 2 of the present invention;
FIG. 4 is an electron microscope image of bismuth metal nanorods prepared in example 3 of the present invention;
FIG. 5 is a schematic diagram of the preparation process of the preparation method provided in examples 1 to 3 of the present invention;
fig. 6 is an X-ray diffraction pattern of the bismuth metal nanospheres prepared in example 1 of the present invention;
FIG. 7 is an X-ray diffraction pattern of the bismuth metal nanoprisms prepared in accordance with example 2 of the present invention;
FIG. 8 is an X-ray diffraction pattern of bismuth metal nanorods prepared according to example 3 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The following steps were carried out under argon atmosphere:
s1: 54mg of bismuth chloride (BiCl) 3 ) Mixing with 1mL of Oleylamine (OLA) and 2mL of Trioctylphosphine (TOP), and then sonicating for 50 minutes to prepare a precursor solution of bismuth;
s2: 25mg of tungsten carbonyl (W (CO) 6 ) Into a three-necked flask, 9mL of Octadecene (ODE) was added, and the solution was heated under continuous argon aeration;
s3: rapidly injecting the precursor solution of bismuth into the three-neck flask obtained in the step S2 at 200 ℃, keeping the temperature at 220 ℃ for 5min, and quenching the brown dark solution to room temperature in a water bath;
s4: adding 15mL of normal hexane and 5mL of ethanol, and centrifuging at the speed of 4000rpm for 8 minutes to obtain the bismuth metal nanospheres. The prepared bismuth metal nanospheres can be dispersed in a solvent (n-hexane) for storage.
Fig. 1 is a schematic flow diagram of a preparation method of a morphology-controllable high-quality bismuth metal nanocrystal provided by the invention, fig. 2 is an electron microscope image of a bismuth metal nanosphere prepared in example 1, and as can be seen from fig. 2, the bismuth metal nanosphere prepared in example 1 has uniform morphology, is all nanospheres with similar sizes, and has a particle size of about 17nm; fig. 6 is an X-ray diffraction pattern of the bismuth metal nanospheres prepared in example 1, and as can be seen from fig. 6, the peaks of the X-ray diffraction pattern of the bismuth metal nanospheres prepared in example 1 can completely correspond to the peaks of the X-ray diffraction pattern of the standard sample, which indicates that the bismuth metal nanospheres synthesized are phase-pure, have no impurities and have high purity.
Example 2
The following steps were carried out under an argon atmosphere:
s1: 54mg of bismuth chloride (BiCl) 3 ) Mixing with 2mL Oleylamine (OLA), 2mL Trioctylphosphine (TOP) and 100mg cetyltrimethylammonium chloride (CTAC), and then sonicating for 50 minutes to prepare a precursor solution of bismuth;
s2: adding 25mg of carbonylRadical tungsten W (CO) 6 Into a three-necked flask, 9mL of Octadecene (ODE) was added, and the solution was heated under continuous argon aeration;
s3: rapidly injecting the precursor solution of bismuth into the three-neck flask obtained in the step S2 at 160 ℃ to obtain a mixture, further heating the mixture to 220 ℃, keeping the temperature at 220 ℃ for 5min, and quenching the brown dark solution to room temperature in a water bath;
s4: adding 15mL of n-hexane and 5mL of ethanol, and centrifuging at the speed of 4000rpm for 8 minutes to obtain the bismuth metal nano triangular plate. The prepared bismuth metal nano triangular plate can be dispersed in a solvent (normal hexane) for storage.
FIG. 3 is an electron microscope image of the bismuth metal nano triangular plate prepared in example 2, and it can be seen from FIG. 3 that the bismuth metal nano triangular plate prepared in example 2 has uniform shape, is a nano triangular plate with similar size, and has a side length of 22nm; fig. 7 is an X-ray diffraction pattern of the bismuth metal nanoprism prepared in example 2, and it can be seen from fig. 7 that the peaks of the X-ray diffraction pattern of the bismuth metal nanoprism prepared in example 2 can completely correspond to the peaks of the X-ray diffraction pattern of the standard sample, indicating that the bismuth metal nanoprism synthesized is high purity and free of impurities.
Example 3
The following steps were carried out under argon atmosphere:
s1: 54mg of bismuth chloride (BiCl) 3 ) Mixing with 1mL of Oleylamine (OLA), 2mL of Trioctylphosphine (TOP) and 30mg of cetyltrimethylammonium bromide (CTAB), followed by sonication for 50 minutes to prepare a precursor solution of bismuth;
s2: 25mg of tungsten carbonyl W (CO) 6 Into a three-necked flask, 9mL of Octadecene (ODE) was added, and the solution was heated under continuous argon aeration;
s3: rapidly injecting the precursor solution of bismuth into the three-neck flask obtained in the step S2 at 160 ℃ to obtain a mixture, further heating the mixture to 220 ℃, keeping the temperature at 220 ℃ for 5min, and quenching the brown dark solution to room temperature in a water bath;
s4: adding 15mL of n-hexane and 5mL of ethanol, and centrifuging at the speed of 4000rpm for 8 minutes to obtain the bismuth metal nanorods. The prepared bismuth metal nano-rod can be dispersed in a solvent (normal hexane) for preservation.
FIG. 4 is an electron microscope image of the bismuth metal nanorods prepared in example 3, and it can be seen from FIG. 4 that the bismuth metal nanorods prepared in example 3 have uniform morphology, are rod-like structures with similar sizes, and have a length of 25nm and a diameter of 15nm; FIG. 8 is an X-ray diffraction pattern of the bismuth metal nanorods prepared in example 3, and it can be seen from FIG. 8 that the peaks of the X-ray diffraction pattern of the bismuth metal nanorods prepared in example 3 can completely correspond to the peaks of the X-ray diffraction pattern of the standard sample, indicating that the synthesized bismuth metal nanorods are high-purity and free of impurities. FIG. 5 is a schematic diagram of the preparation process of the preparation methods provided in examples 1 to 3.
Example 4
The following steps were carried out under argon atmosphere:
s1: 54mg of bismuth chloride (BiCl) 3 ) Mixing with 3mL of Oleylamine (OLA) and 5mL of Trioctylphosphine (TOP), and then sonicating for 30 minutes to prepare a precursor solution of bismuth;
s2: 10mg of tungsten carbonyl (W (CO) 6 ) Into a three-necked flask, 9mL of Octadecene (ODE) was added, and the solution was heated under continuous argon aeration;
s3: rapidly injecting the precursor solution of bismuth into the three-neck flask in the step S2 at 200 ℃, keeping the temperature at 220 ℃ for 6min, quenching the brown dark solution to room temperature in water bath,
s4: adding 15mL of n-hexane and 5mL of ethanol, and centrifuging at the speed of 5000rpm for 8 minutes to obtain the bismuth metal nanospheres with uniform appearance. The electron microscope image and the X-ray diffraction pattern of the bismuth metal nanospheres prepared in example 4 are similar to those of example 1, and pure-phase bismuth metal nanospheres can be obtained, but the size of the bismuth metal nanospheres prepared in example 4 is larger.
Example 5
The following steps were carried out under an argon atmosphere:
s1: 54mg of bismuth chloride (BiCl) 3 ) Mixing with 2mL Oleylamine (OLA), 1mL Trioctylphosphine (TOP) and 120mg cetyltrimethylammonium chloride (CTAC), and then sonicating for 50 minutes to prepare a precursor solution of bismuth;
s2: 50mg of tungsten carbonyl W (CO) 6 Into a three-necked flask, 9mL of Octadecene (ODE) was added, and the solution was heated under continuous argon aeration;
s2: rapidly injecting the precursor solution of bismuth into the three-neck flask obtained in the step S2 at 160 ℃ to obtain a mixture, further heating the mixture to 220 ℃, keeping the temperature at 220 ℃ for 5min, and quenching the brown dark solution to room temperature in a water bath;
s4: adding 15mL of n-hexane and 5mL of ethanol, and centrifuging at the speed of 4000rpm for 8 minutes to obtain the bismuth metal nano triangular plate with uniform appearance. The electron micrograph and the X-ray diffraction pattern of the bismuth metal nanoprism prepared in example 5 are similar to those of example 2, and pure-phase bismuth metal nanoprism can be obtained, but the side length of the bismuth metal nanoprism prepared in example 5 is longer than that of example 2.
Example 6
The following steps were carried out under argon atmosphere:
s1: 54mg of bismuth chloride (BiCl) 3 ) Mixing with 1mL Oleylamine (OLA), 1mL Trioctylphosphine (TOP) and 20mg cetyltrimethylammonium bromide (CTAB), and then sonicating for 50 minutes to prepare a precursor solution of bismuth;
s2: 10mg of tungsten carbonyl W (CO) 6 Into a three-necked flask, 9mL of Octadecene (ODE) was added, and the solution was heated under continuous argon aeration;
s3: rapidly injecting the precursor solution of bismuth into the three-neck flask obtained in the step S2 at 160 ℃ to obtain a mixture, further heating the mixture to 220 ℃, keeping the temperature at 220 ℃ for 5min, and quenching the brown dark solution to room temperature in a water bath;
s4: adding 15mL of n-hexane and 5mL of ethanol, and centrifuging at the speed of 4000rpm for 8 minutes to obtain the bismuth metal nanorod with uniform morphology. The electron microscope image and the X-ray diffraction pattern of the bismuth metal nanorod prepared in example 6 are similar to those of example 3, and a pure-phase bismuth metal nanorod can also be obtained.
The high-quality bismuth metal nanocrystalline with controllable morphology prepared by the invention has a series of excellent physicochemical characteristics, such as no toxicity, high density and low melting point,the bismuth-based cancer diagnosis and treatment integrated platform can be applied to a plurality of high and new technical fields, including cosmetics, metallurgy, catalysis, energy, 3D printing technology, bismuth-based cancer diagnosis and treatment integrated platform and the like. Wherein bismuth as a low cost catalyst can replace noble metal catalysts for CO 2 Electrochemical reduction, etc., and has commercial value.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a shape-controllable high-quality bismuth metal nanocrystal is characterized by comprising the following steps:
s1: mixing bismuth chloride with oleylamine and trioctylphosphine to prepare a precursor solution of bismuth;
s2, adding an octadecene solvent into tungsten carbonyl to obtain a solution, and heating the solution;
s3: controlling the temperature when the precursor solution of bismuth in the step S1 is added into the solution in the step S2, adding the precursor solution of bismuth in the step S1 into the solution in the step S2, then keeping the temperature and cooling to room temperature;
s4: adding an organic solvent, and centrifuging to obtain the high-quality bismuth metal nanocrystalline with controllable morphology;
wherein, the steps S1 to S4 are all carried out in the inert gas atmosphere.
2. The method for preparing high-quality bismuth metal nanocrystals with controllable morphology as claimed in claim 1, wherein the temperature of the bismuth precursor solution of step S1 added to the solution of step S2 is controlled to be 210-230 ℃.
3. The method for preparing high-quality bismuth metal nanocrystals with controllable morphology according to claim 1, wherein the precursor solution of bismuth in the step S1 further comprises a surfactant; in step S3, the temperature of the bismuth precursor solution in the step S1 when the bismuth precursor solution is added into the solution in the step S2 is controlled to be 150-170 ℃.
4. The preparation method of the morphology-controllable high-quality bismuth metal nanocrystal as claimed in claim 3, wherein the surfactant is cetyltrimethylammonium chloride or cetyltrimethylammonium bromide.
5. The method for preparing high-quality bismuth metal nanocrystals with controllable morphology as claimed in claim 1, wherein in step S4, the organic solvent is a combination of n-hexane and ethanol.
6. The preparation method of morphology-controllable high-quality bismuth metal nanocrystals, as claimed in claim 1, wherein in step S1, the mass-to-volume ratio of bismuth chloride to oleylamine and trioctylphosphine is 54mg: (1-3) mL: (1-5) mL.
7. The preparation method of the morphology-controllable high-quality bismuth metal nanocrystal according to claim 1, wherein the mass ratio of bismuth chloride to tungsten carbonyl is 54: (10-50).
8. The preparation method of the morphology-controllable high-quality bismuth metal nanocrystal according to claim 3, wherein the mass ratio of the bismuth chloride to the surfactant is 54: (20-120).
9. The method for preparing high-quality bismuth metal nanocrystals with controllable morphology as claimed in claim 1, wherein in step S4, the centrifugation speed is 4000-5000rpm.
10. A high-quality bismuth metal nanocrystal with controllable morphology, characterized by being prepared according to the preparation method of any one of claims 1 to 9.
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