CN115194174B - Bismuth metal nanocrystalline with controllable morphology and preparation method thereof - Google Patents
Bismuth metal nanocrystalline with controllable morphology and preparation method thereof Download PDFInfo
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 49
- 239000002243 precursor Substances 0.000 claims abstract description 38
- 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 14
- 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
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000002156 mixing 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
- 239000002159 nanocrystal Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 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 description 3
- 239000000243 solution Substances 0.000 abstract description 56
- 239000013078 crystal Substances 0.000 abstract description 10
- 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 17
- 239000000203 mixture Substances 0.000 description 16
- 239000002073 nanorod Substances 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 13
- 229910052786 argon Inorganic materials 0.000 description 7
- 238000005273 aeration Methods 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000001000 micrograph Methods 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
- 239000012535 impurity Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 231100000956 nontoxicity Toxicity 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- -1 salt bismuth chloride Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000004090 dissolution 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000002074 nanoribbon Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 238000001179 sorption measurement Methods 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention discloses a bismuth metal nanocrystalline with controllable morphology and a preparation method thereof, comprising the following steps of S1: mixing bismuth chloride with oleylamine and trioctylphosphine to prepare bismuth precursor solution; s2, adding an octadecene solvent into tungsten carbonyl to obtain a solution, and heating the solution; s3: controlling the temperature when the bismuth precursor solution in the step S1 is added into the solution 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 morphology-controllable high-quality bismuth metal nanocrystalline; wherein, the steps S1-S4 are all carried out under the inert gas atmosphere. The invention realizes the morphology control of bismuth nanocrystalline by regulating and controlling the injection temperature of bismuth precursor solution and adding specific surfactant.
Description
Technical Field
The invention belongs to the technical field of nanometer, and relates to a preparation method of bismuth metal nanocrystalline with controllable morphology.
Background
Efficient, controllable synthesis of metal Nanocrystals (NCs) is a cornerstone of nanotechnology, and is widely used in various practical applications, such as catalysis, photonics, electronics, information storage, optical sensing, energy storage, etc. In the last 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 create novel or enhanced properties for specific applications. Notably, the exposed crystal planes of metal nanocrystals affect their catalytic activity and selectivity. The shape control synthesis and application of precious metal nanocrystals such as Au, ag, pt, pd and the nano alloys thereof have been widely developed, and as a promising substitute, the non-precious metal nanocrystals rich on the earth have the excellent characteristics of no toxicity and low cost, and are more suitable for industrial application (fields of catalysis, batteries and the like). But for most cases the controlled synthesis of high quality non-noble metal nanocrystals remains challenging.
The non-noble metal bismuth (Bi) is an interesting metal, and has stable chemical property, rich reserve and no toxicity. It has a layered rhombohedral atomic arrangement with large lattice spacing, which gives metallic bismuth nanocrystals excellent properties in catalysis, batteries and clinical diagnostics. Scientists now have prepared spherical nanoparticles of BiParticles, nanoribbons and nanowires of bismuth nanomaterial pair CO 2 Or N 2 Has interesting catalytic properties. However, metallic bismuth nanocrystals have multiple morphologies, often a single morphology cannot be obtained in the synthesis, and at present fine morphology control of metallic bismuth nanocrystals is not possible.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a preparation method of bismuth metal nanocrystals with controllable morphology, and the morphology of the prepared bismuth metal nanocrystals can be controlled by controlling the addition temperature of a precursor solution and using a specific surfactant.
The method is realized by the following technical scheme:
the preparation method of the bismuth metal nanocrystalline with controllable morphology comprises the following steps:
s1: mixing bismuth chloride with oleylamine and trioctylphosphine to prepare bismuth precursor solution;
s2, adding an octadecene solvent into tungsten carbonyl to obtain a solution, and heating the solution;
s3: controlling the temperature when the bismuth precursor solution in the step S1 is added into the solution in the step S2, adding the bismuth precursor solution 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 morphology-controllable high-quality bismuth metal nanocrystalline;
wherein, the steps S1-S4 are all carried out under the inert gas atmosphere.
Further, the temperature at which the bismuth precursor solution of step S1 is added to the solution of step S2 is controlled to be 210-230 ℃. The temperature of the bismuth precursor solution added to 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 nanocrystals has approximate surface energy, and all crystal faces are stable, and the spherical shape is preferable because the bismuth precursor solution has the lowest specific surface area, so that the overall surface energy can be reduced, and the isotropic bismuth nanospheres are obtained.
Further, the precursor solution of bismuth in the step S1 further includes a surfactant; in step S3, the temperature at which the bismuth precursor solution of step S1 is added to the solution of step S2 is controlled to be 150-170 ℃. The higher the injection temperature is, the more spherical or spheroid-like nanocrystals tend to be formed, and under low temperature conditions, the surface energy of each crystal face of the nanocrystals is different, so that when the temperature at which the precursor solution of bismuth is added to the solution in step S2 is controlled to be 150-170 ℃, and a surfactant is further added to the precursor solution of bismuth, the surfactant can be adsorbed on a specific crystal face of the nanocrystals, and the surface energy of the crystal face is reduced, thereby obtaining nanocrystals which have a specific morphology and are uniform, such as triangular plates or rods.
Further, the surfactant is cetyl trimethyl ammonium chloride or cetyl trimethyl ammonium bromide. The long-chain alkyl in the surfactant is mainly used for helping the dissolution of metal salt bismuth chloride, and the halogen ion in the surfactant is used for adsorbing 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 different chemical adsorption preferences of halogen ions to bismuth metal nanocrystals determine the formation of unique shapes, which is a key factor in adjusting the morphology of bismuth metal nanocrystals, so that bismuth nanocrystals can be grown into specific non-spherical morphologies, for example, the morphology of bismuth nanocrystals can be controlled to tend to form one-dimensional nanorods or two-dimensional triangular nanoplatelets.
Specifically, in step S4, the organic solvent is a composition of n-hexane and ethanol. N-hexane plays a role in dispersing and ethanol plays a role in precipitating, and the two together help the nano-metal to wash away redundant ligands in the centrifugation process.
Further, in the step S1, the mass volume ratio of bismuth chloride to oleylamine and trioctylphosphine is 54mg: (1-3) mL: (1-5) mL.
Further, the mass ratio of bismuth chloride to 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 centrifugation speed is 4000-5000rpm.
Specifically, the inert gas may be argon or nitrogen.
Further, the heat preservation duration in the step S3 is 5-10min.
Further, in step S3, the crystal is kept at 210-230 ℃ for 5-10min, and the crystal is waited for to finish growing.
The invention also provides the 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 a specific surfactant into the bismuth precursor solution, and the high-quality bismuth metal nanocrystalline with uniform morphology is obtained. For example, the morphology of bismuth metal nanocrystalline can be controlled to grow towards the direction of the nanospheres by controlling the temperature of the bismuth precursor solution to be 210-230 ℃; the specific surfactant is added into the bismuth precursor solution, and the temperature of the bismuth precursor solution is controlled to be 150-170 ℃, so that the morphology of bismuth metal nanocrystalline can be controlled to grow in the rod-shaped and triangular plate-shaped directions.
2. The preparation method of the high-quality bismuth metal nanocrystalline with controllable morphology, provided by the invention, has the advantages of short preparation time and low cost, and the prepared product can be stably dispersed in the n-hexane solution.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of a preparation method of morphology-controllable high-quality bismuth metal nanocrystals;
FIG. 2 is an electron microscope image of bismuth metal nanospheres prepared in example 1 of the present invention;
FIG. 3 is an electron microscope image of the bismuth metal nano-triangular plate 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 illustration of the preparation process of the preparation method provided in examples 1-3 of the present invention;
FIG. 6 is an X-ray diffraction pattern of bismuth metal nanospheres prepared in example 1 of the present invention;
FIG. 7 is an X-ray diffraction pattern of bismuth metal nano-triangular plate prepared in example 2 of the present invention;
fig. 8 is an X-ray diffraction pattern of the bismuth metal nano-rod prepared in example 3 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The following steps are carried out under an argon atmosphere:
s1: 54mg bismuth chloride (BiCl) 3 ) A precursor solution of bismuth was prepared by mixing with 1mL of Oleylamine (OLA) and 2mL of Trioctylphosphine (TOP), followed by sonication for 50 minutes;
s2: 25mg of tungsten carbonyl (W (CO) 6 ) Into a three-necked flask, 9mL of Octadecene (ODE) was added therewith, and the solution was heated under continuous aeration of argon;
s3: rapidly injecting bismuth precursor solution into the three-neck flask in the step S2 at 200 ℃, and quenching the brown dark solution to room temperature in a water bath after maintaining the temperature at 220 ℃ for 5 min;
s4: 15mL of n-hexane and 5mL of ethanol were added, and the mixture was centrifuged at 4000rpm for 8 minutes to obtain bismuth metal nanospheres. The prepared bismuth metal nanospheres can be dispersed in a solvent (n-hexane) for storage.
Fig. 1 is a schematic flow chart of a preparation method of a shape-controllable high-quality bismuth metal nanocrystalline, and fig. 2 is an electron microscope image of bismuth metal nanospheres prepared in example 1, and as can be seen from fig. 2, the bismuth metal nanospheres prepared in example 1 are uniform in shape and are nanospheres with similar sizes, and the particle size of the nanospheres is 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 X-ray diffraction pattern peak of the bismuth metal nanospheres prepared in example 1 can completely correspond to that of a standard sample, which indicates that the synthesized bismuth metal nanospheres are pure phase, no impurity exists, and the purity is high.
Example 2
The following steps are carried out under an argon atmosphere:
s1: 54mg bismuth chloride (BiCl) 3 ) A precursor solution of bismuth was prepared by mixing with 2mL of Oleylamine (OLA) and 2mL of Trioctylphosphine (TOP) and 100mg of cetyltrimethylammonium chloride (CTAC), followed by ultrasonic treatment for 50 minutes;
s2: 25mg of tungsten carbonyl W (CO) 6 Into a three-necked flask, 9mL of Octadecene (ODE) was added therewith, and the solution was heated under continuous aeration of argon;
s3: rapidly injecting bismuth precursor solution into the three-neck flask of the step S2 at 160 ℃ to obtain a mixture, further heating the mixture to 220 ℃, and quenching the brown dark solution to room temperature in a water bath after maintaining the temperature at 220 ℃ for 5 min;
s4: 15mL of n-hexane and 5mL of ethanol were added, and the mixture was centrifuged at 4000rpm for 8 minutes to obtain bismuth metal nano-triangular plates. The prepared bismuth metal nano triangular plate can be dispersed in a solvent (n-hexane) for preservation.
FIG. 3 is an electron microscope image of the bismuth metal nano-triangular plate prepared in example 2. As can be seen from FIG. 3, the bismuth metal nano-triangular plate prepared in example 2 has uniform morphology, is 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 nano-triangular plate prepared in example 2, and as can be seen from fig. 7, the X-ray diffraction pattern peak of the bismuth metal nano-triangular plate prepared in example 2 can completely correspond to the X-ray diffraction pattern peak of the standard sample, which shows that the synthesized bismuth metal nano-triangular plate is high-purity and free of impurities.
Example 3
The following steps are carried out under an argon atmosphere:
s1: 54mg bismuth chloride (BiCl) 3 ) A precursor solution of bismuth was prepared by mixing with 1mL of Oleylamine (OLA), 2mL of Trioctylphosphine (TOP), and 30mg of cetyltrimethylammonium bromide (CTAB), followed by sonication for 50 minutes;
s2: 25mg of tungsten carbonyl W (CO) 6 Into a three-necked flask, 9mL of Octadecene (ODE) was added therewith, and the solution was heated under continuous aeration of argon;
s3: rapidly injecting bismuth precursor solution into the three-neck flask of the step S2 at 160 ℃ to obtain a mixture, further heating the mixture to 220 ℃, and quenching the brown dark solution to room temperature in a water bath after maintaining the temperature at 220 ℃ for 5 min;
s4: 15mL of n-hexane and 5mL of ethanol were added, and the mixture was centrifuged at 4000rpm for 8 minutes to obtain bismuth metal nanorods. The prepared bismuth metal nano-rod can be dispersed in a solvent (n-hexane) for preservation.
FIG. 4 is an electron microscope image of the bismuth metal nanorod prepared in example 3. As can be seen from FIG. 4, the bismuth metal nanorod prepared in example 3 has a uniform morphology and a rod-like structure with similar size, the length of the bismuth metal nanorod is 25nm, and the diameter of the bismuth metal nanorod is 15nm; fig. 8 is an X-ray diffraction pattern of the bismuth metal nano-rod prepared in example 3, and as can be seen from fig. 8, the X-ray diffraction pattern peak of the bismuth metal nano-rod prepared in example 3 can completely correspond to that of a standard sample, which shows that the synthesized bismuth metal nano-rod is high-purity and free of impurities. FIG. 5 is a schematic illustration of the preparation process of the preparation methods provided in examples 1-3.
Example 4
The following steps are carried out under an argon atmosphere:
s1: 54mg bismuth chloride (BiCl) 3 ) Mixed with 3mL of Oleylamine (OLA) and 5mL of Trioctylphosphine (TOP), and then sonicated for 30 minutes to prepare a bismuth precursor solution;
s2: 10mg of carbonylBase tungsten (W (CO) 6 ) Into a three-necked flask, 9mL of Octadecene (ODE) was added therewith, and the solution was heated under continuous aeration of argon;
s3: rapidly injecting bismuth precursor solution into the three-neck flask of the step S2 at 200 ℃, and quenching the brown dark solution to room temperature in a water bath after maintaining the temperature at 220 ℃ for 6min,
s4: 15mL of n-hexane and 5mL of ethanol are added, and the mixture is centrifuged at 5000rpm for 8 minutes, so that bismuth metal nanospheres with uniform morphology are obtained. The electron microscope and X-ray diffraction patterns of the bismuth metal nanospheres prepared in example 4 were similar to those of example 1, and pure-phase bismuth metal nanospheres could be obtained, but the bismuth metal nanospheres prepared in example 4 were larger in size.
Example 5
The following steps are carried out under an argon atmosphere:
s1: 54mg bismuth chloride (BiCl) 3 ) A precursor solution of bismuth was prepared by mixing with 2mL of Oleylamine (OLA) and 1mL of Trioctylphosphine (TOP) and 120mg of cetyltrimethylammonium chloride (CTAC), followed by ultrasonic treatment for 50 minutes;
s2: 50mg of tungsten carbonyl W (CO) 6 Into a three-necked flask, 9mL of Octadecene (ODE) was added therewith, and the solution was heated under continuous aeration of argon;
s2: rapidly injecting bismuth precursor solution into the three-neck flask of the step S2 at 160 ℃ to obtain a mixture, further heating the mixture to 220 ℃, and quenching the brown dark solution to room temperature in a water bath after maintaining the temperature at 220 ℃ for 5 min;
s4: 15mL of n-hexane and 5mL of ethanol are added, and the mixture is centrifuged at 4000rpm for 8 minutes, so that the bismuth metal nano triangular plate with uniform morphology is obtained. The electron microscope and X-ray diffraction patterns of the bismuth metal nano-triangular plate prepared in example 5 are similar to those of example 2, but pure-phase bismuth metal nano-triangular plate can be obtained, but the side length of the bismuth metal nano-triangular plate prepared in example 5 is longer than that of example 2.
Example 6
The following steps are carried out under an argon atmosphere:
s1: 54mg bismuth chloride (BiCl) 3 ) With 1mL of Oleylamine (OLA),1mL of Trioctylphosphine (TOP) and 20mg of cetyltrimethylammonium bromide (CTAB) were mixed and then sonicated 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 therewith, and the solution was heated under continuous aeration of argon;
s3: rapidly injecting bismuth precursor solution into the three-neck flask of the step S2 at 160 ℃ to obtain a mixture, further heating the mixture to 220 ℃, and quenching the brown dark solution to room temperature in a water bath after maintaining the temperature at 220 ℃ for 5 min;
s4: 15mL of n-hexane and 5mL of ethanol are added, and the mixture is centrifuged at 4000rpm for 8 minutes to obtain bismuth metal nano-rods with uniform morphology. The electron microscope and X-ray diffraction patterns of the bismuth metal nanorods obtained in example 6 were similar to those of example 3, and pure-phase bismuth metal nanorods could 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, and 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 can be used as a low cost catalyst in place of noble metal catalysts for CO 2 Electrochemical reduction, etc., and has commercial value.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (7)
1. The preparation method of the bismuth metal nanocrystalline with controllable morphology is characterized by comprising the following steps:
s1: mixing bismuth chloride with oleylamine and trioctylphosphine to prepare bismuth precursor solution;
s2, adding an octadecene solvent into tungsten carbonyl to obtain a solution, and heating the solution;
s3: controlling the temperature of the bismuth precursor solution in the step S1 to be 210-230 ℃ when the bismuth precursor solution in the step S2 is added, adding the bismuth precursor solution in the step S1 into the bismuth precursor solution in the step S2, preserving heat, and cooling to room temperature;
s4: adding an organic solvent, and centrifuging to obtain the bismuth metal nanocrystalline with controllable morphology;
or, the precursor solution of bismuth in the step S1 further comprises a surfactant, and the temperature is controlled to be 150-170 ℃ when the precursor solution of bismuth in the step S1 is added into the solution in the step S2; the surfactant is cetyl trimethyl ammonium chloride or cetyl trimethyl ammonium bromide;
wherein, the steps S1-S4 are all carried out under the inert gas atmosphere.
2. The method for preparing morphology-controllable bismuth metal nanocrystals according to claim 1, wherein in step S4, the organic solvent is a combination of n-hexane and ethanol.
3. The method for preparing the bismuth metal nanocrystalline with controllable morphology according to claim 1, wherein in the step S1, the mass-volume ratio of bismuth chloride to oleylamine to trioctylphosphine is 54mg: (1-3) mL: (1-5) mL.
4. The method for preparing the bismuth metal nanocrystalline with controllable morphology according to claim 1, wherein the mass ratio of bismuth chloride to tungsten carbonyl is 54: (10-50).
5. The method for preparing the bismuth metal nanocrystalline with controllable morphology according to claim 1, wherein the mass ratio of the bismuth chloride to the surfactant is 54: (20-120).
6. The method for preparing morphology-controllable bismuth metal nanocrystals according to claim 1, wherein in step S4, the centrifugation speed is 4000-5000rpm.
7. Bismuth metal nanocrystalline with controllable morphology, characterized in that it is prepared by the preparation method according to any one of claims 1-6.
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