CN117123792B - Preparation method of metal and alloy nanocluster - Google Patents

Preparation method of metal and alloy nanocluster

Info

Publication number
CN117123792B
CN117123792B CN202310950485.XA CN202310950485A CN117123792B CN 117123792 B CN117123792 B CN 117123792B CN 202310950485 A CN202310950485 A CN 202310950485A CN 117123792 B CN117123792 B CN 117123792B
Authority
CN
China
Prior art keywords
metal
solvent
heterocycle
ligand
thione
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202310950485.XA
Other languages
Chinese (zh)
Other versions
CN117123792A (en
Inventor
刘国锋
王学娟
张向阳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tongji University
Original Assignee
Tongji University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tongji University filed Critical Tongji University
Priority to CN202310950485.XA priority Critical patent/CN117123792B/en
Publication of CN117123792A publication Critical patent/CN117123792A/en
Application granted granted Critical
Publication of CN117123792B publication Critical patent/CN117123792B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • B22F1/0553—Complex form nanoparticles, e.g. prism, pyramid, octahedron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/58—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing copper, silver or gold
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/87—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing platina group metals
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/52—Alloys
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biophysics (AREA)
  • Optics & Photonics (AREA)

Abstract

本发明公开了一种金属及合金纳米团簇的制备方法，包括以下步骤：S1、称取一定量的N‑杂环‑2‑硫酮配体和金属盐，加适量溶剂溶解，充分搅拌，混合均匀，得到相应的金属复合物；S2、持续搅拌，观察到颜色变化，继续反应一段时间，得到粗产物；S3、于暗处缓慢挥发，得到金属及合金纳米团簇的单晶；本发明提供了一种简便、产率高、结晶性好的用含N杂环‑2‑硫酮有机配体制备金属及合金纳米团簇的方法。This invention discloses a method for preparing metal and alloy nanoclusters, comprising the following steps: S1, weighing a certain amount of N-heterocyclic 2-thione ligand and metal salt, dissolving in an appropriate amount of solvent, stirring thoroughly, mixing evenly to obtain the corresponding metal complex; S2, continuously stirring, observing color change, continuing the reaction for a period of time to obtain a crude product; S3, slowly evaporating in the dark to obtain single crystals of metal and alloy nanoclusters; This invention provides a simple, high-yield, and well-crystallized method for preparing metal and alloy nanoclusters using N-heterocyclic 2-thione organic ligands.

Description

Preparation method of metal and alloy nanocluster
Technical Field
The invention relates to the technical field of compound synthesis, in particular to a preparation method of metal and alloy nanoclusters.
Background
Metal nanoclusters are relatively stable aggregates composed of several to thousands of metal atoms through physical or chemical bonding forces, whose size can be comparable to the fermi wavelength of electrons, typically less than 3nm. Due to the specific structure of the metal nanoclusters themselves, molecular-like properties are generally exhibited, thereby exhibiting excellent physicochemical properties such as optical, electrical, magnetic, catalytic, chiral, and the like.
The first method is a reduction growth method, the reaction speed depends on the reduction capability of the reducing agent, and sodium borohydride, sodium cyanoborohydride, CO and the like which are strong reducing agents are commonly used. The second is a seed growth method, which adopts smaller-sized metal nanoclusters as seeds and gradually grows into larger-sized metal nanoclusters. The third method is an alloying method, which is a method for realizing metal exchange by gradually exchanging a certain amount of external die bodies (motif) with the die bodies on the surface of the original nanocluster so as to obtain the dissimilar metal doped alloy nanocluster. The fourth is a ligand exchange method, which is a method of generating another ligand-protected or multi-ligand-protected nanocluster by exchanging peripheral protection ligands. However, most metal nanocluster synthesis processes are complex, require strict control of thermodynamic and kinetic processes, and have low yields. In addition, the use of reducing agents can cause pollution, which does not conform to the principles of green chemistry. Therefore, the development of new ligands and synthetic methods for efficient synthesis of nanoclusters is highly desirable.
The ligands currently used for synthesizing the metal nanoclusters mainly comprise three main types of thiol ligands, alkynyl ligands and phosphine ligands, but the yield of the synthesis of the nanoclusters by the ligands is uneven and the method is complex.
Disclosure of Invention
In view of the above problems, the present invention provides a simple, high-yield and good-crystallinity method for preparing metal and alloy nanoclusters from N-heterocycle-2-thione-containing organic ligands (novel ligands).
To achieve the purpose, the invention provides the following technical scheme:
The invention provides a preparation method of metal and alloy nanoclusters, which comprises the following steps:
s1, weighing a certain amount of N-heterocycle-2-thione ligand and metal salt, adding a proper amount of solvent for dissolution, fully stirring, and uniformly mixing to obtain a corresponding metal compound;
s2, continuously stirring, observing color change, and continuously reacting for a period of time to obtain a crude product;
S3, slowly volatilizing in a dark place to obtain the monocrystal of the metal and alloy nanocluster.
Preferably, in step S1, a proper amount of reducing agent can be added to enhance the reducibility of the N-heterocycle-2-thione ligand.
In the present invention, whether or not to add the reducing agent is determined according to the kind of the metal salt. For example, in examples 1 and 2 of the present invention, the silver nanoclusters and copper nanoclusters are prepared without adding a reducing agent. Whereas in example 3 of the present invention, the preparation of gold nanoclusters requires the addition of a reducing agent.
Preferably, step S2 further comprises filtering the crude product obtained, drying in a vacuum oven, repeatedly washing with clean reaction solvent, and dissolving with a suitable solvent.
In the present invention, the metal salt may be theoretically any metal ion-containing salt. But the invention also screens one or more of metal salts comprising HAuCl4·3H2O、Au(SMe2)Cl、Au(tht)Cl、AgNO3、AgBF4、C2AgF3O2、AgPF6、CH3COOAg、Cu(CH3COO)2·H2O、C8H12CuF6N4P、CuCl2、CuCl、CuSO4、H2PtCl6·6H2O、K2PtCl6 with high yield (nearly 100%) of part of nanoclusters, good crystallinity and precise structure.
Preferably, in step S1, the N-heterocyclic-2-thione ligand comprises chiral and achiral N-containing five-membered heterocyclic ring and N-six-membered heterocyclic ring, and more preferably, the structure of the N-heterocyclic-2-thione ligand is shown in figure 1.
Preferably, in step S1, the molar mass ratio of one of the metal salts to the N-heterocyclic-2-thione ligand is 1 (1-4).
Preferably, in step S1, the solvent is one or more of THF, CH 3 CN, DMA, DMF, DMSO and CH2Cl 2.
Preferably, in step S2, the reducing agent comprises triethylamine.
Preferably, in step S2, the color change is observed, meaning that the color of the solution is observed from colorless to pale yellow.
Preferably, in step S2, the solvent comprises THF, CH 2Cl2、DMA、CH3 CN, DMF, aniline, DMSO, cyclohexanone.
In summary, the present invention provides novel ligands that can synthesize metal and alloy nanoclusters, N-heterocycle-2-thione-containing ligands, which are superior ligands for the synthesized clusters due to their specific electronic structure and the existence of tautomers of both thione and thiol structures in the dissolved state. More importantly, the N-heterocycle-2-thioketone-containing ligand is easy to modify, and the nano-cluster can be endowed with good chiral optical activity and excellent luminescence property through the change of the ligand structure. The invention also uses experiments to prove that the N-heterocycle-2-thioketone ligand is used for synthesizing the metal nanocluster, the synthesis method is simple and convenient (a simple one-pot method), the reaction condition is mild (heating is not needed), the synthesis process is environment-friendly (reducing agent is not needed to be added), the yield is high (close to 100%), the crystallinity is good, and the structure is accurate.
Compared with the prior art, the method has the beneficial effects and remarkable progress that the N-heterocycle-2-thioketone-containing organic ligand is utilized to synthesize the metal and alloy nanocluster, the ligand structure is easy to modify, the synthesis method is simple and convenient (a simple one-pot method), the ligand application range is wide, the reaction condition is mild (heating is not needed), the synthesis process is environment-friendly (reducing agents such as sodium borohydride are not needed to be added, the principle of green chemistry is met), the yield is high (close to 100%), the crystallinity is good, and the structure is accurate. Is suitable for mass production.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the following description will briefly explain the drawings used in the embodiments of the present invention.
FIG. 1 is a structural summary of N-containing heterocyclic-2-thione organic ligands encompassed by the present invention;
FIG. 2 is a schematic representation of the reaction mechanism of metal and alloy nanoclusters prepared in accordance with the present invention;
FIG. 3 is a single crystal structure of silver nanoclusters and copper nanoclusters prepared according to the present invention;
Fig. 4 is a Transmission Electron Microscope (TEM) image of silver nanoclusters and copper nanoclusters prepared in accordance with the present invention.
Detailed Description
The application is further illustrated below in connection with specific examples. The examples are only for illustrating the present application and are not intended to limit the scope of the present application. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the disclosure herein, and such equivalents are intended to fall within the scope of the application as defined by the appended claims.
The reaction apparatus and the chemical reagent used in the following examples and comparative examples are commercially available, and the detection instrument and the detection reagent used are commercially available.
In the present invention, as shown in fig. 2, a translation mechanism diagram of a preparation method of metal and alloy nanoclusters is provided, which includes the following steps:
s1, weighing a certain amount of N-heterocycle-2-thione ligand (the structure of the N-heterocycle-2-thione-containing organic ligand is shown as a figure 1) and metal salt, adding a proper amount of solvent for dissolution, fully stirring, and uniformly mixing to obtain a corresponding metal compound;
s2, continuously stirring, observing color change, and continuously reacting for a period of time to obtain a crude product;
S3, slowly volatilizing in a dark place to obtain the monocrystal of the metal and alloy nanocluster.
In a specific embodiment, in step S1, an appropriate amount of a reducing agent may be further added to enhance the reducibility of the N-heterocyclic-2-thione ligand.
In a specific embodiment, step S2 further comprises filtering the resulting crude product, drying in a vacuum oven, repeatedly washing with clean reaction solvent, and then dissolving with a suitable solvent.
In a specific embodiment, in step S1, the metal salt comprises one or more of HAuCl4·3H2O、Au(SMe2)Cl、Au(tht)Cl、AgNO3、AgBF4、C2AgF3O2、AgPF6、CH3COOAg、Cu(CH3COO)2·H2O、C8H12CuF6N4P、CuCl2、CuCl、CuSO4、H2PtCl6·6H2O、K2PtCl6.
In a specific embodiment, in step S1, the N-heterocyclic-2-thione ligand includes chiral and achiral N-containing five-membered and N-six membered heterocycles.
In a specific embodiment, in step S1, the molar mass ratio of one of the metal salts to the N-heterocyclic-2-thione ligand is 1 (1-4).
In a specific embodiment, in step S1, the solvent is one or more of THF, CH 3 CN, DMA, DMF, DMSO and CH2Cl 2.
In a specific embodiment, in step S2, the reducing agent comprises triethylamine.
In a specific embodiment, in step S2, the color change is observed to mean that the color of the solution is observed to be from colorless to pale yellow.
In a specific embodiment, in step S2, the solvent comprises THF, CH 2Cl2、DMA、CH3 CN, DMF, aniline, DMSO, cyclohexanone.
Example 1
The preparation method of the silver nanocluster of the embodiment specifically includes the following steps:
1.1, weighing a certain amount of N-heterocycle-2-thioketone ligand and metal salt (containing silver ions) into a 5mL single crystal bottle, and adding a proper amount of solvent for dissolution;
1.2, fully and uniformly mixing to obtain clear and transparent solution;
1.3, slowly volatilizing in the dark (the obtained clear solution is filtered by a needle filter of 0.22 μm, sealed by a sealing film, and slowly volatilizing in the dark at room temperature for 3-15 days) to obtain silver nanocluster crystals (the crystal structure of the silver nanocluster is shown in fig. 3 a).
The N-heterocycle-2-thione ligand mainly refers to chiral and achiral five-membered N-heterocycle and six-membered N-heterocycle, the metal salt mainly refers to one of AgNO 3、AgBF4、C2AgF3O2、AgPF6、CH3 COOAg, the molar mass ratio of the metal salt to the N-heterocycle-2-thione ligand is one of 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5 and 1:4, the proper amount of solvent refers to the volume of the solvent being 1-4mL, the added solvent is two of THF, CH 3 CN, DMA, DMF, DMSO and CH 2Cl2, the volume ratio of the mixed solvent is one of 1:1, 2:1, 3:1 and the mixing process can be ultrasonic and stirring.
Example 2
The preparation method of the copper nanocluster of the embodiment specifically comprises the following steps:
2.1, weighing a certain amount of N-heterocycle-2-thioketone ligand and metal salt (containing copper ions) into a 25mL single-port bottle, adding a proper amount of solvent for dissolution, fully stirring, and uniformly mixing to obtain a corresponding metal compound.
Wherein the metal salt used is one of Cu(CH3COO)2·H2O、C8H12CuF6N4P、CuCl2、CuCl、CuSO4. The N-containing heterocyclic 2-thiones used encompass chiral and achiral five-membered N-heterocycles and six-membered N-heterocycles. The molar mass ratio of the metal salt to the N-heterocyclic-2-thione ligand is one of 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4. The volume of the proper amount of solvent is 5-15mL, and the stirring speed is 500-800r/min. The added solvent is one or two of THF, CH 3 CN, DMA, DMF, DMSO and CH 2Cl2.
2.2, Filtering the obtained crude product, drying in a vacuum drying oven, repeatedly washing with a clean reaction solvent, and then selecting a proper solvent for dissolution;
wherein, the repeated washing with the reaction liquid means washing until the filtrate becomes colorless. Then choosing proper solvent to dissolve, wherein the solvent mainly comprises THF, CH 2Cl2、DMA、CH3 CN, DMF, aniline, DMSO, cyclohexanone and the like.
2.3, Slowly volatilizing in the dark (after dissolution, the liquid was filtered with a 0.22 μm needle filter, sealed with a sealing film, and 1-3 unequal holes were punched with a 10mL syringe needle, and slowly volatilizing in the dark at room temperature for 3-15 days), to obtain copper nanocluster crystals (the crystal structure of the copper nanoclusters is shown in fig. 3 b).
Example 3
The preparation method of the gold nanocluster of the embodiment specifically comprises the following steps:
3.1, preparing the N-heterocycle-2-thioketone ligand into a mother solution with a certain concentration, adding a proper amount of triethylamine, fully stirring for a period of time, preparing the metal salt (containing gold ions) into the mother solution with a certain concentration, adding the mother solution into the mixed system, and reacting for a specific time;
Wherein the metal salt is one of HAuCl 4·3H2O、Au(SMe2) Cl and Au (tht) Cl. The N-heterocycle-2-thioketone-containing organic ligand mainly refers to chiral and achiral five-membered N-heterocycle and six-membered N-heterocycle. The mother liquor concentration of the N-heterocycle-2-thioketone ligand is one of 5,6, 7 or 8mg/mL, and the mother liquor concentration of the gold salt is one of 5,6, 7 or 8 mg/mL. The volume of triethylamine added was varied from 5 to 15. Mu.L. The total volume of the reaction solution is 2-5mL, and the stirring speed is 500-800r/min. The stirring time is 3-10min after adding triethylamine. The reaction time after the addition of the metal salt is 10min-2h. The solvent used for preparing the N-heterocycle-2-thioketone mother liquor is one of THF and CH 2Cl2、DMA、DMF、DMSO、CH2Cl3, and the solvent used for preparing the metal salt mother liquor is one of CH 3 CN, meOH and EtOH;
3.2, fully and uniformly mixing;
And 3.3, after the reaction is finished, centrifuging (the speed of a centrifugal machine is 8000-12000 r/min), and slowly volatilizing the supernatant in a dark place to obtain gold nanocluster crystals.
Example 4
The preparation method of the alloy nanocluster of the embodiment specifically comprises the following steps:
4.1, weighing a certain amount of N-heterocycle-2-thioketone ligand and metal salt (two of copper ions and silver ions) into a 25mL single-port bottle, adding a proper amount of solvent for dissolution, fully stirring, and uniformly mixing to obtain a corresponding metal compound;
Wherein, the metal salts are two of AgNO3、AgBF4、C2AgF3O2、AgPF6、CH3COOAg、Cu(CH3COO)2·H2O、C8H12CuF6N4P、CuCl2、CuCl、CuSO4. The N-containing heterocyclic 2-thiones used encompass chiral and achiral five-membered N-heterocycles and six-membered N-heterocycles. The molar mass ratio of the metal salt to the N-heterocyclic-2-thione ligand is one of 1:1:2, 1:1:3, 1:1:4, 1:1:5, 1:1:6. The volume of the proper amount of solvent is 5-15mL, and the stirring speed is 500-800r/min. The added solvent is one or two of THF, CH 3 CN, DMA, DMF, DMSO and CH 2Cl2.
Filtering the obtained crude product, drying in a vacuum drying oven, repeatedly washing with a clean reaction solvent, and then selecting a proper solvent for dissolution;
wherein, the repeated washing with the reaction liquid means washing until the filtrate becomes colorless. Then choosing proper solvent to dissolve, wherein the solvent mainly comprises THF, CH 2Cl2、DMA、CH3 CN, DMF, aniline, DMSO, cyclohexanone and the like.
4.3, Slowly volatilizing in dark (after dissolution, filtering the liquid with a needle filter of 0.22 mu m, sealing with a sealing film, puncturing 1-3 different holes with a needle of a 10mL syringe, and slowly volatilizing in dark at room temperature for 3-15 days) to obtain the alloy nanocluster crystal.
Example 5
The silver nanoclusters prepared in example 1 and the copper nanoclusters prepared in example 2 were observed under a transmission electron microscope. The Transmission Electron Microscope (TEM) test method comprises grinding the silver nanoclusters prepared in example 1 and the copper nanoclusters prepared in example 2 into powder, then performing ultrasonic dispersion in ethanol for 10min, and taking 5 mu L of hanging drops on a copper mesh. The prepared nanoparticles were dissolved in ultrapure water to prepare a mother solution of 0.01M, and then diluted 100 times, and 5 μl of the mother solution was dropped onto a copper mesh. Oven drying at 60deg.C, and observing under transmission electron microscope.
As shown in fig. 4, the micro morphology of the synthesized Ag nanoclusters and Cu nanoclusters was spherical, the nanocluster was well dispersed, the size was uniform, and the average particle diameter was about 2nm, which confirmed the expected results.
In summary, the present invention utilizes N-containing heterocyclic-2-thione as a ligand and corresponding metal salts in a suitable solvent environment to produce metal and alloy nanoclusters. The method has the advantages of simple synthesis (a simple one-pot method), mild reaction conditions (no need of heating), environment-friendly synthesis process (no need of adding reducing agents such as sodium borohydride and the like, and conforming to the principle of green chemistry), high yield (nearly 100%), and good crystallinity. The method can obtain crystals suitable for X-ray single crystal diffraction, and accurately know the structure of nanoclusters. In addition, the prepared nanoclusters are spherical in microstructure, good in dispersibility, uniform in size and about 2nm in average particle size as can be seen from a Transmission Electron Microscope (TEM) image.
Applicant states that during the description of the above specification:
The terms "this embodiment," an embodiment of the invention, "" such as "further," "further improved technical solutions," etc., mean that a particular feature, structure, material, or characteristic described in this embodiment or example is included in at least one embodiment or example of the invention, that a schematic representation of the above terms in this specification is not necessarily for the same embodiment or example, and that the particular feature, structure, material, or characteristic described, etc., may be combined or combined in any one or more embodiments or examples in a suitable manner, and that, furthermore, different embodiments or examples and features of different embodiments or examples described in this specification may be combined or combined by persons of ordinary skill in the art without creating contradictions.
Finally, it should be noted that:
the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting thereof;
Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will appreciate that modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some or all of the technical features thereof, without departing from the spirit of the technical solutions of the embodiments of the present invention, and that insubstantial improvements and modifications or substitutions by one skilled in the art from the disclosure herein are within the scope of the invention as claimed.

Claims (5)

1. The preparation method of the metal and alloy nanocluster is characterized by comprising the following steps:
S1, weighing a certain amount of N-heterocycle-2-thione ligand, a reducing agent triethylamine and metal salt, adding a proper amount of solvent for dissolution, fully stirring, and uniformly mixing to obtain a corresponding metal compound, wherein the metal salt comprises one or more of HAuCl 4•3H2O、Au(SMe2) Cl and Au (tht) Cl, the N-heterocycle-2-thione ligand comprises chiral and achiral N-containing five-membered heterocycle and N-six-membered heterocycle, the molar mass ratio of one metal salt to the N-heterocycle-2-thione ligand is 1 (1-4), the concentration of mother liquor of the N-heterocycle-2-thione ligand is one of 5, 6, 7 or 8 mg/mL, and the volume of added triethylamine is 5-15 mu L;
s2, continuously stirring, observing the color of the solution from colorless to pale yellow, and continuously reacting for a period of time to obtain a crude product;
S3, slowly volatilizing in a dark place to obtain the monocrystal of the metal and alloy nanocluster.
2. The method for preparing metal and alloy nanoclusters according to claim 1, wherein step S2 further includes filtering the obtained crude product, drying in a vacuum oven, repeatedly washing with clean reaction solvent, and dissolving with a proper solvent.
3. The method of claim 1, wherein in step S1, the metal salt further comprises one or more of AgNO3、AgBF4、C2AgF3O2、AgPF6、CH3COOAg、Cu(CH3COO)2•H2O、C8H12CuF6N4P、CuCl2、CuCl、CuSO4、H2PtCl6•6H2O、K2PtCl6.
4. The method of claim 1, wherein in step S1, the solvent is one or more of THF, CH 3 CN, DMA, DMF, DMSO and CH 2Cl2.
5. The method of claim 1, wherein in step S2, the solvent comprises THF, CH 2Cl2、DMA、CH3 CN, DMF, aniline, DMSO, cyclohexanone.
CN202310950485.XA 2023-07-31 2023-07-31 Preparation method of metal and alloy nanocluster Active CN117123792B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310950485.XA CN117123792B (en) 2023-07-31 2023-07-31 Preparation method of metal and alloy nanocluster

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310950485.XA CN117123792B (en) 2023-07-31 2023-07-31 Preparation method of metal and alloy nanocluster

Publications (2)

Publication Number Publication Date
CN117123792A CN117123792A (en) 2023-11-28
CN117123792B true CN117123792B (en) 2026-04-10

Family

ID=88853626

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310950485.XA Active CN117123792B (en) 2023-07-31 2023-07-31 Preparation method of metal and alloy nanocluster

Country Status (1)

Country Link
CN (1) CN117123792B (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110330513A (en) * 2019-07-31 2019-10-15 郑州大学 A kind of high stable shines by force the chiral nano silver clustered materials of high quantum production rate

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS576092B2 (en) * 1971-12-28 1982-02-03
US6803177B2 (en) * 2002-07-30 2004-10-12 Eastman Kodak Company Silver compounds and compositions, thermally developable materials containing same, and methods of preparation
CN110883341B (en) * 2018-09-11 2021-03-30 清华大学 Preparation method of gold nanoclusters
CN116199642B (en) * 2023-02-07 2024-09-03 河南理工大学 A chiral copper cluster material with high efficiency near-infrared luminescence and its application in night vision imaging
CN116037951B (en) * 2023-02-20 2025-11-07 安徽大学 Gold-copper alloy nanocluster and preparation method and application thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110330513A (en) * 2019-07-31 2019-10-15 郑州大学 A kind of high stable shines by force the chiral nano silver clustered materials of high quantum production rate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
巯基氮杂环类配体荧光配合物的合成、结构及性能研究;辛利东;《中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑)》2018年第08期;20180815;第2页 *

Also Published As

Publication number Publication date
CN117123792A (en) 2023-11-28

Similar Documents

Publication Publication Date Title
CN104646683B (en) Controllable ball shape silver powder of a kind of granularity and preparation method thereof
CN102581294B (en) Method for preparing nano-metallic copper powder
EP3042727B1 (en) Composition containing fine silver particles, production method thereof, method for producing fine silver particles, and paste having fine silver particles
EP1873117B1 (en) Methods for producing ultrafine particle of prussian blue-type metal complex and of a dispersion liquid thereof
EP3508291A1 (en) Method for preparing solution containing ligand-bonded gold nanoclusters
JP5484442B2 (en) Method for preparing silver nanoparticles
US10226822B2 (en) Method for preparing metal nanoparticles using a multi-functional polymer and a reducing agent
CN103817319A (en) Copper-bearing bimetallic nanometer material with dentritic structure and method for manufacturing copper-bearing bimetallic nanometer material
CN113600825B (en) A kind of micron spherical silver powder and preparation method thereof
JPS59209647A (en) Nickel base catalyst, production and application thereof
WO2017005132A1 (en) Nano metal particle and preparation method thereof
CN114523122A (en) Preparation method of irregular silver powder
CN108817414B (en) A kind of preparation method of gold nanoflowers in ionic liquid aqueous solution
US8313797B2 (en) In-situ growth of magnetic metal nanoparticles in a matrix
JP2018104724A (en) Production method of silver-coated copper powder
Du et al. Origin of symmetry breaking in the seed-mediated growth of bi-metal nano-heterostructures
CN110041531A (en) The method of one step solvent structure Zn-MOF or Zn-Sn-MOF metal organic framework
CN117123792B (en) Preparation method of metal and alloy nanocluster
CN105693639B (en) A kind of high core nickel cluster compound and preparation method thereof based on sulfur-bearing Triazole ligand
CN106112006B (en) A kind of gold nanoparticle aqueous solution and its preparation method and application
JP5647415B2 (en) Preparation of nanoparticles containing iron and titanium
CN103920874A (en) Preparation method of hollow composite nano-particles
JPS63125605A (en) Manufacturing method of metal fine powder
CN110732678B (en) Nano-micron tin-bismuth alloy spherical powder and wet chemical preparation method thereof
CN105081340A (en) Dispersed nano iron particle and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant