CN117123792A - A method for preparing metal and alloy nanoclusters - Google Patents
A method for preparing metal and alloy nanoclusters Download PDFInfo
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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。The invention discloses a method for preparing metal and alloy nanoclusters, which includes the following steps: S1. Weigh a certain amount of N-heterocycle-2-thione ligand and metal salt, add an appropriate amount of solvent to dissolve it, and stir thoroughly. Mix evenly to obtain the corresponding metal complex; S2, continue stirring, observe the color change, and continue the reaction for a period of time to obtain a crude product; S3, slowly volatilize in the dark to obtain single crystals of metal and alloy nanoclusters; the present invention A simple, high-yield, and good crystallinity method for preparing metal and alloy nanoclusters using N-containing heterocycle-2-thione organic ligands is provided.
Description
Technical Field
The application 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 general synthesis method of the metal nanoclusters mainly comprises the following four methods: the first is the method of the reduction growth, the reaction speed depends on the reducing capability of the reducing agent, and the strong reducing agent sodium borohydride, the mild reducing agent sodium cyanoborohydride, CO and the like 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 application 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 application provides the following technical scheme:
the application 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 application, 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 application, the silver nanoclusters and copper nanoclusters are prepared without adding a reducing agent. Whereas in example 3 of the present application, the preparation of gold nanoclusters requires the addition of a reducing agent.
Preferably, step S2 further includes: the crude product obtained is filtered, dried in a vacuum oven, repeatedly washed with clean reaction solvent, and then dissolved by selecting an appropriate solvent.
In the present application, the metal salt may be theoretically any metal ion-containing salt. However, the application also screens metal salts comprising HAuCl with high yield (nearly 100%) of part of nanoclusters, good crystallinity and precise structure 4 ·3H 2 O、Au(SMe 2 )Cl、Au(tht)Cl、AgNO 3 、AgBF 4 、C 2 AgF 3 O 2 、AgPF 6 、CH 3 COOAg、Cu(CH 3 COO) 2 ·H 2 O、C 8 H 12 CuF 6 N 4 P、CuCl 2 、CuCl、CuSO 4 、H 2 PtCl 6 ·6H 2 O、K 2 PtCl 6 One or more of the following.
Preferably, in step S1, the N-heterocyclic-2-thione ligand comprises chiral and achiral N-containing five-membered heterocyclic ring and N-containing six-membered heterocyclic ring; still more preferably, the structure of the N-heterocyclic-2-thione ligand is shown in FIG. 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 THF, CH 3 CN, DMA, DMF, DMSO and CH2Cl 2.
Preferably, in step S2, the reducing agent comprises triethylamine.
Preferably, in step S2, the observation of a color change means: the color of the solution was observed to range from colorless to pale yellow.
Preferably, in step S2, the solvent comprises THF, CH 2 Cl 2 、DMA、CH 3 CN, DMF, aniline, DMSO, cyclohexanone.
In summary, the present application 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 application 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 technical scheme of the application has the beneficial effects and remarkable progress that: according to the application, the N-heterocycle-2-thione-containing organic ligand is used for synthesizing metal and alloy nanoclusters, the ligand structure is easy to modify, the synthesis method is simple and convenient (a simple one-pot method), the ligand is wide in application range, mild in reaction condition (without heating), environment-friendly in the synthesis process (without adding reducing agents such as sodium borohydride and the like, according with the principle of green chemistry), high in yield (close to 100%), and good in crystallinity and accurate in structure. Is suitable for mass production.
Drawings
In order to more clearly illustrate the technical solution of the present application, the following description will briefly explain the drawings used in the embodiments of the present application.
FIG. 1 is a structural summary of N-containing heterocyclic-2-thione organic ligands encompassed by the present application;
FIG. 2 is a schematic representation of the reaction mechanism of metal and alloy nanoclusters prepared in accordance with the present application;
FIG. 3 is a single crystal structure of silver nanoclusters and copper nanoclusters prepared according to the present application;
fig. 4 is a Transmission Electron Microscope (TEM) image of silver nanoclusters and copper nanoclusters prepared in accordance with the present application.
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 application, 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 includes: the crude product obtained is filtered, dried in a vacuum oven, repeatedly washed with clean reaction solvent, and then dissolved by selecting an appropriate solvent.
In a specific embodiment, in step S1, the metal salt comprises HAuCl 4 ·3H 2 O、Au(SMe 2 )Cl、Au(tht)Cl、AgNO 3 、AgBF 4 、C 2 AgF 3 O 2 、AgPF 6 、CH 3 COOAg、Cu(CH 3 COO) 2 ·H 2 O、C 8 H 12 CuF 6 N 4 P、CuCl 2 、CuCl、CuSO 4 、H 2 PtCl 6 ·6H 2 O、K 2 PtCl 6 One or more of the following.
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 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 observed color change means: the color of the solution was observed to range from colorless to pale yellow.
In a specific embodiment, in step S2, the solvent comprises THF, CH 2 Cl 2 、DMA、CH 3 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).
Wherein the N-heterocycle-2-thioketone ligand mainly refers to chiral and achiral five-membered N-heterocycle and six-membered N-heterocycle, and the metal salt mainly refers to AgNO 3 、AgBF 4 、C 2 AgF 3 O 2 、AgPF 6 、CH 3 One of 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 means that the volume of the solvent is 1-4 mL; the added solvent is THF, CH 3 CN, DMA, DMF, DMSO and CH 2 Cl 2 Two of (a) and (b); the volume ratio of the mixed solvent is one of 1:1, 2:1, 3:1 and the like; 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 Cu (CH) 3 COO) 2 ·H 2 O、C 8 H 12 CuF 6 N 4 P、CuCl 2 、CuCl、CuSO 4 One of them. 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 THF, CH 3 CN, DMA, DMF, DMSO and CH 2 Cl 2 One or two of the following solvents.
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 for dissolution, wherein the solvent mainly comprises THF and CH 2 Cl 2 、DMA、CH 3 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 HAuCl 4 ·3H 2 O、Au(SMe 2 ) Cl, 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 THF, CH 2 Cl 2 、DMA、DMF、DMSO、CH 2 Cl 3 One of them, the solvent used for preparing mother liquor of metal salt is CH 3 CN, meOH, 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 salt is AgNO 3 、AgBF 4 、C 2 AgF 3 O 2 、AgPF 6 、CH 3 COOAg、Cu(CH 3 COO) 2 ·H 2 O、C 8 H 12 CuF 6 N 4 P、CuCl 2 、CuCl、CuSO 4 Two of which are described below. 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 THF, CH 3 CN, DMA, DMF, DMSO and CH 2 Cl 2 One or two of the following solvents.
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 for dissolution, wherein the solvent mainly comprises THF and CH 2 Cl 2 、DMA、CH 3 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. Wherein the Transmission Electron Microscope (TEM) test method comprises: silver nanoclusters prepared in example 1 and copper nanoclusters prepared in example 2 were ground into powder, then ultrasonically dispersed in ethanol for 10min, and 5 μl of the powder was dropped onto 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 in vacuum, 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 application 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 application," "as shown in … …," "further improved embodiments," and the like, mean that a particular feature, structure, material, or characteristic described in the embodiment or example is included in at least one embodiment or example of the application; in this specification, a schematic representation of the above terms is not necessarily directed to the same embodiment or example, and the particular features, structures, materials, or characteristics described, etc. may be combined or combined in any suitable manner in any one or more embodiments or examples; furthermore, various embodiments or examples, as well as features of various embodiments or examples, described in this specification may be combined or combined by one of ordinary skill in the art without undue experimentation.
Finally, it should be noted that:
the above embodiments are only for illustrating the technical solution of the present application, and are not limiting thereof;
although the present application 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 application, and that insubstantial improvements and modifications or substitutions by one skilled in the art from the disclosure herein are within the scope of the application as claimed.
Claims (10)
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 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.
2. The method for preparing metal and alloy nanoclusters according to claim 1, wherein a proper amount of a reducing agent is added in step S1 to enhance the reducibility of the N-heterocyclic-2-thione ligand.
3. The method of claim 1, wherein step S2 further comprises: the crude product obtained is filtered, dried in a vacuum oven, repeatedly washed with clean reaction solvent, and then dissolved by selecting an appropriate solvent.
4. The method of claim 1, wherein in step S1, the metal salt comprises HAuCl 4 ·3H 2 O、Au(SMe 2 )Cl、Au(tht)Cl、AgNO 3 、AgBF 4 、C 2 AgF 3 O 2 、AgPF 6 、CH 3 COOAg、Cu(CH 3 COO) 2 ·H 2 O、C 8 H 12 CuF 6 N 4 P、CuCl 2 、CuCl、CuSO 4 、H 2 PtCl 6 ·6H 2 O、K 2 PtCl 6 One or more of the following.
5. The method of claim 1, wherein the N-heterocyclic-2-thione ligand in step S1 comprises chiral and achiral N-containing five-membered heterocyclic rings and N-six-membered heterocyclic rings.
6. The method of claim 5, wherein in step S1, the molar mass ratio of the metal salt to the N-heterocyclic-2-thione ligand is 1 (1-4).
7. The method of claim 1, wherein in step S1, the solvent is THF or CH 3 CN, DMA, DMF, DMSO and CH2Cl 2.
8. The method of claim 2, wherein in step S2, the reducing agent comprises triethylamine.
9. The method of claim 1, wherein in step S2, the color change is observed by: the color of the solution was observed to range from colorless to pale yellow.
10. The method of claim 3, wherein in step S2, the solvent comprises THF, CH 2 Cl 2 、DMA、CH 3 CN, DMF, aniline, DMSO, cyclohexanone.
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