CN111606932A - Forty-five-core silver nanocluster with metal core containing chlorine ions and synthesis method thereof - Google Patents
Forty-five-core silver nanocluster with metal core containing chlorine ions and synthesis method thereof Download PDFInfo
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 95
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000004332 silver Substances 0.000 title claims abstract description 86
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 36
- 239000002184 metal Substances 0.000 title claims abstract description 36
- -1 chlorine ions Chemical class 0.000 title claims abstract description 8
- 239000000460 chlorine Substances 0.000 title abstract description 41
- 238000001308 synthesis method Methods 0.000 title abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 title abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 54
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 125000001424 substituent group Chemical group 0.000 claims abstract description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- 239000003446 ligand Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 230000002194 synthesizing effect Effects 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 11
- 150000001345 alkine derivatives Chemical class 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 5
- 229910001504 inorganic chloride Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- PVYPHUYXKVVURH-UHFFFAOYSA-N boron;2-methylpropan-2-amine Chemical compound [B].CC(C)(C)N PVYPHUYXKVVURH-UHFFFAOYSA-N 0.000 claims description 3
- 150000003841 chloride salts Chemical class 0.000 claims description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- 229960002635 potassium citrate Drugs 0.000 claims description 3
- 239000001508 potassium citrate Substances 0.000 claims description 3
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 3
- 235000011082 potassium citrates Nutrition 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 229910001544 silver hexafluoroantimonate(V) Inorganic materials 0.000 abstract description 6
- 230000009471 action Effects 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 229910017744 AgPF6 Inorganic materials 0.000 abstract description 2
- 101710134784 Agnoprotein Proteins 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000004020 luminiscence type Methods 0.000 abstract description 2
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 150000003378 silver Chemical group 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000004383 yellowing Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical group 0.000 description 2
- 150000001793 charged compounds Chemical class 0.000 description 2
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 239000002244 precipitate Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 238000013096 assay test Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/10—Silver compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention relates to a silver nanocluster, in particular to a forty-five core silver nanocluster with a metal core containing chlorine ions and a synthesis method thereof. The invention creatively prepares the silver alkyne precursor AgC ≡ CR (R is tert-butyl, phenyl or phenyl with substituent), silver salt (AgNO)3、AgSbF6、AgPF6、AgBF4、AgClO4、AgCH3COO、AgCF3COO or AgCF3SO3) And a trace amount of chloride ions are mixed and then react under the action of a reducing agent to obtain the forty-five-core silver nanocluster compound with the metal core containing the chloride ions. The synthesized silver nanocluster disclosed by the invention is rich and adjustable in structure, and because chloride ions are introduced into the metal core of the silver nanocluster, the finally prepared silver nanocluster is stable in structure, high in yield and excellent in performance, and is suitable for popularization and application in the fields of luminescence and catalysis.
Description
Technical Field
The invention relates to a silver nanocluster, in particular to a forty-five core silver nanocluster with a metal core containing chlorine ions and a synthesis method thereof.
Background
The size of the metal nanocluster is in the range of a few tenths to ten nanometers, and the metal nanocluster is different from the conventional large metal particles, and has various properties which are mainly represented by quantum size effect, extremely high surface atom distribution and high specific surface area. Because the silver nanoclusters have unique molecular structures and unique properties, the silver nanoclusters have wide application in the fields of luminescence, catalysis and the like, and are paid more and more attention by scientists.
However, most of the silver nanoclusters still have the problems of low stability and low yield, and are difficult to utilize the specific optical, catalytic, electrochemical, magnetic properties and the like.
Therefore, the development of a silver nanocluster with high stability and yield has become a problem to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the present invention provides a forty-five core silver nanocluster in which the metal core contains chloride ions, which is directed to the problems of the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a forty-five core silver nanocluster having a chloride ion-containing metal core, the silver nanocluster being [ Ag ]45Cl6(RC≡C)32]X4And the molecular structure of the silver nanoclusters is as follows:
wherein R is tert-butyl, phenyl or phenyl with substituent; the substituent is at least-F, -Cl, -Br, -I and-NO2、-OCH3One of (1);
x is an anionic group; and X is SbF6 -、PF6 -、BF4 -、ClO4 -、NO3 -、CH3COO-、CF3COO-Or CF3SO3 -。
Further, [ Ag ]45Cl6(RC≡C)32]4+Is a cationic group and the structure of the cationic group is as follows:
it is worth mentioning that the silver nanocluster compound isThe silver metal core in the structure contains chloride ions, and the technical point is never reported in the prior art documents. And the structure of the forty-five core silver nanocluster is determined by single crystal X diffraction as follows: [ Ag ]45Cl6(RC≡C)32]X4。
Meanwhile, the cation moiety [ Ag ]45Cl6(RC≡C)32]4+Is a forty-five-core silver cluster synthesized by Cl-serving as a template, the central Ag atom is encapsulated in an Ag8 cluster, the Ag8 cluster is covered by an Ag36 cluster shell, and the surfaces of three shells Ag @ Ag8@ Ag36 are covered by 32 ButC.ident.C protection, the template silver atom is combined with 8 silver atoms to construct Ag @ Ag8, the Ag8 unit can be regarded as a hexahedral body-centered cubic framework, six square faces of the hexahedron are covered by six Cl atoms, an octahedral arrangement is adopted between silver and silver, and eight vertexes of the Ag8 unit are stabilized by eight RC.ident.C ligands adopting a cubic arrangement.
And, the Ag @ Ag8 cluster is further attached to the outer shell by interaction of the Ag-philic Ag … Ag and Ag … C bonds, respectively. The Ag36 cluster is formed by 36 silver atoms and forms 24 triangles, 6 quadrangles and 8 twisted hexagons.
A second object of the present invention is to provide a method for synthesizing the forty-five core silver nanocluster in which the metal core contains chloride ions.
In order to achieve the above purpose, the invention provides the following technical scheme:
the method for synthesizing the forty-five-core silver nanocluster with the metal core containing the chloride ions comprises the following steps:
I. synthesizing an alkyne silver precursor AgC ≡ CR: mixing Ag with water2Dissolving O in ammonia water to prepare a silver-ammonia solution, then dropping alkyne HC ≡ CR into the silver-ammonia solution under vigorous stirring, filtering, washing and drying to finally prepare AgC ≡ CR;
specifically, Ag is added2Dissolving O in ammonia water to obtain silver-ammonia solution, stirring to dissolve it as much as possible, filtering to obtain colorless transparent clear solution (wherein, tin foil paper is used to avoid light during dissolving and filtering), dropping alkyne (HC ≡ CR) into the silver-ammonia solution under vigorous stirring, generating a large amount of white precipitate, after dropping,and (3) carrying out suction filtration, sequentially washing with water, ethanol and diethyl ether, and carrying out vacuum drying overnight to obtain the alkyne silver precursor AgC ≡ CR.
II. And (3) adding the AgC ≡ CR obtained in the step (I) into a polar solvent, adding a silver salt and a small amount of chloride ions, adding a reducing agent after ultrasonic dispersion is uniform, stirring or heating to react to obtain a yellow clear solution, and removing the solvent to obtain the forty-five-core silver nanocluster with the metal core containing the chloride ions.
It is worth to say that the synthesis method disclosed and protected by the invention is simple, the product (the tetrapentadecanuclear silver nanoclusters with high stability and metal cores containing chloride ions) can be obtained only by mixing AgC ≡ CR, silver salt and trace chloride ions and then reacting for several hours under the action of a reducing agent, and the yield is high (about 68%).
Further, in the step I, Ag2The molar ratio of O to ammonia water is 1: 10, the molar ratio of HC ≡ CR to silver ions in silver ammonia is 1.2: 1.
in the step II, the molar ratio of AgC ≡ CR to silver salt is (3: 1) to (1: 3), and the molar ratio of chloride ions to silver salt is (1/20-1/50): 1, the molar ratio of the reducing agent to the silver salt is 1: (10-20).
Still further, the chloride ion is at least one of an inorganic chloride salt and an organic chloride, the polar solvent includes methanol, ethanol, acetonitrile or tetrahydrofuran, and the reducing agent is at least one of sodium borohydride, sodium cyanoborohydride, potassium citrate and borane-tert-butylamine.
Wherein the inorganic chloride is NaCl, and the organic chloride is NH4Cl、NMe4Cl, and the like.
Further, the reaction in the step II is stirring for 5-10 h or heating at 60 ℃ for 1-5 h, so as to obtain a yellow clear solution.
Further, the reaction in step II further comprises adding a phosphine ligand PPh3To help form a uniform dispersion.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the structural stability of the silver nanocluster compound is closely related to chloride ions, the chloride ions are used as an anion template for constructing a multi-atom metal core, the electronic state of the metal core is regulated and controlled due to the large electronegativity of the chloride ions in the synthesis process so as to stabilize the metal core, the chloride ions are also used as inorganic ligands to protect the metal core, and the chloride ions can occupy some loose silver sites on the outermost layer and the secondary outer layer to balance partial positive charges on the outer layer, so that the anion doping strategy disclosed by the invention provides more possibilities and bases for preparing the silver nanocluster with stable structure.
2. The silver nanocluster [ Ag ] provided by the invention45Cl6(RC≡C)32]X4Not only has stable structure, but also is applicable to various alkyne ligands HC ≡ CR, R is tertiary butyl, phenyl with substituent (such as F, Cl, Br, I, NO)2、OCH3Etc.), the structure is rich and adjustable.
3. The synthesis method provided by the invention is simple, the raw materials are easy to obtain, the synthesis steps are few, the synthesis conditions are mild, the yield is high, and the method has the potential of industrial application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts
Fig. 1 is a molecular structural view of the forty-five core silver nanocluster of the present invention.
FIG. 2 shows a cationic group ([ Ag ]) of the forty-five core silver nanocluster of the present invention45Cl6(RC≡C)32]4+) The molecular structure of (1).
Fig. 3 is a photograph of a crystal of the forty-five core silver nanocluster of the present invention.
Fig. 4 is a metal core anatomical view of the forty-five core silver nanoclusters of the present invention.
Fig. 5 is a ligand coordination diagram of the forty-five core silver nanoclusters of the present invention.
Fig. 6 is a high resolution mass spectrum of the forty-five core silver nanocluster of the present invention.
Fig. 7 is an absorption spectrum of the forty-five core silver nanocluster of the present invention.
Fig. 8 is a time-dependent absorption spectrum of the forty-five core silver nanoclusters of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the specification, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The present invention will be further specifically illustrated by the following examples for better understanding, but the present invention is not to be construed as being limited thereto, and certain insubstantial modifications and adaptations of the invention by those skilled in the art based on the foregoing disclosure are intended to be included within the scope of the invention.
A method for synthesizing forty-five-core silver nanoclusters with chloride ions in metal cores specifically comprises the following steps:
I. synthesizing an alkyne silver precursor AgC ≡ CR: mixing Ag with water2Dissolving O in ammonia water to prepare silver-ammonia solution, stirring to dissolve the silver-ammonia solution as much as possible, filtering to obtain colorless transparent clear solution (tin foil paper is used for keeping out of the light in the dissolving and filtering processes), dropwise adding alkyne (HC ≡ CR) into the silver-ammonia solution under vigorous stirring, generating a large amount of white precipitates, after dropwise adding, carrying out suction filtration, washing with water, ethanol and diethyl ether in sequence, and carrying out vacuum drying overnight to obtain the alkyne-silver precursor AgC ≡ CR;
II. Adding AgC ≡ CR obtained in step I into methanol (polar solvent such as ethanol, acetonitrile, tetrahydrofuran, etc.), and adding silver salt (AgNO)3、AgSbF6、AgPF6、AgBF4、AgClO4、AgCH3COO、AgCF3COO or AgCF3SO3) And a small amount of chloride ions, ultraAnd (3) obtaining uniform dispersion liquid by sound, adding a reducing agent, stirring or heating to obtain a yellow clear solution, and removing the solvent to obtain the target silver nanocluster.
Further, in the step I, Ag2The molar ratio of O to ammonia water is 1: 10, the molar ratio of HC ≡ CR to silver ions in silver ammonia is 1.2: 1.
in the step II, the molar ratio of AgC ≡ CR to silver salt is (3: 1) to (1: 3), and the molar ratio of chloride ions to silver salt is (1/20-1/50): 1, the molar ratio of the reducing agent to the silver salt is 1: (10-20).
Still further, the chloride ion is at least one of an inorganic chloride salt and an organic chloride, the polar solvent includes methanol, ethanol, acetonitrile or tetrahydrofuran, and the reducing agent is at least one of sodium borohydride, sodium cyanoborohydride, potassium citrate and borane-tert-butylamine.
Wherein the inorganic chloride is NaCl, and the organic chloride is NH4Cl、NMe4Cl, and the like.
Further, the reaction in the step II is stirring for 5-10 h or heating at 60 ℃ for 1-5 h, so as to obtain a yellow clear solution.
Further, the reaction in step II further comprises adding a phosphine ligand PPh3To help form a uniform dispersion.
The technical solutions envisioned and protected by the present application will be explained with reference to specific examples, which are specifically as follows:
example 1:
a method for synthesizing forty-five-core silver nanoclusters with metal cores containing chloride ions specifically comprises the following steps:
preferably, the molar ratio of AgC ≡ CR to silver salt is 1: and 2, the molar ratio of the chloride ions to the silver salts is 1: 30, the molar ratio of the reducing agent to the silver salt is 1: 15.
Namely 0.1mmol of AgC ≡ CButWith 0.2mmol of AgSbF6Mixing and dissolving in 10mL of methanol, and adding NMe containing 0.01mmol4Adding 0.02mmol of NaBH into Cl methanol solution under stirring4Ethanol solution, and slowly yellowing to obtain moleculesIs of the formula [ Ag45Cl6(ButC≡C)32(SbF6)4Silver nanoclusters in 68% yield.
Example 2:
a method for synthesizing forty-five-core silver nanoclusters with metal cores containing chloride ions specifically comprises the following steps:
the molar ratio of AgC ≡ CR to silver salt is 1: and 3, the molar ratio of the chloride ions to the silver salts is 1: 50, the molar ratio of the reducing agent to the silver salt is 1: 20.
Namely 0.1mmol of AgC ≡ CButWith 0.3mmol of AgSbF6Mixing and dissolving in 10mL of methanol, and adding NMe containing 0.006mmol4Adding 0.015mmol of NaBH into Cl methanol solution under stirring4Ethanol solution, and slowly yellowing to obtain the product with the molecular formula [ Ag45Cl6(ButC≡C)32(SbF6)4Silver nanoclusters in 48% yield.
Example 3:
a method for synthesizing forty-five-core silver nanoclusters with metal cores containing chloride ions specifically comprises the following steps:
preferably, the molar ratio of AgC ≡ CR to silver salt is 1: and 2, the molar ratio of the chloride ions to the silver salts is 1: 30, the molar ratio of the reducing agent to the silver salt is 1: 15.
Namely 0.1mmol of AgC ≡ CPh and 0.2mmol of AgSbF6Mixing and dissolving in 10mL of methanol, and adding NMe containing 0.01mmol4Adding 0.02mmol of NaBH into Cl methanol solution under stirring4Slowly yellowing the ethanol solution, and volatilizing to obtain the product with the molecular formula [ Ag45Cl6(PhC≡C)32](SbF6)4The yield of the silver nanocluster of (1) was 63%.
Example 4:
a method for synthesizing forty-five-core silver nanoclusters with metal cores containing chloride ions specifically comprises the following steps:
preferably, the molar ratio of AgC ≡ CR to silver salt is 1: and 3, the molar ratio of the chloride ions to the silver salts is 1: 50, the molar ratio of the reducing agent to the silver salt is 1: 20.
Namely, 0.1mmol of AgC ≡ CPh and0.2mmol AgSbF6mixing and dissolving in 10mL of methanol, and adding NMe containing 0.006mmol4Adding 0.015mmol of NaBH into Cl methanol solution under stirring4Slowly yellowing the ethanol solution, and volatilizing to obtain the product with the molecular formula [ Ag45Cl6(PhC≡C)32](SbF6)4The yield of the silver nanocluster of (1) was 43%.
To further demonstrate the advantageous effects of the present invention for a better understanding of the present invention, the forty-five core silver nanoclusters [ Ag ] having a metal core containing chloride ions according to the present invention are further illustrated by the following assay tests45Cl6(RC≡C)32]X4The properties and applications of the present invention are not limited to the above-mentioned properties, and the properties of the product and applications based on the above-mentioned properties obtained by other determination experiments performed by those skilled in the art according to the above-mentioned summary of the invention are also considered to fall within the scope of the present invention.
Experimental example 1: structural characterization
The crystal structures of the silver nanoclusters synthesized as disclosed in the above examples 1 to 2 are characterized, and refer to fig. 3 to 6.
It can be seen from fig. 3 that the forty-five core silver nanoclusters prepared by the synthesis method disclosed by the present invention are yellow bulk crystals.
As can be seen from FIG. 4 and FIG. 5, the cation moiety [ Ag ]45Cl6(ButC≡C)32]4+Is a forty-five-core silver cluster synthesized by Cl-serving as a template, the central Ag atom is encapsulated in an Ag8 cluster, the Ag8 cluster is covered by an Ag36 cluster shell, and the surfaces of three shells Ag @ Ag8@ Ag36 are covered by 32 ButC is identical to C protection, the template silver atom is combined with 8 silver atoms to construct Ag @ Ag8, the Ag8 unit can be regarded as a hexahedron body-centered cubic framework, six square faces of the hexahedron are covered by six Cl atoms, octahedron arrangement is adopted between silver and silver, and eight vertexes of the Ag8 unit are formed by eight Bu in cubic arrangementtThe C ≡ C ligand is stable.
And, the Ag @ Ag8 cluster is further attached to the outer shell by interaction of the Ag-philic Ag … Ag and Ag … C bonds, respectively. The Ag36 cluster is formed by 36 silver atoms and forms 24 triangles, 6 quadrangles and 8 twisted hexagons.
[Ag45Cl6(ButC≡C)32(SbF6)4The stability is closely related to the chloride ion, the chloride ion is used as an anion template for constructing the polyatomic metal core, in the synthesis process, the electronic state of the metal core is regulated and controlled due to the large electronegativity of the chloride ion so as to stabilize the metal core, the chloride ion is also used as an inorganic ligand to protect the metal core, the chloride ion can occupy some loose silver sites on the outermost layer and the secondary outer layer to balance partial positive charges of the outer layer, and therefore the anion doping strategy provides more possible and theoretical bases for preparing the silver nanocluster with a stable structure.
Fig. 6 is a mass spectrum of the forty-five core silver nanocluster solution. The black part in the mass spectrogram is the experimental value of the molecular ion peak, and the red trace is the simulated value, so that the molecular ion peak experimental value and the red trace are well matched, wherein [ Ag [ -45Cl6(ButC≡C)32Cl2]2+Has the largest content of [ Ag ]45Cl6(ButC≡C)31Cl3]2+Secondly, thirdly [ Ag45Cl6(ButC≡C)33Cl1]2+From this, [ Ag ] can be found45Cl6(ButC≡C)32Cl2]2+Ligand ratio of [ Ag ]45Cl6(ButC≡C)31Cl3]2+One more ButA C ≡ C ligand, and [ Ag ≡ C45Cl6(ButC≡C)32Cl2]2+Ligand ratio of [ Ag ]45Cl6(ButC≡C)33Cl1]2+One Cl ligand less and one Bu moretC.ident.C ligands, and therefore can be obtained primarily, [ Ag ]45Cl6(ButC≡C)32(SbF6)4Cl ligand and Bu in mass spectrometry ionization environmenttThe C ≡ C ligands are often exchanged while the forty-five core silver nanoclusters with the host structure containing six chloride ions remain unchanged, indicating that the forty-five core silver isThe nanoclusters are stable in solution.
Experimental example 2: measurement of Performance
Absorption spectrum measurement was performed on the prepared forty-five core silver nanoclusters as shown in fig. 7.
Ag can be obtained from FIG. 745Has absorption peaks at 387nm and 456nm, and the metal silver nano particle has a sharp absorption peak at 400nm, which shows that Ag45Wherein the absorption band can be attributed to the result of metal chloride ligand interaction.
Experimental example 3: stability determination
The stability of the prepared forty-five core silver nanoclusters was examined as shown in fig. 8.
It can be seen from FIG. 8 that the absorption spectrum remained at 387nm and in the vicinity of 456nm after 7 days, indicating that Ag45Are stable on storage at ambient conditions.
In conclusion, the silver nanocluster synthesized by the method disclosed by the invention is high in yield and good in stability, contains six chloride ions, and induces Ag under the combined action of the alkyne ligand and the reducing agent45High yield of silver nanoclusters with forty-five nuclei is obtained. The yield of the silver nanoclusters prepared by the method is up to more than 68%, the synthesis efficiency of the silver nanoclusters is greatly improved, and the method has the advantages of simplicity in operation, strong applicability and convenience in industrial production.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A forty-five core silver nanocluster having a chloride ion contained in a metal core, wherein the silver nanocluster is characterized in that silver nanoparticlesThe rice cluster is [ Ag ]45Cl6(RC≡C)32]X4And the structure of the silver nanoclusters is as follows:
wherein R is tert-butyl, phenyl or phenyl with substituent; the substituent is at least-F, -Cl, -Br, -I and-NO2、-OCH3One of (1);
x is an anionic group; and X is SbF6 -、PF6 -、BF4 -、ClO4 -、NO3 -、CH3COO-、CF3COO-Or CF3SO3 -。
2. The forty-five core silver nanocluster with chloride ion containing metal core as claimed in claim 1, wherein [ Ag [ ]45Cl6(RC≡C)32]4+Is a cationic group and the cationic group has the following structure:
3. the method for synthesizing the forty-five-core silver nanoclusters with the metal cores containing chloride ions according to claim 1, wherein the method specifically comprises the following steps:
I. synthesizing an alkyne silver precursor AgC ≡ CR: mixing Ag with water2Dissolving O in ammonia water to prepare a silver-ammonia solution, then dropping alkyne HC ≡ CR into the silver-ammonia solution under vigorous stirring, filtering, washing and drying to finally prepare AgC ≡ CR;
II. And (3) adding the AgC ≡ CR obtained in the step (I) into a polar solvent, adding a silver salt and a small amount of chloride ions, adding a reducing agent after ultrasonic dispersion is uniform, stirring or heating to react to obtain a yellow clear solution, and removing the solvent to obtain the forty-five-core silver nanocluster with the metal core containing the chloride ions.
4. The method as claimed in claim 3, wherein in step I, Ag is added to the silver nanoclusters having a metal core containing chloride ions2The molar ratio of O to ammonia water is 1: 10, the molar ratio of HC ≡ CR to silver ions in silver ammonia is 1.2: 1.
5. the method for synthesizing forty-five-core silver nanoclusters with chloride ions in metal cores as claimed in claim 3, wherein in the step II, the molar ratio of AgC ≡ CR to silver salt is (3: 1) - (1: 3), and the molar ratio of chloride ions to silver salt is (1/20-1/50): 1, the molar ratio of the reducing agent to the silver salt is 1: (10-20).
6. The method as claimed in claim 5, wherein the chloride ion is at least one of an inorganic chloride salt and an organic chloride, the polar solvent includes methanol, ethanol, acetonitrile or tetrahydrofuran, and the reducing agent is at least one of sodium borohydride, sodium cyanoborohydride, potassium citrate and borane-tert-butylamine.
7. The method for synthesizing forty-five core silver nanoclusters with chloride ions as claimed in claim 3 or 6, wherein the reaction in step II is stirring for 5-10 h or heating at 60 ℃ for 1-5 h, so as to obtain yellow clear solution.
8. The method as claimed in claim 7, wherein the reaction of step II further comprises adding phosphine ligand PPh3To help form a uniform dispersion.
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| CN114106039B (en) * | 2021-11-16 | 2022-06-24 | 河南科技学院 | Silver nanocluster and preparation method thereof |
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