CN114525125A - Water-soluble 'atom accurate' Ag6Nanocluster and macro synthesis method and application thereof - Google Patents
Water-soluble 'atom accurate' Ag6Nanocluster and macro synthesis method and application thereof Download PDFInfo
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- CN114525125A CN114525125A CN202210149612.1A CN202210149612A CN114525125A CN 114525125 A CN114525125 A CN 114525125A CN 202210149612 A CN202210149612 A CN 202210149612A CN 114525125 A CN114525125 A CN 114525125A
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- 238000001308 synthesis method Methods 0.000 title claims abstract description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003446 ligand Substances 0.000 claims abstract description 27
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 13
- 239000007850 fluorescent dye Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 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 description 31
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 25
- 239000013078 crystal Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 13
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 229910002699 Ag–S Inorganic materials 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical group SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 claims description 3
- -1 sulfhydryl pyridine Chemical compound 0.000 claims description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 34
- 229910052709 silver Inorganic materials 0.000 abstract description 29
- 239000004332 silver Substances 0.000 abstract description 29
- 230000015572 biosynthetic process Effects 0.000 abstract description 20
- 239000000126 substance Substances 0.000 abstract description 18
- 230000007547 defect Effects 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000002585 base Substances 0.000 description 13
- WYKHFQKONWMWQM-UHFFFAOYSA-N 2-sulfanylidene-1h-pyridine-3-carboxylic acid Chemical compound OC(=O)C1=CC=CN=C1S WYKHFQKONWMWQM-UHFFFAOYSA-N 0.000 description 12
- 238000000527 sonication Methods 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 150000003378 silver Chemical class 0.000 description 9
- 238000002296 dynamic light scattering Methods 0.000 description 8
- 150000003573 thiols Chemical class 0.000 description 7
- 239000002994 raw material Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001506 fluorescence spectroscopy Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 238000002114 high-resolution electrospray ionisation mass spectrometry Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- 238000013094 purity test Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- JWWGTYCXARQFOT-UHFFFAOYSA-N 6-sulfanylidene-1h-pyridine-3-carboxylic acid Chemical compound OC(=O)C1=CC=C(S)N=C1 JWWGTYCXARQFOT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000000119 electrospray ionisation mass spectrum Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 244000195895 saibo Species 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Abstract
The invention relates to water-soluble 'atom precise' Ag6Nanoclusters and macro synthesis methods and applications thereof. The invention creatively protects the silver core through the strongly coordinated sulfhydryl ligand, successfully constructs a partThe water-soluble silver cluster with accurate atoms greatly overcomes the defects of difficult assembly and poor solubility of the oil-soluble silver cluster, can effectively expand the physical and chemical properties of the silver cluster, and provides possibility and basis for the synthesis of other types of water-soluble clusters. At the same time, the prepared water-soluble Ag with accurate atoms6The nanocluster has good stability and outstanding optical property, can be suitable for popularization and application in the fields of fluorescent probes and light conversion materials, and more importantly, the water-soluble Ag with accurate atoms6The nanoclusters can be synthesized in a large quantity, have the advantage of industrial production potential, and greatly make up for the defect of low yield of most of the nanoclusters. The water-soluble 'atom accurate' Ag of the invention6The macro preparation method of the nanoclusters is simple and low in cost.
Description
Technical Field
The invention relates to a water-soluble 'atom precise' silver nanocluster, in particular to a silver nanocluster with mercapto-group and carboxyl-group-containing bifunctional ligand protection and 6 silver ions in a kernel, and a synthesis method and application thereof.
Background
The metal nanoclusters are relatively stable aggregates consisting of several to several thousands of metal atoms through physical or chemical bonding forces, and have quantum size dependence in physical and chemical properties, and the size thereof is comparable to the Ferimi wavelength of electrons, and is generally less than 3 nm. Due to the special structure of the metal cluster, the metal cluster can show molecular-like properties, thereby showing excellent physicochemical properties such as optics, electrics, magnetism, catalysis, chirality and the like.
Silver nanoclusters are a common one, and there are many patent documents reported, for example: CN111606932A discloses a forty-five core silver nanocluster with a metal core containing chloride ions and a synthesis method thereof, CN111748340A discloses a novel fluorescent silver nanocluster and a synthesis method and application thereof, and CN111606931A discloses an octa core silver nanocluster with a perfluoro glutaric acid-protected atomic structure and an accurate atomic structure and a preparation method and application thereof. The silver clusters have accurate atom nanostructures, but are all oil-soluble clusters without water-solubility characteristics, so that the application and development of the silver clusters are greatly limited. More importantly, the method cannot realize macro synthesis and is difficult to promote industrialization.
However, the problems with the current silver nanoclusters are: no precise structure; the yield is low, and macro synthesis cannot be realized; the stability is poor; most of the oil-soluble silver clusters are synthesized. A water-soluble, atom-accurate Ag synthesized in the prior art9Nanoclusters, however, do not exhibit fluorescent properties at room temperature and are less stable. This is also the majority of the silver clustersThe method has the defects that the silver nanocluster does not emit light at room temperature, and the existing silver nanoclusters with precise atoms cannot be synthesized massively. The above disadvantages greatly limit the development and application of silver clusters in many fields.
Therefore, it is urgently needed to develop a macro-synthetic water-soluble 'atom-accurate' silver cluster, which not only can provide a good reference for the subsequent synthesis of the water-soluble cluster, but also can expand the application field of the silver cluster.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides water-soluble Ag with accurate atoms6Nanoclusters and macro synthesis methods and applications thereof.
Description of terms:
Ag6: is a six-core 'atom precise' silver nanocluster, and because the luminescent Ag with good water solubility is constructed through the introduction of strong coordination element S, the introduction of rigid ligand benzene ring and the introduction of hydrophilic group through coordination6Nanoclusters.
The technical scheme of the invention is as follows:
water-soluble Ag with accurate atoms6Nanoclusters of said Ag6The molecular formula of the nanocluster is X6[Ag6(SR)6]，
Wherein SR is mercaptopyridine, pyridine with substituent groups or benzene ring, and X is a cationic group; the substituent is at least-CH3、-F、-Cl、-Br、-COOH、-OCH3One kind of (1).
According to the invention, X is preferably (CH)3)4N+，(CH3CH2CH2CH2)4N+，(CH3CH2CH2)4N+，(CH3CH2)4N+，Na+，K+Or NH4 +。
According to the invention, preferably, the Ag is6Nanoclusters are crystallized in the triclinic space group P-1 with one half of the asymmetric units made of Ag6And 4.5 waters.
According to the invention, preferably, the Ag is6The silver skeleton of the nanocluster is of an octahedral structure and is protected by 6 sulfydryl ligands, and Ag-S bonds are arranged on
Within the range.
According to the invention, the Ag6A model of the single crystal molecular structure of the nanoclusters is shown in fig. 1.
According to the invention, the water-soluble "atomically precise" Ag6The macro synthesis method of the nanoclusters comprises the following steps:
dispersing silver salt and sulfhydryl ligand in polar solvent, ultrasonic treating, adding alkaline solution into the mixture during ultrasonic treatment to obtain Ag6A solution; mixing Ag with water6Filtering the solution, standing, and naturally volatilizing at room temperature to obtain Ag6Nanocluster crystals. The invention can be prepared in large quantity, and mainly has the advantages of better anti-interference environment capability in the aspect of selection of preparation process conditions, wide crystallization conditions and simple synthesis conditions. This is a condition that cannot be met by macro-synthesis of other metal clusters.
The crystallization conditions are broad: the invention is macro Ag6The means for obtaining nanocluster crystals can be liquid-liquid diffusion besides natural volatilization (under normal temperature and low temperature conditions), which is difficult to achieve by synthesis of other metal clusters, and often the metal cluster synthesis is obtained by only one crystallization means.
The synthesis conditions are simple: the invention is macro Ag6The reaction reagent for synthesizing the nanoclusters is a single solvent, so that the purity of the nanoclusters is kept to a great extent, the precipitation of crystals is guaranteed, most of nanoclusters are synthesized in a mixed solvent, the quality of the crystals cannot be guaranteed, and the yield is limited; and secondly, the physical ultrasonic cost, operability and safety are beneficial to the macro-synthesis of clusters, and the defects of high cost and high risk of part of clusters by adopting solvothermal reaction are greatly overcome.
Capability of resisting environment: the invention is macro Ag6Nanocluster synthesisThe prepared material has strong adaptability to the humidity, temperature, ultrasonic time, frequency and power of the ambient environment, which most macro cluster synthesis does not have, and has high requirements for the ambient environment and high standards for the synthesis time and the parameter limitation of physical operation.
According to the invention, preferably, the silver salt is Ag2O、CF3COOAg、CF3SO3Ag、AgBF4、AgNO3Or CH3PhSO3Ag。
According to the present invention, it is preferred that said mercapto ligand (SR) is a mercaptopyridine, a pyridine having a substituent of at least-CH or a benzene ring3、-F、-Cl、-Br、-COOH、-OCH3One kind of (1).
According to the present invention, preferably, the polar solvent includes at least one of methanol, ethanol, water and acetonitrile.
According to the present invention, preferably, the base in the basic solution is sodium hydroxide, potassium hydroxide, ammonia, triethylamine, sodium methoxide, tetramethylethylenediamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, tetrapropylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium chloride or tetrabutylammonium chloride.
According to the invention, the molar ratio of silver salt to thiol ligand is preferably (4:1) to (1:4), preferably 4:1, 3:1, 2:1, 1:2, 1:3, 1: 4;
preferably, the molar ratio of the base to the silver salt in the alkaline solution is (10:1) to (1:10), preferably 6:1, 8:1, 1: 3. 1: 6. It is noted that Ag can be obtained by enlarging the ratio of the silver salt to the thiol ligand (SR) by 50 times, 100 times, 1000 times, and more than 1000 times6And (4) crystals.
According to the invention, the ultrasonic frequency of ultrasonic treatment is preferably 30-50 kHz, the ultrasonic power is 50-70W, and the ultrasonic time is preferably 30-60 minutes.
According to the invention, the alkaline solution is preferably added in an amount such that the precipitate is completely dissolved. The resulting solution was a yellow clear solution.
According to the invention, Ag6The raw materials for synthesizing the nanoclusters have hydrophilic groups and rigid benzene rings, and a good design starting point is provided for developing water-soluble luminescent silver clusters. It is noteworthy that the first water-soluble silver cluster with an atomically precise structure synthesized by the present invention. Its Ag can be clearly defined by single crystal X diffraction6The spatial arrangement of (a). The Ag is6Nanoclusters are crystallized in the triclinic space group P-1 with one half of the asymmetric units made of Ag6And 4.5 waters. The silver skeleton is a typical octahedron through the silver affinity effect, wherein Ag6Protected by 6 mercapto ligands, Ag-S bond at
Within the range, the obvious silver affinity function exists, and a good basis is provided for photoluminescence.
According to the invention, the above Ag6The nanoclusters have outstanding optical properties at room temperature, making them particularly useful for fluorescent probes.
The principle of the invention is as follows:
the 'atom precise' Ag prepared by the invention6Through coordination bond and electrostatic action, under the introduction of alkali, the method is favorable for removing hydrogen on sulfydryl and Ag+And S2-The thermodynamically stable Ag with strong luminescence at room temperature is obtained6Nanoclusters.
The invention has the outstanding characteristics and beneficial effects that:
1. "atom accurate" Ag of the present invention6The preparation method of the nanocluster is simple, low in cost, easy in raw material obtaining, mild in synthesis condition, capable of performing macro synthesis most importantly, capable of overcoming the defect that the nanocluster is difficult to synthesize in a macro mode, providing a basis for macro synthesis of the nanocluster, and having the potential of industrial production.
2. Ag in the invention6The silver nanocluster is a water-soluble atom-accurate silver nanocluster with the size smaller than 2nm, belongs to a novel inorganic-organic hybrid material, adopts a sulfydryl ligand to protect a silver core, successfully constructs an atom-accurate water-soluble cluster, and greatly overcomes the defects that an oil-soluble silver cluster is difficult to assemble and dissolveThe limited defect can effectively expand the physical and chemical properties of the silver cluster and provide possibility and basis for the synthesis of other types of water-soluble clusters.
3. The 'atom accurate' Ag prepared by the invention6The nanoclusters are stable in structure, and the defect that most of silver clusters do not emit light at room temperature is effectively overcome.
4. "atom accurate" Ag of the present invention6The nanoclusters solve the problem of the existing synthetic Ag by adopting a proper ligand engineering9The nanoclusters do not emit light and their stability is poor.
5. The invention creatively protects the silver core through the strongly coordinated sulfhydryl ligand, successfully constructs a water-soluble silver cluster with accurate atoms, greatly overcomes the defects of difficult assembly and poor solubility of the oil-soluble silver cluster, can effectively expand the physical and chemical properties of the silver cluster, and provides possibility and basis for the synthesis of other types of water-soluble clusters. At the same time, the prepared water-soluble Ag with accurate atoms6The nanoclusters have the advantages of good stability, outstanding optical properties, suitability for popularization and application in the field of light conversion, more important capability of mass synthesis and industrial production potential.
The material characteristics described in the present invention were tested in the following way:
1. x-ray single crystal diffractometer. The spatial arrangement of the silver clusters can be observed by single crystal X-ray diffraction.
2. Fluorescence spectroscopy. Testing of Ag by fluorescence Spectrophotometer6Fluorescence intensity of nanoclusters.
3. X-ray diffraction (XRD). Ag can be characterized by XRD6Purity of crystals and powder.
4. Electrospray mass spectrometry (ESI-MS). Ag can be characterized by ESI-MS spectrogram6Molecular ion peak of (1).
5. Dynamic Light Scattering (DLS). Ag can be characterized by Dynamic Light Scattering (DLS)6Size in aqueous phase.
Drawings
FIG. 1 shows Ag as a synthesized substance in example 1 of the present invention6A molecular structure model diagram of (1).
FIG. 2 shows Ag as a synthesized substance in example 2 of the present invention6The macro-synthesis picture of (1).
FIG. 3 shows Ag, a substance synthesized in example 1 of the present invention6ESI-MS spectrum of (A).
FIG. 4 shows the Ag substance synthesized in example 1 of the present invention6DLS graph of (a).
FIG. 5 shows Ag, a substance synthesized in example 1 of the present invention6Fluorescence spectrum of (2).
FIG. 6 shows Ag, a substance synthesized in example 1 of the present invention6Under the irradiation of an ultraviolet lamp having a wavelength of 365nm in various solvents.
FIG. 7 shows Ag as a synthesized substance in example 1 of the present invention6Fluorescence spectra under different solvents.
FIG. 8 shows Ag as a synthesized substance in example 2 of the present invention6XRD diffractograms of crystals and powders.
Detailed Description
The present invention will now be described more fully hereinafter with reference to the accompanying drawings, in which some, but not all embodiments of the invention are shown. Based on this, the embodiments described in the present invention, and other embodiments obtained without obvious innovation by other workers in the field, belong to the protection scope of the present invention.
The raw materials used in the examples are conventional raw materials, commercially available products, wherein: silver salts were purchased from Kemiou Chemicals, Inc., Tianjin, sulfydryl ligand (SR) was purchased from Sigma Aldrich, and various basic substances were purchased from Saibo Chemicals, Inc., Jinan.
Example 1
Water-soluble Ag with accurate atoms6The micro-synthesis of the nanoclusters comprises the following steps:
preferably the molar ratio of silver salt to sulfhydryl ligand (SR) is 3:1, the molar ratio of base to silver salt is 6: 1.
Namely accurately weighing Ag2O (3mmol, 696mg) and 2-mercaptonicotinic acid (1mmol, 155mg) were dispersed in 10mL methanol and sonicated in a KQ52DE instrument for 30 minutes (5)0W,40kHz), sodium methoxide (1.5mL) was added to the above mixture during sonication to give yellow transparent Ag6The solution was allowed to evaporate naturally at room temperature for about 1 week, and crystals were precipitated. The yield was 65%.
Example 2
Water-soluble Ag with accurate atoms6Macro-synthesis of nanoclusters, comprising the steps of:
on the basis of example 1, all ratios are controlled to be constant, i.e. the molar ratio of silver salt to thiol ligand (SR) is preferably 3:1, the molar ratio of base to silver salt is 6:1, all starting materials are scaled up by an equal factor of 50.
Namely accurately weighing Ag2O (150mmol, 34.8g) and 2-mercaptonicotinic acid (50mmol, 7.75g) were dispersed in 500mL of methanol and sonicated in a KQ52DE instrument for 30 minutes (50W,40kHz), sodium methoxide (75mL) was added to the above mixture during sonication to give yellow, transparent Ag6The solution naturally volatilizes for 1 week at room temperature, the yield is 64.3%, and the yield of macro synthesis and micro synthesis can be considered to be consistent within the allowable range of experimental error.
Example 3
Water-soluble Ag with accurate atoms6Macro-synthesis of nanoclusters, comprising the steps of:
preferably, the molar ratio of silver salt to sulfhydryl ligand (SR) is 1:4 and the molar ratio of base to silver salt is 6: 1.
Namely accurately weighing Ag2O (50mmol, 11.6g) and 2-mercaptonicotinic acid (200mmol, 31.0g) were dispersed in 500mL of methanol and sonicated in a KQ52DE apparatus for 30 minutes (50W,40kHz), sodium methoxide (75mL) was added to the above mixture during sonication to give yellow, transparent Ag6The solution was allowed to evaporate naturally at room temperature for about 1 week, and crystals were precipitated. The yield was 23.8%,
example 4
Water-soluble Ag with accurate atoms6Macro-synthesis of nanoclusters, comprising the steps of:
preferably, the molar ratio of silver salt to mercaptonicotinic acid is 4:1 and the molar ratio of base to silver salt is 6: 1.
Namely accurately weighing Ag2O (200mmol, 46.4g) and 2-mercaptonicotinic acid (50mmol, 7.75g) were dispersed in
Dispersed in 500mL of water and sonicated in a KQ52DE apparatus for 30 minutes (50W,40kHz), sodium methoxide (75mL) was added to the mixture during sonication to give yellow, transparent Ag6The solution was allowed to evaporate naturally at room temperature for about 1 week, and crystals were precipitated. The yield was 31.5%,
example 5
Water-soluble Ag with accurate atoms6Macro-synthesis of nanoclusters, comprising the steps of:
preferably, the molar ratio of silver salt to mercaptonicotinic acid is 1:1 and the molar ratio of base to silver salt is 10: 1.
Namely accurately weighing Ag2O (50mmol, 11.6g) and 2-mercaptonicotinic acid (50mmol, 7.75g) were dispersed in 500mL of water and sonicated in a KQ52DE apparatus for 30 minutes (50W,40kHz) and sodium methoxide (125mL) was added to the above mixture during sonication to give yellow, transparent Ag6The solution naturally volatilizes at room temperature. The yield was 53.6%.
Example 6
Water-soluble Ag with accurate atoms6Macro-synthesis of nanoclusters, comprising the steps of:
preferably, the molar ratio of silver salt to thiol ligand is 3:1, the molar ratio of base to silver salt is 6: 1.
Namely accurately weighing Ag2O (150mmol, 34.5g) and 2-mercaptonicotinic acid (50mmol, 7.75g) were dispersed in 500mL of methanol and sonicated in a KQ52DE instrument for 30 minutes (50W,40kHz) and a tetramethylammonium hydroxide (52mL) solution was added to the above mixture during sonication to give yellow, transparent Ag6The solution was allowed to evaporate naturally at room temperature for 1 week, giving a yield of 41.8%.
Example 7
Water-soluble Ag with accurate atoms6Macro-synthesis of nanoclusters, comprising the steps of:
on the basis of example 1, all the ratios are controlled to be constant, i.e. the molar ratio of the silver salt to the mercapto ligand (SR) is preferably 3:1, the molar ratio of base to silver salt is 6:1, all starting materials are scaled up by an equal factor of 50.
Namely accurately weighing Ag2O (150mmol, 34.8g) and 6-mercaptonicotinic acid (50mmol, 7.75g) were dispersed in 500mL of methanol and sonicated in a KQ52DE instrument for 30 minutes (50W,40kHz), sodium methoxide (75mL) was added to the above mixture during sonication to give yellow, transparent Ag6The solution was allowed to evaporate naturally at room temperature for 1 week, giving a yield of 60.7%.
Example 8
Water-soluble Ag with accurate atoms6Macro-synthesis of nanoclusters, comprising the steps of:
on the basis of example 1, all ratios are controlled to be constant, i.e. the molar ratio of silver salt to thiol ligand (SR) is preferably 3:1, the molar ratio of base to silver salt is 6:1, all starting materials are scaled up by an equal factor of 50.
Namely, CF is accurately weighed3COOAg (150mmol, 33.15g) and 2-mercaptonicotinic acid (50mmol, 7.75g) were dispersed in 500mL of methanol and sonicated in a KQ52DE instrument for 30 minutes (50W,40kHz), sodium methoxide (75mL) was added to the above mixture during sonication to give yellow, transparent Ag6The solution was allowed to evaporate naturally at room temperature for 1 week, giving a yield of 59.7%.
Example 9
Water-soluble 'atom accurate' Ag6Macro-synthesis of nanoclusters, comprising the steps of:
on the basis of example 1, all ratios are controlled to be constant, i.e. the molar ratio of silver salt to thiol ligand (SR) is preferably 3:1, the molar ratio of base to silver salt is 6:1, all starting materials are scaled up by an equal factor of 1000.
Namely accurately weighing Ag2O (3000mmol, 696g) and 2-mercaptonicotinic acid (1000mmol, 155g) were dispersed in 10000mL of methanol and sonicated in a KQ52DE instrument for 30 minutes (50W,40kHz), sodium methoxide (1500mL) was added to the above mixture during sonication to give yellow transparent Ag6The solution naturally volatilizes for 1 week at room temperature, the yield is 62.7 percent, and the macro synthesis and the micro synthesis of the solution can be considered within the allowable range of experimental errorThe yield was consistent. It can be seen that the magnification of the raw material for Ag in the present invention is increased6The yield is not greatly influenced.
Comparative example 1
Water-soluble Ag with accurate atoms6The micro-synthesis of the nanoclusters comprises the following steps:
preferably, the molar ratio of silver salt to sulfhydryl ligand (SR) is 3:1, the molar ratio of base to silver salt is 6: 1.
Namely accurately weighing Ag2O (3mmol, 696mg) and 2-mercaptonicotinic acid (1mmol, 155mg) were dispersed in 10mL of methanol and shaken, and sodium methoxide (1.5mL) was added to the above mixture to give cloudy yellow Ag6The solution was allowed to evaporate naturally at room temperature for about 1 week, and crystals were precipitated. The yield was 7.5%.
On the basis of example 1, all ratios are controlled to be constant, i.e. the molar ratio of silver salt to thiol ligand (SR) is preferably 3:1, the molar ratio of base to silver salt is 6:1, all starting materials are scaled up by an equal factor of 50.
Namely accurately weighing Ag2O (150mmol, 34.8g) and 2-mercaptonicotinic acid (50mmol, 7.75g) were dispersed in 500mL of methanol and shaken, and sodium methoxide (75mL) was added to the above mixture to give cloudy yellow Ag6The solution was allowed to evaporate naturally at room temperature for 1 week, giving a 1.3% yield.
It can be seen that the sonication in the present invention is for Ag6Yield improvement has a significant impact.
Experimental example 1, structural characterization
Ag synthesized as disclosed in examples 1 to 26The nanocluster crystal structure is characterized, and the results are shown in FIGS. 1-4. Wherein, FIG. 1 shows Ag, a substance synthesized in example 1 of the present invention6A molecular structure model diagram of (1). FIG. 2 shows Ag as a synthesized substance in example 2 of the present invention6The macro-synthesis picture of (1).
As can be seen from FIG. 1, Ag6The X-ray single crystal diffraction data of (2) show that the hexagonal cluster is crystallized in the triclinic space group P-1 with half of the asymmetric units of Ag6And 4.5 waters. Triclinic space group P-1. The built silver skeleton is typical through the silver affinity effectOctahedra of wherein Ag6Is composed of 6 mna2-Ligand protection, Ag-S bond at
Within the range, the obvious silver affinity function exists, and a good basis is provided for photoluminescence.
From FIG. 2, it can be seen that Ag by the present invention6The nanoclusters are yellow bulk crystals.
FIG. 3 shows Ag6High resolution electrospray mass spectrometry (HR-ESI-MS) of aqueous solutions, Ag6HR-ESI-MS of (D) shows two main signals. The main signals are concentrated in m/z 1260.3918(1a) and 1282.3745(1b) in the range of 1000-6(mna)4H]-(calculation result: m/z-1260.3904) and [ Ag6(mna)4Na]-(calculation result: m/z-1282.3723), indicating that Ag is present6Is stable in aqueous solution.
FIG. 4 shows Ag6Dynamic Light Scattering (DLS) of aqueous solution, the average size of Ag6 determined by Dynamic Light Scattering (DLS) is about 1.5nm, which is comparable to Ag determined by X-ray Single Crystal diffraction6Are consistent in size.
Experimental example 2 optical Properties
Prepared Ag as described in example 16The nanoclusters were subjected to fluorescence spectroscopy measurements of solid and solution, respectively, as shown in fig. 5. As can be seen from FIG. 5, Ag6The solid has good optical properties, has a wide generation peak, an optimal emission of 550nm, a half-peak width of about 120nm, and a large Stokes shift (>100 nm). This makes Ag6The luminescent property with good quality has obvious application in the aspect of light conversion materials.
FIG. 6 and FIG. 7 show Ag6Luminescence behavior of crystals in different organic solvents. As can be seen from FIGS. 6 and 7, Ag6In different solvents, different emission energies were exhibited, indicating that Ag6Has obvious solvation effect, so that the fluorescence adjustable characteristic is shown under different solvent conditions, and different emission energies are realizedAnd (4) customizing the material. This is not common in most silver clusters, and the cause of these phenomena is mainly ligand-metal charge transfer (LMCT), which is mixed with Cluster Center (CC) switching.
Experimental example 3 purity test
Prepared Ag as described in example 16The nanoclusters were subjected to a purity test as shown in fig. 8. As can be seen from FIG. 8, it was found that the crystals were highly coincident with the diffraction peak of the powder left for 1 month, indicating that Ag6The powder has high purity and good stability.
Although the embodiments of the present invention have been described with reference to the accompanying drawings, the scope of the present invention is not limited thereto, and various modifications and changes that can be made by those skilled in the art without inventive efforts based on the technical solutions of the present invention are within the scope of the present invention.
Claims (10)
1. Water-soluble 'atom accurate' Ag6Nanoclusters characterized in that said Ag is6The molecular formula of the nanocluster is X6[Ag6(SR)6]，
Wherein SR is mercaptopyridine, pyridine with substituent groups or benzene ring, and X is a cationic group; the substituent is at least-CH3、-F、-Cl、-Br、-COOH、-OCH3One kind of (1).
2. The water-soluble "atomically accurate" Ag of claim 16Nanoclusters characterized in that X is (CH)3)4N+，(CH3CH2CH2CH2)4N+，(CH3CH2CH2)4N+，(CH3CH2)4N+，Na+，K+Or NH4 +。
3. The water-soluble "atomically accurate" Ag of claim 16Nanoclusters, characterized in that said Ag6Nanoclusters are crystallized in the triclinic space group P-1 with one half of the asymmetric units made of Ag6And 4.5 water;
preferably, the Ag is6The silver skeleton of the nanocluster is of an octahedral structure and is protected by 6 sulfydryl ligands, and Ag-S bonds are arranged on
Within the range.
4. The water-soluble "atomically accurate" Ag of claim 16The macro synthesis method of the nanoclusters comprises the following steps:
dispersing silver salt and sulfhydryl ligand in polar solvent, ultrasonic treating, adding alkaline solution into the mixture during ultrasonic treatment to obtain Ag6A solution; mixing Ag with water6Filtering the solution, standing, and naturally volatilizing at room temperature to obtain Ag6Nanocluster crystals.
5. The water-soluble "atomically accurate" Ag of claim 46The macro synthesis method of the nanocluster is characterized in that the silver salt is Ag2O、CF3COOAg、CF3SO3Ag、AgBF4、AgNO3Or CH3PhSO3Ag。
6. The water-soluble "atomically accurate" Ag of claim 46The macro-synthesis method of the nanocluster is characterized in that the sulfhydryl ligand (SR) is sulfhydryl pyridine, pyridine with substituent groups or benzene ring, and the substituent groups are at least-CH3、-F、-Cl、-Br、-COOH、-OCH3To (3) is provided.
7. The water-soluble "atomically accurate" Ag of claim 46The macro-synthesis method of the nanoclusters is characterized in that the polar solvent comprises at least one of methanol, ethanol, water and acetonitrile;
preferably, the alkali in the alkaline solution is sodium hydroxide, potassium hydroxide, ammonia, triethylamine, sodium methoxide, tetramethylethylenediamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, tetrapropylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium chloride or tetrabutylammonium chloride.
8. The water-soluble "atomically accurate" Ag of claim 46The macro-synthesis method of the nanoclusters is characterized in that the molar ratio of the silver salt to the mercapto ligand is (4:1) - (1: 4);
preferably, the molar ratio of the alkali to the silver salt in the alkaline solution is (10:1) to (1: 10).
9. The water-soluble "atomically accurate" Ag of claim 46The macro-synthesis method of the nanoclusters is characterized in that ultrasonic frequency of ultrasonic treatment is 30-50 kHz, ultrasonic power is 50-70W, and ultrasonic time is 30-60 minutes.
10. Ag according to claim 16Application of nanoclusters in fluorescent probes.
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| CN107254307A (en) * | 2017-06-13 | 2017-10-17 | 山东大学 | A kind of silver nanoclusters fluorescence vesica and preparation method thereof and detection Fe3+Application |
| CN110330512A (en) * | 2019-07-30 | 2019-10-15 | 山东大学 | A kind of ag nano-cluster fluorescence nano stick and preparation method thereof and the application in white light LEDs |
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| CN107254307A (en) * | 2017-06-13 | 2017-10-17 | 山东大学 | A kind of silver nanoclusters fluorescence vesica and preparation method thereof and detection Fe3+Application |
| CN110330512A (en) * | 2019-07-30 | 2019-10-15 | 山东大学 | A kind of ag nano-cluster fluorescence nano stick and preparation method thereof and the application in white light LEDs |
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