CN115582552B - Preparation method for improving gold cluster based on solvent-assisted two-phase synthesis strategy - Google Patents
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- 239000010931 gold Substances 0.000 title claims abstract description 108
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 70
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 69
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- 238000002360 preparation method Methods 0.000 title abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 123
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
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- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000006722 reduction reaction Methods 0.000 claims abstract description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
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- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 231100000053 low toxicity Toxicity 0.000 abstract description 3
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- XYYVDQWGDNRQDA-UHFFFAOYSA-K trichlorogold;trihydrate;hydrochloride Chemical compound O.O.O.Cl.Cl[Au](Cl)Cl XYYVDQWGDNRQDA-UHFFFAOYSA-K 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
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- CMWKITSNTDAEDT-UHFFFAOYSA-N 2-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC=C1C=O CMWKITSNTDAEDT-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
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- JYJVVHFRSFVEJM-UHFFFAOYSA-N iodosobenzene Chemical compound O=IC1=CC=CC=C1 JYJVVHFRSFVEJM-UHFFFAOYSA-N 0.000 description 1
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- XUZLXCQFXTZASF-UHFFFAOYSA-N nitro(phenyl)methanol Chemical compound [O-][N+](=O)C(O)C1=CC=CC=C1 XUZLXCQFXTZASF-UHFFFAOYSA-N 0.000 description 1
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- 150000003462 sulfoxides Chemical class 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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Abstract
The invention discloses a preparation method of an improved gold cluster based on a solvent-assisted two-phase synthesis strategy, which comprises the following steps: firstly, adding an auxiliary solvent and a toluene solution into chloroauric acid solution, then adding a sodium thiophenol solution, reacting at room temperature, and adding a sodium hydroxide solution after full reaction; adding sodium borohydride solution into the reaction system, and carrying out reduction reaction at room temperature to obtain Au@SPh gold nanocluster solution; and (3) purifying and drying the Au@SPh gold nanocluster solution to obtain the solid powdery Au@SPh gold nanocluster. The invention successfully uses the sodium thiophenol with low toxicity to realize the synthesis of Au@SPh gold clusters, avoids using highly toxic thiophenol, and reduces the production safety risk and the synthesis threshold.
Description
Technical Field
The invention belongs to the field of improved synthetic nano materials, and particularly relates to a preparation method of an improved gold cluster based on a solvent-assisted two-phase synthesis strategy.
Background
With the continuous development of economy, the industrial process of the chemical industry, which is one of the most important props of national economy, is gradually accelerated. The chemical makes a great contribution to the world economic development and the improvement of the human living standard, and at the same time, the pollution can not be avoided in the industrial production process, and the living environment of human beings is damaged. Against this background, the concept of green chemistry was proposed with the aim of reducing or stopping the use and production of raw materials, catalysts, solvents and reagents, products, by-products, etc. which are harmful to human health, community safety, ecological environment, using chemical techniques and methods. Green chemistry represents a common trend in the traditional chemistry industry and material chemistry.
Jin Zuowei is a well-known noble metal and has the characteristics of good chemical inertness, excellent biocompatibility and the like. Gold clusters are composed of several to hundreds of gold atoms, typically below three nanometers in size. The structure of the core consists of two parts, namely an inner core consisting of gold atoms, and the second is a shell formed by outer gold atoms and protective ligands. As the cluster size approaches the fermi wavelength of the electrons, its quasi-continuous energy level becomes discrete or the energy gap becomes wider, and its optical, thermal, magnetic, electrical, catalytic and superconductive properties all exhibit physicochemical properties that differ significantly from those of large-sized particles. Meanwhile, the gold cluster is in an intermediate state between an independent molecule and a large nanoparticle, has an adjustable geometry and an electronic structure, changes the composition of a core and various surface ligand modifications, and can endow the gold cluster with different properties. For example, gold clusters with proteins or polypeptides as protecting ligands have excellent performance in regulating protein conformational diseases and treating neuroinflammation, and gold clusters with triphenylphosphine and other large rigid benzene ring structures have excellent fluorescence performance.
The Aux (SPh) y gold nanocluster has been reported to be applied to catalysis in the prior art, for example, jing et al (Rongchao Jin et al, journal of The American Chemical Society, 2014) found a thermally stable Au99 (SPh) 42 cluster capable of selectively hydrogenating nitrobenzaldehyde to nitrobenzyl alcohol and having high catalytic activity on a series of nitrobenzaldehyde derivatives. Li et al (Gao Li et al, nanoscales, 2015) showed high catalytic activity by supporting Au102 (SPh) 44 on titania and selectively oxidizing sulfides to sulfoxides by iodosyl benzene oxidizer.
The existing technology for synthesizing Aux (SPh) y gold nanoclusters generally adopts a Brous-Schiffrin synthesis method, and uses a ligand containing sulfhydryl groups for synthesis, and the main thinking is as follows: firstly, transferring trivalent gold ions in an aqueous phase into an organic phase through a quaternary ammonium salt and other transfer catalysts, so that the gold ions are combined with thiophenol in the organic phase to form monovalent gold complexes bridged with phenyl mercaptan; finally, the gold clusters are formed by nucleation growth through reduction of sodium borohydride in an organic phase. However, the synthesis method adopts thiophenol as a synthesis raw material, the thiophenol is used as a highly toxic substance, the raw material is strictly controlled, the industrialized production of Aux (SPh) y gold nanoclusters is difficult to realize, health risks are inevitably caused in the production synthesis, and the production safety is required to be strictly ensured. Meanwhile, synthesis by this method is often required to be carried out at high temperature under an inert gas atmosphere. Therefore, finding a method for synthesizing Aux (SPh) y gold clusters with high efficiency and low energy consumption, which can replace thiophenol, is a technical problem to be solved.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method for improving a gold cluster based on a solvent-assisted two-phase synthesis strategy, which adopts the solvent-assisted two-phase synthesis strategy, and enables water-soluble substances and water-insoluble substances to migrate between two phases in the reaction process by setting up a water-phase-organic phase transmission channel, so that the problem that sodium thiophenol is water-soluble substances but becomes water-insoluble after being coordinated with gold ions is solved, the synthesis of Au@SPh gold cluster is successfully realized by using sodium thiophenol which is a low-toxicity raw material, the use of highly toxic thiophenol is avoided, and the production safety risk and the synthesis threshold are reduced. Meanwhile, the method solves the problems of high temperature, inert gas atmosphere and the like of the traditional method, has milder reaction conditions, low production energy consumption and simple synthesis flow.
In order to achieve the above purpose, the present invention is realized by the following technical scheme:
the invention provides a preparation method of an improved gold cluster based on a solvent-assisted two-phase synthesis strategy, which comprises the following steps:
firstly, adding an auxiliary solvent and a toluene solution into chloroauric acid solution, then adding a sodium thiophenol solution, reacting at room temperature, and adding a sodium hydroxide solution after full reaction;
adding sodium borohydride solution into the reaction system, and carrying out reduction reaction at room temperature to obtain Au@SPh gold nanocluster solution;
and (3) purifying and drying the Au@SPh gold nanocluster solution to obtain the solid powdery Au@SPh gold nanocluster.
The preparation method of the chloroauric acid solution comprises the following steps: and weighing chloroauric acid trihydrate, and dissolving in ultrapure water and acetonitrile to prepare chloroauric acid solution. The preparation method of the sodium thiophenol solution comprises the following steps: weighing sodium thiophenol powder, and dissolving in ultrapure water to obtain sodium thiophenol solution. The preparation method of the sodium hydroxide solution comprises the following steps: and weighing sodium hydroxide, and dissolving in water to obtain sodium hydroxide aqueous solution.
Preferably, the molar ratio of chloroauric acid, sodium thiophenol and sodium borohydride is 1: (3-6): (1.5-3). Further, the molar ratio of chloroauric acid, sodium thiophenol and sodium borohydride is 1:5:2.
preferably, the auxiliary solvent is acetonitrile or ethanol.
Preferably, the volume ratio of the auxiliary solvent to toluene is (1:1) - (5:7).
Preferably, the reaction time after the addition of the sodium thiophenol solution is 30-50min. Further, the reaction time after adding the sodium thiophenol solution was 40min.
Preferably, the reaction time after the addition of the sodium borohydride solution is 2.5-3.5 hours. Further, the reaction time after the addition of the sodium borohydride solution was 3 hours.
Preferably, the sodium hydroxide solution concentration is 0.5-0.8M. Further, the concentration of sodium hydroxide solution was 0.5M. And a proper amount of sodium hydroxide solution is added, so that the reaction rate can be regulated.
Preferably, the specific steps of purifying and drying the Au@SPh gold nanocluster solution are as follows: and (3) carrying out high-speed centrifugal phase separation on the Au@sph gold nanocluster solution, taking an upper layer solution, filtering, then placing the upper layer solution in a water bath kettle with a set temperature for standing, evaporating the solution by spin after standing, washing and centrifuging by adopting methanol, discarding supernatant, taking precipitate to dissolve by using dichloromethane, centrifuging again, taking supernatant to evaporate by spin, repeating for three times, and finally drying the product by spin evaporation in vacuum to obtain a solid powder sample.
Further, the temperature of the water bath kettle is 35-45 ℃, and the standing time is 1.5-2.5h. Further preferably, the water bath temperature is 40 ℃ and the standing time is 2 hours.
Further, the filtration was performed using a 0.22 μm nylon filter.
Compared with the prior art, the invention has the following advantages:
the main idea of the invention is as follows: firstly, mixing chloroauric acid with a proper amount of acetonitrile (or ethanol), and then adding a certain amount of toluene solution to serve as a supporting phase of monovalent gold complex; then adding sodium thiophenol aqueous solution into the system, using acetonitrile or ethanol as mass transfer channel to transfer water insoluble monovalent gold complex into receiving phase in time, adding proper quantity of sodium hydroxide solution to make reaction at a certain speed, finally reducing monovalent gold complex on water phase-organic phase interface by means of sodium borohydride to make nucleation and growth, and dissolving formed gold cluster in organic phase.
The invention selects the auxiliary solvent as the phase transfer agent to prepare the gold cluster, and utilizes the characteristics that sodium thiophenol has water solubility and is easy to ionize, and the binding force of gold ions and sulfur ions is larger than that of sodium ions and sulfur ions in aqueous solution, so that monovalent gold complex bridged by phenyl mercaptan is formed in aqueous phase. Then, acetonitrile and other high-polarity organic solvents are used as phase transfer auxiliary solvents, organic phases for product polar phase affinity are selected as product receiving phases, a water phase-organic phase two-phase mass transfer interface in the reaction is built, so that migration of water-insoluble monovalent gold complex from the water phase to the organic phases is realized, finally sodium borohydride is introduced to reduce nucleation growth on the water phase-organic phase interface, and all formed gold clusters are transferred into the oil phase due to small polarity of surface ligands. Compared with the traditional preparation method of the Brust-Schiffrin gold cluster, the method uses the thiol-containing ligand thiophenol containing the virulent, and the method adopts the sodium thiophenol with low toxicity as the raw material for synthesis. Meanwhile, the reduction reaction of the gold clusters is generated on the water phase-organic phase interface, the reaction can be driven to occur only by less energy, the reaction can occur in a room temperature environment, and the conditions are milder. In addition, the water-oil amphipathy difference exists among all substances in the system, so that products can be well separated from other substances, and the purification cost of the products is saved.
Drawings
FIG. 1 is a schematic diagram of the synthesis flow of Au@sph gold nanoclusters of the present invention.
FIG. 2 is an ultraviolet absorption spectrum of Au@sph gold nanoclusters of example 1 of the present invention.
FIG. 3 is an infrared spectrum of Au@sph gold nanoclusters of example 1 of the present invention.
FIG. 4 is a transmission electron microscope image of Au@sph gold nanoclusters of example 1 of the present invention.
FIG. 5 is a graph showing the dynamic light scattering particle size distribution of Au@sph gold nanoclusters of example 1 of the present invention.
FIG. 6 is a STEM image of an Au@sph gold nanocluster of example 1 of the present invention.
FIG. 7 is an EDS mapping image of the gold element of FIG. 6 of the Au@sph gold nanoclusters of example 1 of the present invention.
FIG. 8 is an EDS mapping image of the sulfur element of FIG. 6 of the Au@sph gold nanoclusters of example 1 of the present invention.
FIG. 9 is an XPS full spectrum image of Au@sph gold nanoclusters of example 1 of the present invention.
FIG. 10 is XPS Au 4f fine spectra of Au@sphgold nanoclusters of example 1 of the present invention.
Detailed Description
In order that those skilled in the art will better understand the technical solution of the present invention, preferred embodiments of the present invention will be described below with reference to specific examples, but the present invention should not be construed as being limited thereto, but only by way of example.
The test methods or test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are obtained from conventional commercial sources or prepared in conventional manner.
Example 1
The embodiment provides a preparation method of an improved gold cluster based on a solvent-assisted two-phase synthesis strategy, which comprises the following steps:
step one, preparing gold clusters:
41.2mg of chloroauric acid trihydrate was weighed and dissolved in 0.5mL of ultrapure water and 0.5mL of acetonitrile to prepare an aqueous chloroauric acid solution, which was charged into a 50mL round-bottomed flask. To this was added 11.5mL of acetonitrile and 12mL of toluene solution in sequence. 66.1mg of sodium thiophenol powder was weighed and dissolved in 1.5mL of ultrapure water, and added to the system, the rotation speed was increased, and the reaction was carried out at room temperature for 40 minutes. 0.2g of sodium hydroxide was weighed and dissolved in 5mL of water to prepare 1M aqueous sodium hydroxide solution, 1mL of each aqueous sodium hydroxide solution was simultaneously added to 1mL of each aqueous sodium hydroxide solution, and 4mL of each aqueous sodium hydroxide solution was prepared by adding 1mL of each aqueous sodium hydroxide solution to prepare 0.5M aqueous sodium hydroxide solution and 0.2M aqueous sodium hydroxide solution. To the reaction system was added 1mL of 0.5M sodium hydroxide solution, and the mixture was stirred for 5 minutes. Then 7.6mg of sodium borohydride solution was weighed into 0.6ml of 0.2M sodium hydroxide solution and added to the round bottom flask and reacted for 3 hours at room temperature and 1000 rpm.
Step two, purifying gold clusters:
purification of gold nanoclusters: and (3) centrifuging the solution obtained after the reaction in the step (I) in a centrifuge tube at a rotating speed of 8000rpm for 5min, and taking the supernatant after the centrifugation. The obtained solution was filtered with a 0.22 μm nylon filter membrane and placed in a 40℃water bath for 2h. Subsequently, the solution was spin-evaporated to dryness, washed with methanol, centrifuged at 10000rpm for 8min, the supernatant was discarded, the precipitate was taken out and dissolved with dichloromethane, centrifuged again, the supernatant was spin-evaporated, the procedure was repeated three times, and finally the spin-evaporated product was vacuum-dried to obtain a solid powder sample.
Example 2
The embodiment provides a preparation method of an improved gold cluster based on a solvent-assisted two-phase synthesis strategy, which comprises the following steps:
step one, preparing gold clusters:
41.2mg of chloroauric acid trihydrate was weighed and dissolved in 0.5mL of ultrapure water and 0.5mL of acetonitrile to prepare an aqueous chloroauric acid solution, which was charged into a 50mL round-bottomed flask. To this was added 11.5mL of acetonitrile and 12mL of toluene solution in sequence. 39.7mg of sodium thiophenol powder was weighed and dissolved in 1.5mL of ultrapure water, and added to the system, the rotation speed was increased, and the reaction was carried out at room temperature for 30 minutes. 0.2g of sodium hydroxide was weighed and dissolved in 5mL of water to prepare 1M aqueous sodium hydroxide solution, 1mL of each aqueous sodium hydroxide solution was simultaneously added to 1mL of each aqueous sodium hydroxide solution, and 4mL of each aqueous sodium hydroxide solution was prepared by adding 1mL of each aqueous sodium hydroxide solution to prepare 0.5M aqueous sodium hydroxide solution and 0.2M aqueous sodium hydroxide solution. To the reaction system was added 0.6mL of a 0.5M sodium hydroxide solution, and the mixture was stirred for 5 minutes. Subsequently, 5.7mg of sodium borohydride solution was weighed into 0.42mL of 0.2M sodium hydroxide solution, and added to a round bottom flask, and reacted at room temperature for 2.5 hours at 1000 rpm.
Step two, purifying gold clusters:
purification of gold nanoclusters: and (3) centrifuging the solution obtained after the reaction in the step (I) in a centrifuge tube at a rotating speed of 8000rpm for 5min, and taking the supernatant after the centrifugation. The obtained solution was filtered with a 0.22 μm nylon filter membrane and placed in a 35℃water bath for 2.5h. Subsequently, the solution was spin-evaporated to dryness, washed with methanol, centrifuged at 10000rpm for 8min, the supernatant was discarded, the precipitate was taken out and dissolved with dichloromethane, centrifuged again, the supernatant was spin-evaporated, the procedure was repeated three times, and finally the spin-evaporated product was vacuum-dried to obtain a solid powder sample.
Example 3
The embodiment provides a preparation method of an improved gold cluster based on a solvent-assisted two-phase synthesis strategy, which comprises the following steps:
step one, preparing gold clusters:
41.2mg of chloroauric acid trihydrate was weighed and dissolved in 0.5mL of ultrapure water and 0.5mL of acetonitrile to prepare an aqueous chloroauric acid solution, which was charged into a 50mL round-bottomed flask. To this was added 11.5mL of acetonitrile and 12mL of toluene solution in sequence. 79.3mg of sodium thiophenol powder was weighed and dissolved in 2.0mL of ultrapure water, and added to the system, the rotation speed was increased, and the reaction was carried out at room temperature for 50 minutes. 0.2g of sodium hydroxide was weighed and dissolved in 5mL of water to prepare 1M aqueous sodium hydroxide solution, 1mL of each aqueous sodium hydroxide solution was simultaneously added to 1mL of each aqueous sodium hydroxide solution, and 4mL of each aqueous sodium hydroxide solution was prepared by adding 1mL of each aqueous sodium hydroxide solution to prepare 0.5M aqueous sodium hydroxide solution and 0.2M aqueous sodium hydroxide solution. To the reaction system was added 1.2mL of 0.5M sodium hydroxide solution, and the mixture was stirred for 5 minutes. Subsequently, 11.4mg of sodium borohydride solution was weighed into 0.9mL of 0.2M sodium hydroxide solution, and added to the round bottom flask, and reacted at room temperature for 2.5 hours at 1000 rpm.
Step two, purifying gold clusters:
purification of gold nanoclusters: and (3) centrifuging the solution obtained after the reaction in the step (I) in a centrifuge tube at a rotating speed of 8000rpm for 5min, and taking the supernatant after the centrifugation. The obtained solution was filtered with a 0.22 μm nylon filter membrane and placed in a 45℃water bath for 1.5h. Subsequently, the solution was spin-evaporated to dryness, washed with methanol, centrifuged at 10000rpm for 8min, the supernatant was discarded, the precipitate was taken out and dissolved with dichloromethane, centrifuged again, the supernatant was spin-evaporated, the procedure was repeated three times, and finally the spin-evaporated product was vacuum-dried to obtain a solid powder sample.
The invention takes the product of the example 1 as an example to describe the characterization result of the exchanged product in detail, and the method specifically comprises the following steps:
FIG. 2 is an ultraviolet absorption spectrum of Au@sph gold nanoclusters of example 1 of the present invention, which reflects the Au@sph ultraviolet-visible light absorption.
FIG. 3 is an infrared spectrum of Au@sphgold nanoclusters of example 1 of the present invention, 1580.5, 1466.4, 1443.2cm in the Au@sph infrared spectrum -1 The bending shock absorption peak for benzene ring c=h demonstrates successful ligand binding to gold.
FIG. 4 is a transmission electron microscope image of Au@SPh gold nanoclusters of example 1 of the present invention, from which it can be seen that the size of the Au@SPh gold nanoclusters is about 2 to 3 nm.
FIG. 5 is a graph showing the distribution of the dynamic light scattering particle diameters of Au@sph gold nanoclusters of example 1 of the present invention, and as a result, it can be seen that the number and size distribution of Au@sph is about 2 to 3 nm.
Fig. 6 is a STEM image of the au@sph gold nanocluster of example 1 of the present invention, and the morphology condition of au@sph is seen.
FIG. 7 is an EDS mapping image of the gold element of FIG. 6 of the Au@sph gold nanocluster of example 1 of the present invention, showing the distribution of the gold element of FIG. 6.
FIG. 8 is an EDS mapping image of the sulfur element of FIG. 6 of the Au@sph gold nanocluster of example 1 of the present invention, showing the distribution of the sulfur element of FIG. 6, and demonstrating the presence of Au-S bonding in the material.
FIG. 9 is an XPS full spectrum image of the Au@sph gold nanocluster of example 1 of the present invention, which proves that the material contains Au, S, C, O and other elements.
FIG. 10 is XPS Au 4f fine spectrum of Au@SPh gold nanoclusters of example 1 of the present invention showing Au 4f orbitals.
In order to more conveniently illustrate that the Au@SPh gold nanoclusters can be successfully prepared by adopting the technical scheme of the invention, the preferred embodiment 1 of the invention is illustrated as an example, and both embodiments 2 and 3 are successfully synthesized.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that the above-mentioned preferred embodiment should not be construed as limiting the invention, and the scope of the invention should be defined by the appended claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.
Claims (4)
1. A method for preparing an improved gold cluster based on a solvent-assisted two-phase synthesis strategy, comprising:
firstly, adding an auxiliary solvent and a toluene solution into chloroauric acid solution, then adding a sodium thiophenol solution, reacting at room temperature, and adding a sodium hydroxide solution after full reaction;
adding sodium borohydride solution into the reaction system, and carrying out reduction reaction at room temperature to obtain Au@SPh gold nanocluster solution;
purifying and drying the Au@SPh gold nanocluster solution to obtain solid powder Au@SPh gold nanoclusters;
the auxiliary solvent is acetonitrile or ethanol, and the molar ratio of chloroauric acid, sodium thiophenol and sodium borohydride is 1: (3-6): (1.5-3), the volume ratio of the auxiliary solvent to toluene is (1:1) - (5:7), the reaction time is 30-50min after adding the sodium thiophenol solution, the reaction time is 2.5-3.5h after adding the sodium borohydride solution, and the concentration of the sodium hydroxide solution is 0.5-0.8M.
2. The method for preparing the improved gold cluster based on the solvent-assisted two-phase synthesis strategy according to claim 1, wherein the molar ratio of chloroauric acid, sodium thiophenol and sodium borohydride is 1:5:2.
3. the method for preparing the improved gold cluster based on the solvent-assisted two-phase synthesis strategy according to claim 1, wherein the specific steps of purifying and drying the au@sph gold nanocluster solution are as follows: and (3) carrying out high-speed centrifugal phase separation on the Au@sph gold nanocluster solution, taking an upper layer solution, filtering, then placing the upper layer solution in a water bath kettle with a set temperature for standing, evaporating the solution by spin after standing, washing and centrifuging by adopting methanol, discarding supernatant, taking precipitate to dissolve by using dichloromethane, centrifuging again, taking supernatant to evaporate by spin, repeating for three times, and finally drying the product by spin evaporation in vacuum to obtain a solid powder sample.
4. The method for preparing the improved gold cluster based on the solvent-assisted two-phase synthesis strategy according to claim 3, wherein the temperature of the water bath kettle is 35-45 ℃, and the standing time is 1.5-2.5h.
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