CN109420774A - A kind of preparation of the controllable AgAu alloy nanocluster of atom number, size - Google Patents

A kind of preparation of the controllable AgAu alloy nanocluster of atom number, size Download PDF

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Publication number
CN109420774A
CN109420774A CN201710750161.6A CN201710750161A CN109420774A CN 109420774 A CN109420774 A CN 109420774A CN 201710750161 A CN201710750161 A CN 201710750161A CN 109420774 A CN109420774 A CN 109420774A
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cluster
nano
atom number
agau
controllable
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黄家辉
刘超
任秀清
林欣章
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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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
    • 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
    • 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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  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
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Abstract

A kind of synthesis of atom number, the controllable AgAu alloy nanocluster of size, the method can be prepared on a large scale various sizes of AgAu alloy nanocluster.Be specifically related to: silver nitrate is first dissolved in methylene chloride with mercaptan ligand and stirring by the first step, half an hour to be reacted, and sodium borohydride reduction is added and obtains the Ag nanoparticle of zeroth order, with the lengthening in reaction time, finally obtains the Ag nano-cluster of accurate atom number.Second step, by AuCl3It is dissolved in methanol with mercaptan ligand and stirs a period of time, the Ag nano-cluster of first step preparation is then added, reaction a period of time, the AuAg alloy nanocluster of accurate atom number can be obtained.Nanocluster size and accurate atom number are controlled by changing the ratio of two kinds of source metals.The method that the invention is related to has feasibility, and operability is simple, and can obtain various sizes of AgAu nano-cluster by the different mol ratio of regulation gold, silver.

Description

A kind of preparation of the controllable AgAu alloy nanocluster of atom number, size
Technical field:
The invention belongs to the preparation of AgAu alloy nanocluster, present invention illustrates two-step methods to prepare atom number, size can The AgAu nano-cluster of control.
Background technique:
In the research boom of nano material, since noble metal nanometer material has the characteristics such as unique light, electricity, catalysis, So having broad application prospects in fields such as new energy, photoelectric information storage, biologic medicals, physics, chemistry, material are caused The extensive concern of the various fields researchers such as material.Metal nanometre cluster refers under certain ligand protection, by several to several hundred Metastable nanoparticle composed by the metallic atoms such as gold, silver and platinum.Its partial size is generally less than 2nm (comprising sub-nanometer grain Son), particle of the number containing metallic atom between 20-200.And nano-cluster has accurate atom number and ligand number Mesh, so different from the Wuli-Shili-Renli system approach of metallic atom and metal nanoparticle.
Currently, the report about gold nanoclusters is more and has obtained their complete structure, such as Au25、Au38、Au67、 Au102And Au144Deng.The fine silver nano-cluster for having complete structure of mercaptan protection is also gradually concerned, such as Ag44、Ag25、Ag29 And Ag64Deng, since the stability of silver nanoclusters is bad, silver nanoparticle protected about mercaptan, with accurate atom number The report of cluster and silver-colored billon nano-cluster is less.Most in the past few years, the properties such as the synthesis, catalysis of alloy nanocluster and optics also by The concern of researchers is arrived.2013, Zheng Nanfeng et al. successfully synthesized a series of Ag protected by mercaptan for the first time44With Au12Ag32Nano-cluster, and obtained their crystal structure (Zheng Nanfeng.Nature communication.2013.4:1-8).2016, Osman M.Bakr et al. used Ag25(SPhMe2)18It is successfully closed as template At the Ag of high-purity24Au(SPhMe2)18And obtain its crystal structure.(Osman M.Bakr.Angew.Chem.Int.Ed.2016,55:922-926)
Usually preparing alloy nanocluster is to mix two kinds of source metals, and ligand reaction is added and generates monovalence compound, later Use NaBH4Reduction, but this method hardly results in a kind of pure alloy nanocluster.This patent in response to this problem, is explored to one Kind simple and easy synthetic method prepares electrum nano-cluster, uses a kind of nano-cluster as templated synthesis alloy nanocluster, Obtained alloy nanocluster purity is higher.The method can be commonly utilized in synthesis noble-metal nanoclusters.
Summary of the invention:
The purpose of the present invention is to provide a kind of method of AgAu alloy nanocluster that synthesis atom number, size are controllable, The preparation method is feasible, easy to operate.The AgAu nano-cluster controllable mainly for the preparation of atom number, size is controllable, nanometer Cluster size is in 2nm hereinafter, and having accurate atom number.
The preparation for the AgAu nano-cluster that a kind of atom number of the invention is controllable, size is controllable, specific step: first The ligand of the silver nitrate of 10~50mg and 0.05~0.5 ratio is dissolved in 10~20mL methylene chloride and stirs 20~60 points by step Then clock is added sodium borohydride and is restored, obtains Ag nano-cluster.Second step, by AuCl3It is dissolved in methanol and stirring with mercaptan ligand A period of time is mixed, the Ag nano-cluster of first step preparation is then added, reaction a period of time, accurate atom number can be obtained AuAg alloy nanocluster.Reaction time depends on the ultraviolet-visible absorption spectroscopy of sample in experimentation.In order to prepare high-purity Nano-cluster, methylene chloride product will be dissolved in and be spin-dried for, be centrifuged, extraction then is spin-dried for.
Change the ratio of two kinds of source metals, the silver-colored billon nano-cluster with different accurate atom numbers of synthesis.
The controllable AgAu nano-cluster of atom number is obtained using simple method.
Use silver nanoclusters that can prepare a kind of pure alloy nanocluster as template.
The ratio for adjusting two kinds of source metals can prepare different sized nanostructures clusters
Compared with the preparation method for having reported AgAu nano-cluster, advantages of the present invention is as follows:
A) present invention synthesis AgAu nano-cluster, can be used for various other alloy nanoclusters.
B) present invention can control the ratio of two kinds of source metals, prepare the controllable AgAu nano-cluster of atom number.
C) AgAu nano-cluster prepared by the present invention, it is easy to operate, it is easily controllable.
Detailed description of the invention:
Fig. 1 is to obtain the ultraviolet-visible absorption spectroscopy figure of product in example 1；
Fig. 2 is to obtain the ultraviolet-visible absorption spectroscopy figure of product in example 2.
Specific embodiment
Specific description is done to the present invention below in conjunction with example:
The synthesis of example 1:AgAu nano-cluster
20mL methylene chloride is dissolved in by the silver nitrate of 10~50mg and with silver-colored molar ratio for the ligand (benzene ethyl mercaptan) of 1:1 In, it stirs 30 minutes, the sodium borohydride of 3:1 is dissolved in 0~4 DEG C of ice water of 2mL under room temperature then, be added above-mentioned molten It is restored in liquid, solution slowly becomes brown, shows that Ag nanoparticle generates.Again by AuCl3With 5:1 mercaptan ligand (benzene ethyl mercaptan) It is dissolved in 2mL methanol and stirs 30~60min (molar ratio of chlorauride and silver nitrate is 0.1:1), first step preparation is then added Ag nano-cluster, react 24 hours, pass through the absorption peak that ultraviolet-visible absorption spectroscopy characterizes product, it was demonstrated that obtain accurate atom Several AuAg alloy nanoclusters.In order to improve AuAg alloy nanocluster purity, methylene chloride product will be dissolved in and be spin-dried for, first is then used Alcohol washs 3 times, is extracted with dichloromethane, is finally spin-dried for.
Such as Fig. 1, embodiment 1 prepares the ultraviolet-visible absorption spectroscopy of AgAu nano-cluster.
The synthesis of example 2:AgAu nano-cluster
It is that 1:1 ligand (benzene ethyl mercaptan) is dissolved in 20mL methylene chloride by the silver nitrate of 10~50mg and with silver-colored molar ratio, It stirs 30 minutes under room temperature, then the sodium borohydride of 3:1 is dissolved in 0~4 DEG C of ice water of 2mL, above-mentioned solution is added Middle reduction, solution slowly become brown, show that Ag nanoparticle generates.Again by AuCl3It is molten with 5:1 mercaptan ligand (benzene ethyl mercaptan) (molar ratio of chlorauride and silver nitrate is 0.3:1) is stirred 30~60min time in 2mL methanol, and first step system is then added Standby Ag nano-cluster reacts 24 hours, the absorption peak of product is characterized by ultraviolet-visible absorption spectroscopy, it was demonstrated that obtain accurate atom The AuAg alloy nanocluster of number.In order to improve AuAg alloy nanocluster purity, methylene chloride product will be dissolved in and be spin-dried for, then used Methanol washs 3 times, is extracted with dichloromethane, is finally spin-dried for.
Such as Fig. 2, embodiment 2 prepares the ultraviolet-visible absorption spectroscopy of AgAu nano-cluster.

Claims (6)

1. a kind of synthetic method for the AgAu alloy nanocluster that atom number is controllable, which is characterized in that operate according to the following steps: The first step stirs the silver nitrate of 10~50mg and silver-colored molar ratio 0.05~5:1 mercaptan ligand in 10~20mL methylene chloride, 10~60min is reacted, sodium borohydride is eventually adding and is restored, obtain Ag nano-cluster；
Second step, by AuCl3It is dissolved in 30~60min of stirring in 1~10mL methanol with the mercaptan ligand of golden 0.05~5:1 of molar ratio, Then the Ag nano-cluster of first step preparation is added, reacts 1~2 day, the AuAg alloy nanocluster of accurate atom number can be obtained；
And the molar ratio of Jin Yuanyu silver nitrate is 0.001~0.5:1.
2. a kind of synthetic method of AgAu nano-cluster that atom number is controllable according to claim 1, which is characterized in that adjust The ratio 1:1 of mercaptan ligand and source metal is controlled, after sodium borohydride reduction, product is the controllable AgAu nanometer of atom number Cluster, reaction time depend on the ultraviolet-visible absorption spectroscopy of sample in experimentation.
3. according to claim 1 a kind of synthetic method for the AgAu nano-cluster that atom number is controllable, it is characterised in that: be The nano-cluster of preparation high-purity, will be dissolved in methylene chloride product and is spin-dried for, and be centrifuged, extraction, then be spin-dried for.
4. according to claim 1 a kind of synthetic method for the AgAu nano-cluster that atom number is controllable, which is characterized in that use Silver nanoclusters prepare AgAu alloy nanocluster as template.
5. according to claim 1 a kind of synthetic method for the AgAu nano-cluster that atom number is controllable, which is characterized in that adjust The ratio of whole two kinds of source metals can prepare different sized nanostructures clusters, 1.3~1.9nm of size range.
6. according to claim 1 a kind of synthetic method for the AgAu nano-cluster that atom number is controllable, which is characterized in that sulphur Alcohol structure is aromatic mercaptans.
CN201710750161.6A 2017-08-28 2017-08-28 A kind of preparation of the controllable AgAu alloy nanocluster of atom number, size Pending CN109420774A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110227559A (en) * 2019-07-01 2019-09-13 郑州大学 The titanium dioxide optical catalyst and preparation method and application being sensitized with the Ag nano-cluster of ligand protection
CN114522733A (en) * 2022-03-04 2022-05-24 安徽大学 Method for preparing nano composite material by using bond breaking strategy and application of nano composite material in CO catalysis2Application in ethynylation reaction

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KR20150048295A (en) * 2013-10-25 2015-05-07 한국과학기술원 Synthesis method for AuNPCs with tuned size and shape
CN105382269A (en) * 2015-11-09 2016-03-09 东南大学 Method for preparing water-soluble light-emitting gold nanoclusters based on substitution method and aggregation inducement
CN106807935A (en) * 2015-12-01 2017-06-09 中国科学院大连化学物理研究所 A kind of activation method of the gold nano grain protected by organic ligand
CN106807397A (en) * 2015-12-01 2017-06-09 中国科学院大连化学物理研究所 The preparation method and alloy atom cluster of one class alloy atom cluster

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CN1899733A (en) * 2006-07-18 2007-01-24 大连理工大学 New method for preparing functional metal nano particles
KR20150048295A (en) * 2013-10-25 2015-05-07 한국과학기술원 Synthesis method for AuNPCs with tuned size and shape
CN105382269A (en) * 2015-11-09 2016-03-09 东南大学 Method for preparing water-soluble light-emitting gold nanoclusters based on substitution method and aggregation inducement
CN106807935A (en) * 2015-12-01 2017-06-09 中国科学院大连化学物理研究所 A kind of activation method of the gold nano grain protected by organic ligand
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110227559A (en) * 2019-07-01 2019-09-13 郑州大学 The titanium dioxide optical catalyst and preparation method and application being sensitized with the Ag nano-cluster of ligand protection
CN110227559B (en) * 2019-07-01 2021-12-10 郑州大学 Ligand-protected Ag nano-cluster-sensitized titanium dioxide photocatalyst and preparation method and application thereof
CN114522733A (en) * 2022-03-04 2022-05-24 安徽大学 Method for preparing nano composite material by using bond breaking strategy and application of nano composite material in CO catalysis2Application in ethynylation reaction

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