CN110788345A - Size-controllable Pt1Ag28Synthesis method of alloy nanocluster - Google Patents

Size-controllable Pt1Ag28Synthesis method of alloy nanocluster Download PDF

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CN110788345A
CN110788345A CN201810864176.XA CN201810864176A CN110788345A CN 110788345 A CN110788345 A CN 110788345A CN 201810864176 A CN201810864176 A CN 201810864176A CN 110788345 A CN110788345 A CN 110788345A
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ligand
alloy
single crystal
silver precursor
dichloromethane
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黄家辉
林欣章
刘超
付雪梅
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Dalian Institute of Chemical Physics of CAS
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    • B22—CASTING; POWDER METALLURGY
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    • 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
    • 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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    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/52—Alloys
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/02—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent
    • C30B7/06—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent using non-aqueous solvents

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Abstract

The invention aims to synthesize the alloy nanoclusters with controllable atomic number and size in one pot by a simple one-step method and obtain a single crystal structure. The invention belongs to the synthesis of metal alloy nanoclusters, and Pt is synthesized in one pot mainly through the selection and proportion adjustment of a metal precursor and a ligand1Ag28Alloy nanoclusters, in particular to: reducing a metal silver precursor, a doped platinum source, a thiol ligand and a phosphorus ligand by sodium borohydride to obtain a crude product, and purifying at low temperature and separating a solvent to obtain pure Pt1Ag28Alloy nanoclusterAnd obtaining the single crystal by a solution volatilization method. The present invention relates to the synthesis of Pt1Ag28Compared with the previously reported ligand exchange method, the method for preparing the alloy nanocluster has the advantages of high yield, simple and convenient process, simple operation, easy control and the like.

Description

Size-controllable Pt1Ag28Synthesis method of alloy nanoclusterMethod of
Technical Field
The invention belongs to the synthesis of metal alloy nanoclusters, and Pt is synthesized in one pot mainly through the selection and proportion adjustment of a metal precursor and a ligand1Ag28The invention discloses an alloy nano-cluster, and relates to a method for synthesizing Pt from a metal precursor and a ligand in one step1Ag28A method for synthesizing an alloy nano-cluster.
Background
As a novel nano material, the metal nanocluster attracts extensive attention and research in the fields of nano science, nano technology and the like. Nanoclusters generally refer to ligand-protected nanoparticles having a size of less than 2nm with a precise number of atoms. The nano-cluster has an accurate crystal structure, completely different from the traditional gold nano-particles, the surface plasmon resonance effect disappears, a discrete electronic structure is displayed, and an electronic energy band is changed from a continuous conduction band to a discontinuous energy band, so that the nano-cluster shows quantum size effect and unique properties of optics, magnetism, chirality, electrochemistry, catalysis and the like.
In recent years, the synthesis of a single nanocluster has been extensively studied and extensively reported. The synthesis of the alloy nanoclusters is also concerned due to the advantages of controllable composition, synergistic effect and the like. For example, Ag3Au15(Nanoscale.2015,7,18278-18283.)，Ag1Au16(Inorg Chem.2018,57,335-342.)，Cu2Au13(Angew Chem Int EdEngl.2018,57,3421-3425.)，Cd4Au20(Angew Chem Int Ed Engl.2018,57,3421-3425.)，Pd1Ag24(J Am Chem Soc.2015,137,11880-11883.)，Au1Ag24(Angew Chem Int EdEngl.2016,55,922-926.)，Au4Ag13(Sci Adv.2017,3,e1700956.)，Cu12Ag28(J Am ChemSoc.2016,138,12751-12754.)，Au24Ag46(J Am Chem Soc.2016,138,12751-12754.)，Au1Ag28(Angew Chem Int Ed Engl.2016,55,5749-53.). Among them, the silver nanocluster doped with Pt with controllable size has been found to be important in catalysis, due to the relatively low cost of silver and the metal synergySome reports have been made, including Pt1Ag24(J Am Chem Soc.2015,137,11880-11883.)，Pt1Ag26(J Am Chem Soc.2018,140,3487-3490.)，Pt2Ag23(J Am Chem Soc.2017,139,1053-1056.)，Pt5Ag22(Chem-Eur J.2017,23,17885-17888.)，Pt1Ag42(Chem-Asian J.2017,12,2904-2907.)。
The synthesis method of the alloy nanocluster mainly comprises a typical 'size clustering' method, a 'ligand exchange' method and an 'Anti-galvanic Reduction' method, the latter two methods are often used for synthesizing the nanocluster which is difficult to synthesize by the 'size clustering' method, and the method has the defects of low yield, complex process and the like. Pt according to the present patent1Ag28The synthesis of Pt nanoclusters by the ligand exchange method has been previously reported by OsmanM.Bakr (nanoscale.2017,9,9529-9536.) and Manzhou Zhu (Chem Sci.2017,8,2581-2587.), et al1Ag28Alloy nanoclusters and the latter yielding Pt1Ag28Single crystal structure of the alloy nanocluster. However, Pt was synthesized using the ligand exchange method1Ag28The process of the alloy nanocluster is complicated, and the yield is low (about 5%).
Disclosure of Invention
The invention aims to synthesize the alloy nanoclusters with controllable atomic number and size in one pot and obtain a single crystal structure by a simple one-step method, and the preparation method has the advantages of high yield, simple process and easy control. Mainly synthesizes Pt in one pot through the selection and the proportion adjustment of a metal precursor and a ligand1Ag28Alloy nanoclusters and obtain a single crystal structure.
Size-controllable Pt1Ag28The synthesis method of the alloy nanocluster comprises the following specific steps: dissolving a metallic silver precursor, a doped platinum source, a thiol ligand and a phosphorus ligand in an organic solution, adding tetraphenyl phosphine bromide, reducing by sodium borohydride, stirring for reaction for 4-12h to obtain a crude product, storing in a refrigerator, purifying at low temperature, testing by ultraviolet visible absorption spectrum, observing the sample concentration by peak shape, and storing for 15-30 days to obtain pure Pt1Ag28The alloy nanocluster is further eluted to obtain pure Pt1Ag28Alloy nanoclusters and single crystals obtained by a solution evaporation method, and Pt measured by single crystal X-ray diffraction1Ag28Single crystal structure of the alloy nanocluster.
The metal silver precursor is silver nitrate or silver tetrafluoroborate; the doped platinum source is potassium tetrachloroplatinate or chloroplatinic acid.
The molar ratio of the doped platinum source to the metallic silver precursor is 0.04-0.3.
The organic solvent is a mixed solution of dichloromethane and methanol, and the volume ratio of the dichloromethane to the methanol is about 2: 1-6: 1.
The mercaptan ligand is adamantane mercaptan or 1, 3-benzene dithiol, and the molar ratio of the mercaptan ligand to the metal silver precursor is 1: 1-4: 1.
The phosphorus ligand is triphenylphosphine, and the molar ratio of the phosphorus ligand to the metal silver precursor is 3: 1-7: 1.
The temperature of the low-temperature purification is 0-8 ℃.
The single crystal culture uses a solution volatilization method, and mainly uses a dichloromethane and normal hexane system.
Dissolving a metallic silver precursor and a doped platinum source in methanol, adding a thiol ligand and a phosphorus ligand, stirring for 40-50 minutes, adding dichloromethane and tetraphenyl phosphine bromide, and reducing by sodium borohydride.
And reported Pt1Ag28Compared with the synthesis method of the alloy nanocluster, the synthesis method of the invention has the following advantages:
a) the invention is to synthesize Pt1Ag28The alloy nanocluster provides a new method, is simple to operate and is easy to control.
b) The invention greatly simplifies Pt1Ag28In the synthesis process of the alloy nanocluster, the previously adopted ligand exchange method needs to synthesize and process to obtain a pure nanocluster and then obtain Pt through ligand exchange1Ag28The method is directly synthesized in one pot, and is simple to operate and easy to control.
c) Book (I)The invention is synthesized by a one-step method, reduces the process loss, has high conversion rate and selectivity, and can greatly improve Pt1Ag28Yield of alloy nanoclusters (30% or more based on silver precursor).
The invention synthesizes Pt in one pot by selecting and adjusting the proportion of metal precursor and ligand1Ag28The method has the advantages of feasibility, simple process, high yield, simple operation and easy control.
Drawings
FIG. 1 Synthesis of Pt in example 11Ag28An ultraviolet-visible absorption spectrogram of the alloy nanocluster in a low-temperature purification process;
FIG. 2 pure Pt in example 11Ag28An ultraviolet-visible absorption spectrum of the alloy nanocluster;
FIG. 3 example 1 Pt1Ag28Single crystal structure of the alloy nanocluster.
Detailed Description
The invention is described in more detail below with reference to examples:
example 1 Pt1Ag28Synthesis of alloy nanoclusters
Dissolving 25mg of silver nitrate and 5mg of potassium tetrachloroplatinate in 5mL of methanol; then 30mg of adamantane thiol and 200mg of triphenylphosphine were added; after stirring for 50 minutes, 12mL of dichloromethane and 3mg of tetraphenylphosphonium bromide were added; finally, 100mg of sodium borohydride (the sodium borohydride is dissolved in ice water, and the concentration is 40mg/mL) is added; stirring and reacting for 8 hours to obtain an alloy nano-cluster primary product. Storing in a refrigerator at 4 deg.C, purifying at low temperature, testing ultraviolet and visible absorption spectrum during the purification process, and synthesizing Pt as shown in FIG. 11Ag28Ultraviolet-visible absorption spectrogram of the alloy nanocluster in the low-temperature purification process.
After 21 days in the refrigerator, the organic solution was taken out, spin-dried, and washed three times with methanol, at which time the methanol solution was almost colorless; washing with n-hexane for several times, adding methanol, performing ultrasonic treatment, dissolving part of the solution, and collecting the solution as shown in FIG. 2 to obtain pure Pt1Ag28Alloy nanoclusterThe methanol was spin-dried, the sample weight was obtained by weighing, and the yield of the alloy nanoclusters was calculated to be 37.9% (based on the silver precursor). Finally, using dichloromethane and n-hexane system to grow crystals to obtain red square single crystals, obtaining single crystal structure by single crystal X-ray diffraction (figure 3), and determining that Pt is1Ag28An alloy nanocluster.
Example 2 Pt1Ag28Synthesis of alloy nanoclusters
31mg of silver tetrafluoroborate and 7mg of chloroplatinic acid hexahydrate were dissolved in 5mL of methanol; then 35mg of adamantane thiol and 200mg of triphenylphosphine were added; after stirring for 40 minutes, 17mL of dichloromethane and 4mg of tetraphenylphosphonium bromide were added; finally, 120mg of sodium borohydride (the sodium borohydride is dissolved in ice water, and the concentration is 40mg/mL) is added; stirring and reacting for 9 hours to obtain an alloy nano-cluster primary product. Storing in a refrigerator at 4 deg.C, purifying at low temperature, and testing in the process of ultraviolet visible absorption spectrum.
After 18 days in the refrigerator, the organic solution was taken out, spin-dried, and washed three times with methanol, at which time the methanol solution was almost colorless; washing with n-hexane for several times, adding methanol, ultrasonic treating to partially dissolve, and spin-drying methanol to obtain pure Pt1Ag28An alloy nanocluster. The sample weight was obtained by weighing and the yield of alloy nanoclusters was calculated to be 31.2% (based on silver precursor).

Claims (9)

1. Size-controllable Pt1Ag28The synthesis method of the alloy nanocluster comprises the following specific steps: dissolving a metallic silver precursor, a doped platinum source, a thiol ligand and a phosphorus ligand in an organic solution, adding tetraphenyl phosphine bromide, reducing by sodium borohydride, stirring for reaction for 4-12h to obtain a crude product, and purifying at low temperature and separating a solvent to obtain pure Pt1Ag28And (4) alloying the nano-cluster, and obtaining a single crystal structure through single crystal culture.
2. The method of claim 1, wherein: the metal silver precursor is silver nitrate or silver tetrafluoroborate; the doped platinum source is potassium tetrachloroplatinate or chloroplatinic acid.
3. The method of claim 1, wherein: the molar ratio of the doped platinum source to the metallic silver precursor is 0.04-0.3.
4. The method of claim 1, wherein: the organic solvent is a mixed solution of dichloromethane and methanol, and the volume ratio of the dichloromethane to the methanol is about 2: 1-6: 1.
5. The method of claim 1, wherein: the mercaptan ligand is adamantane mercaptan or 1, 3-benzene dithiol, and the molar ratio of the mercaptan ligand to the metal silver precursor is 1: 1-4: 1.
6. The method of claim 1, wherein: the phosphorus ligand is triphenylphosphine, and the molar ratio of the phosphorus ligand to the metal silver precursor is 3: 1-7: 1.
7. The method of claim 1, wherein: the temperature of the low-temperature purification is 0-8 ℃.
8. The method of claim 1, wherein: the single crystal culture uses a solution volatilization method, and mainly uses a dichloromethane and normal hexane system.
9. The method of claim 1, wherein: dissolving a metallic silver precursor and a doped platinum source in methanol, adding a thiol ligand and a phosphorus ligand, stirring for 40-50 minutes, adding dichloromethane and tetraphenyl phosphine bromide, and reducing by sodium borohydride.
CN201810864176.XA 2018-08-01 2018-08-01 Size-controllable Pt1Ag28Synthesis method of alloy nanocluster Pending CN110788345A (en)

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WO2013074822A1 (en) * 2011-11-15 2013-05-23 The Regents Of The University Of California Templated synthesis of metal nanorods in silica nanotubes
CN106180751A (en) * 2016-08-03 2016-12-07 红河学院 A kind of Platinum Nanoparticles nickel alloy and preparation and application thereof
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
CN106807952A (en) * 2015-12-01 2017-06-09 中国科学院大连化学物理研究所 One kind synthesis Au25The method and Au of nanosphere25Nanosphere
CN106862584A (en) * 2015-12-13 2017-06-20 中国科学院大连化学物理研究所 A kind of synthetic method of atom number and the controllable silver nanoclusters of particle size
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Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013074822A1 (en) * 2011-11-15 2013-05-23 The Regents Of The University Of California Templated synthesis of metal nanorods in silica nanotubes
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
CN106807952A (en) * 2015-12-01 2017-06-09 中国科学院大连化学物理研究所 One kind synthesis Au25The method and Au of nanosphere25Nanosphere
CN106862584A (en) * 2015-12-13 2017-06-20 中国科学院大连化学物理研究所 A kind of synthetic method of atom number and the controllable silver nanoclusters of particle size
CN106180751A (en) * 2016-08-03 2016-12-07 红河学院 A kind of Platinum Nanoparticles nickel alloy and preparation and application thereof
CN108115149A (en) * 2016-11-28 2018-06-05 中国科学院大连化学物理研究所 A kind of synthetic method of the controllable AgM alloy nanoclusters of atom number

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Application publication date: 20200214