EP2222883B1 - Synthèse de nano ou microcristaux de au, pd, pt ou ag par la réduction des sels métalliques par la cellulose dans le liquide ionique chlorure de 1-butyl-3-méthyl-imidazolium - Google Patents

Synthèse de nano ou microcristaux de au, pd, pt ou ag par la réduction des sels métalliques par la cellulose dans le liquide ionique chlorure de 1-butyl-3-méthyl-imidazolium Download PDF

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EP2222883B1
EP2222883B1 EP08865205A EP08865205A EP2222883B1 EP 2222883 B1 EP2222883 B1 EP 2222883B1 EP 08865205 A EP08865205 A EP 08865205A EP 08865205 A EP08865205 A EP 08865205A EP 2222883 B1 EP2222883 B1 EP 2222883B1
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Prior art keywords
cellulose
gold
particles
metal salt
microcrystals
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EP2222883A1 (fr
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Andreas Taubert
Zhonghao Li
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Universitaet Postdam
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Universitaet Postdam
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00—Obtaining noble metals
    • C22B11/04—Obtaining noble metals by wet processes
    • 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
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • B22F1/068—Flake-like particles
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • 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
    • B22F2009/245—Reduction reaction in an Ionic Liquid [IL]
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • 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
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the invention deals about a simple and partly sustainable approach towards nano- or microcrystals ofAu, Pd, Pt and Ag with defmed properties.
  • Ionic liquids have successfully been used in organic, inorganic, and electrochemical synthesis of new or improved materials.
  • inorganic materials chemistry in ionic liquids has recently attracted quite some attention. This is due to the fact that in ILs, some inorganic compounds can be prepared easily and occasionally with superior properties than via conventional pathways.
  • ILs with a long range order can not only act as efficient solvents or templates for inorganic materials synthesis, but also as "all-in-one" solvent-template-reactants, so-called ionic liquid crystal precursors (ILCPs; see A. Taubert Angew. Chem. Int. Ed. 2004, 43, 5380 ).
  • ILCPs ionic liquid crystal precursors
  • Zhu et al. have shown that the solvent-template-reactant principle is also applicable to ionic liquids without a long range order (see H. Zhu; J.-F. Huang; Z. Pan; S. Dai Chem. Mater. 2006, 18, 4473 ).
  • ILPs reactive ILs
  • Some IL(C)Ps have been studied in quite some detail, in particular the CuCl platelet formation from ascorbic acid-containing ILCPs (see e.g. A. Taubert; C. Palivan; O. Casse; F. Gozzo; B. Schmitt J. Phys. Chem. C 2007, 111, 4077 ). Few reports have shown that silver and gold can be grown from IL(C)Ps (see A. Taubert; I. Arbell; A. Mecke; P. Graf Gold Bulletin 2006, 39, 205 ; K.-S. Kim; S. Choi; J.-H. Cha; S.-H.
  • Gold particles are among the best-studied particles in modem materials science. This is due to the ease of their preparation, their high (chemical) stability, and the wide range of applications from catalysis to sensing and biological tagging. There are countless examples of spherical and near-spherical gold particles, including, for example, spherical particles with bimodal size distributions and porous self-assembled solid state structures.
  • Gold plates have been fabricated via wet chemistry ( X. Sun; S. Dong; E. Wang Angew. Chem. Int. Ed. 2004, 43, 6360 ), via biological methods (see S.S. Shankar; A. Rai; B. Ankamwar; A. Singh; A. Ahmad; M. Sastry Nature Mater. 2004, 3, 482 ), via a polyol process (see C.C. Li; W.P. Cai; B.Q. Cao; F.Q. Sun; Y. Li; C.X. Kan; L.D. Zhang Adv. Funct. Mater.
  • Truncated gold tetrahedral, cubes, and icosahedra have been prepared by a polyol process.
  • Gold octahedra were synthesized by thermal decomposition of HAuCl 4 in block copolymer micelles.
  • Decahedra were synthesized by ultrasound-induced reduction of HAuCl 4 on pre-synthesized gold seeds with poly(vinylpyrrolidone) (PVP) as a stabilizing polymer.
  • PVP poly(vinylpyrrolidone)
  • the shapes, sizes, size distributions, and therefore the physical properties of gold particles strongly depend on the reducing agent used in particle synthesis.
  • Common reducing agents are, for example, NaBH 4 , PVP, glycol, and ascorbic acid.
  • Carbohydrates can also act as reducing agents, but their limited solubility in water or organic solvents prevented their use in the past.
  • the present invention shows that solutions of cellulose and metal salts can be transformed into metal particles with a tunable structure.
  • the IL can be recycled (although in the current case, this will be a major challenge due to the presence of many small organic residues and some remaining metal salt in the IL), cellulose is a renewable raw material, the reaction temperatures are usually below 220 °C, and the only side products are the oxidation products of cellulose and the metal salt.
  • the present invention therefore introduces a cheap, simple, and at least partly sustainable process towards metallic microparticles (including also nanostructures of the metals).
  • the unique solubility of cellulose in ionic liquids simplifies processing and chemical transformation of this otherwise hard-to-process biological material.
  • a method of preparing nano-or microcrystals of Au, Pd, Pt and Ag (especially gold microcrystals) comprising the steps of:
  • the metal salt is selected from the group consisting of M(NO 3 ) x , MCl x , MBr x , MI x , M(OAc) x , M(TfO) x , M(acac) x and HAuCl 4 * 3 H 2 O, wherein M represents Au, Pd, Pt or Ag and x is an integer from 1 to 4. Most preferred, the metal salt is HAuCl 4 * 3 H 2 O.
  • the cellulose is present in the mixture in an equimolar amount to or in a molar excess to the metal salt.
  • a molar ratio of cellulose to metal salt may be from 1:1 to 20:1.
  • the metal salt is an Au salt and step b) (i) of thermally inducing the reduction is performed at a temperature in the range of 180 to 220°C for preparing gold microcrystals having a plate-like shape and a plate thickness in the range of 700 to 1.000 nm.
  • the above described method provides nano- or microcrystals of Au, Pd, Pt or Ag, especially gold microcrystals.
  • ionic liquids to dissolve cellulose can be exploited for the fabrication of for example gold microparticles via the thermally induced reduction of an Au(III) salt by cellulose or the photoreduction by irradiation with UV light. Because of the high thermal stability of the IL, the reaction can be conducted at various temperatures, which enables the tuning of the reaction in terms of particle sizes, shapes, and connectivity. The change of the particle shapes can be assigned to the role of the cellulose as a template in conjunction with an effect provided by the ionic liquid.
  • the approach reported here presents a simple and partly sustainable approach in particular towards nano- and microparticles of Au, Pd, Pt or Ag with defined properties. It uses a metal salt and a reducing agent/template from renewable raw materials. The only side products of the reaction are oxidized cellulose fragments and oxidation products from the metal salt. In principle, the IL can be recycled, although purification may cause some difficulties because of the presence of small organic fragments from cellulose decomposition and the further presence of inorganic ions from the metal, respectively gold salt precursor.
  • X-ray diffraction was done on a Nonius PDS 120 with CuK ⁇ radiation and position sensitive detector and on a Nonius D8 with CuK ⁇ radiation.
  • SEM was done on a LEO 1550 Gemini operated at 20 kV.
  • TGA and DTA were done on a Linseis L81 thermal analyzer working in perpendicular mode from 25 to 1400 °C in air.
  • Calibration was done with Al 2 O 3 .
  • Optical microscopy was done with Zeiss Primo star at 20, 40, and 100 x.
  • Figure 1 shows a typical X-ray diffraction (XRD) pattern of a sample recovered from a solution after 20 hours. All products are pure face-centered cubic (fcc) gold (JCPDS 04-0784). All XRD patterns exhibit narrow reflections with full widths at half maximum (FWHM) below 0.2 degrees 2 . Estimations of the crystallite size (the coherence length) using the Scherrer equation give values well above 200 nm. Therefore, the Scherrer equation is not applicable anymore and the crystallite sizes are beyond of what can be determined from XRD.
  • XRD X-ray diffraction
  • the relative intensities of the five gold reflections differ from what is expected for a purely isotropic bulk gold sample.
  • the (200)/(111) and (220)/(111) intensity ratios are 0.041 and 0.019, respectively. This is lower than the values reported for bulk, isotropic gold samples (0.52 and 0.32, JCPDS 04-0784) and suggests that the resulting gold particles are dominated by (111) facets.
  • a high intensity of the (111) reflection and the absence of other reflections is an indication of plate-like crystals with very large (111) faces.
  • XRD indicates that the samples are not (or not entirely) plate-like, but rather have other morphologies that are dominated by (111) facets.
  • Figure 2 and Table 1 show the effect of reaction temperature on the particle morphologies.
  • Scanning electron microscopy (SEM) clearly shows that the samples are not uniform and contain particles with a variety of shapes and sizes in the micrometer range. This is consistent with XRD, as there, the narrow reflections and the presence of reflections besides (111) indicate that the particles are not nanoparticles and not only plate-like.
  • particles with octahedral, decahedral, twinned polyhedral, and only partially developed tetrahedral shapes are observed in the samples prepared at 110 °C.
  • the fraction of plates increases to ca. 100% at 200 °C.
  • the number of polyhedral particles decreases to close to zero at a reaction temperature of 200 °C.
  • Figure 3 and Table 2 show the effect of cellulose concentration on the particle morphology.
  • the samples again consist of plates and polyhedral gold particles.
  • the amount of gold plates decreases slightly, but all samples obtained at low temperatures still mainly contain polyhedral gold crystals.
  • the number of gold plates slightly decreases with increasing concentration, the other particles still have many different shapes. There is thus no focusing effect in the sense that above a certain threshold cellulose concentration, there are only, for example, octahedral particles in the sample.
  • Variation of the gold salt concentration reveals that also here, there is no focusing on a certain morphology or particle size with increasing gold concentration (data not shown).
  • Figure 4 shows that the cellulose does, however, lead to a peculiar variation in the gold particles. Even though the overall morphologies and particle sizes do not depend on the cellulose concentration, particles grown at low cellulose concentrations and temperatures below 160 °C have a flat and smooth surface. In contrast, particles grown at higher cellulose concentrations have a rougher surface. SEM suggests that these structures could be due to adsorbed and mineralized cellulose because some of the structures resemble fibers deposited on a surface.
  • TEM shows that the particles are single crystal-like ( Figure 5 ).
  • the diffraction patterns of individual particles can either be assigned to a single crystal or to a twinned particle.
  • TEM often finds pentagonal particles, which are 2D projections of the decahedra found in SEM.
  • the decahedron is a typical twin crystal, which can be considered as a junction of five tetrahedra with twin-related adjoining faces.
  • FIG. 6 shows thermal analysis data of some samples.
  • Thermogravimetric analysis (TGA) of the particles shows that there is only a minor weight loss of below 5% overall up to a temperature of 1400 °C.
  • TGA shows a first weight loss between ca. 50 and 200 °C. This process is followed by a minor weight gain and a final slight weight loss until 1400 °C.
  • Differential thermal analysis (DTA) shows that the first weight loss is endothermic until ca. 170 °C. Thereafter, an exothermic process begins and lasts until ca. 800 °C. Upon further heating, the DTA curve increases again and a sharp endothermic peak is observed at 1064 to 1066 °C.
  • the endothermic part of the weight loss below 170 °C is assigned to desorption of residual solvent molecules from the purification process. TGA/DTA therefore shows that about 1 wt% of solvent is kept in the samples after drying. This indicates that some ionic liquid is still adsorbed on the surface of the final particles even after washing and drying.
  • the exothermic contribution to the first weight loss is assigned to the thermal decomposition (the "burning") of a small fraction of cellulose present in the sample. Samples grown with higher cellulose concentrations show a very similar mass loss. This indicates that only a small fraction of the cellulose present in the reaction solution is incorporated in the final product.
  • the exothermic process (decomposition of the residual organic material) lasts until ca. 800 °C.
  • the slow increase of the DTA signal above ca. 800 °C indicates that all organic material is decomposed above this temperature.
  • the sharp endothermic peak at 1064 to 1066 °C is due to the melting of gold.
  • the fact that the peak is narrow and corresponds to the bulk melting temperature of gold indicates that our particles are large particles with bulk gold behavior. They are not aggregates of gold nanoparticles, which would melt at lower temperatures.
  • TGA/DTA data are therefore in agreement with SEM and XRD, which show that the gold is not present as a nanoscale material, but rather as a bulk-like solid with larger dimensions.
  • Figure 7 shows the times between the start of the reaction and the first observation of a shiny gold sediment at the bottom of the reaction vessel.
  • the lag time decreases with increasing reaction temperature. This is a clear indication that the reaction is thermally activated, similar to the formation of CuCl nanoplatelets from an ILCP. Indeed, experiments at temperatures below 110 °C have shown that there, no reaction occurs within 20 hours and no product can be retrieved.
  • Figure 7 also shows that the lag time decreases with increasing cellulose and with increasing gold concentration. This clearly shows that the cellulose is an integral part of the reaction and that, not surprisingly, an increased amount of cellulose increases the reduction rate of the Au(III) ions and hence nucleation efficiency of the Au(0) particles. Further measurements to determine the order of the reaction, the kinetics, and the activation energy are underway.
  • Figure 8 shows SEM images of a sample prepared at 200 °C in the absence of cellulose. SEM shows that many particles in these samples have a sheet or plate morphology. Other crystals are either spherical or small polyhedral particles. The plates are large and reach sizes of over 50 ⁇ m, similar to an earlier study, where gold sheets have been obtained by microwave heating of gold salts in [BMIM]BF 4 or [BMIM]PF 6 .
  • cellulose/gold(III) solutions in the IL [BMIM]Cl can be used for the fabrication of micrometer-sized gold particles.
  • the morphologies, particle sizes, and fractions of particles with different morphologies depend on the synthesis conditions, especially on the reaction temperature. Especially at high temperatures, plate-like crystals are obtained.
  • Two-dimensional (gold) nanostructures such as plates or sheets, have attracted a growing interest in materials research due to their potential applications in the areas of electrochemistry, gas sensors, efficient surface-enhanced Raman scattering substrates and new nanodevices.
  • the ease of synthesis, the tunability, the potential to scale the process up, and the availability of the reactants make our process a good candidate for the fabrication of large amounts of complex gold structures for the above and other applications. It is assumed that further the system is assignable for metals, especially noble metals.
  • the materials obtained at 160 and 200 °C are different from other reports on gold plates. Usually, large plates with smooth surfaces and rather low thicknesses are found. These results suggest that the microphase-separated structure of the ILs is partly responsible for the formation of the gold plates, possibly because the metal ion (and hence nucleus and primary particle) distribution in the IL is not homogeneous. This is supported by a recent study showing that gold plates can also form within a crystalline IL analog, where hydrophobic and hydrophilic domains are well-separated. There, the presence of an organic template with a long-range order is of crucial importance for the shape control over the products. The formation of platelets is in this case attributed to the stiff matrix at low temperature.
  • cellulose is the reducing agent for Au(III).
  • cellulose acts as a morphology and size-directing agent, which drives the crystallization towards polyhedral particles or thick plates. The differences between the control and the cellulose-containing samples can qualitatively be explained with heterogeneous nucleation on existing crystals and the relative growth rates along different crystallographic axes.
  • the shape of a face centered cubic (fcc) crystal is mainly determined by the ratio R of the growth rate along the [100] vs. the [111] direction. Crystal growth rates along different directions are proportional to their surface energies.
  • the relative surface energies ⁇ of the low-index crystallographic planes are ⁇ 110 ⁇ > ⁇ 100 ⁇ > ⁇ 111 ⁇ .
  • the surface energies and hence the relative growth rates along different crystallographic axes in fcc metals can, like in many other inorganics, be modulated through the (selective) adsorption of growth modifiers on different crystal faces.
  • the IL has an effect on the mineralization.
  • Many ILs have ordered structures. 1,3-dialkyl imidazolium ILs such as [BMIM]Cl form two-dimensional polymeric assemblies. It is therefore reasonable to assume that the organized structure of the IL has a template effect on the formation of the gold particles.
  • the order within the IL may be changed or destroyed due to the higher amount of foreign ions.
  • the IL is "softer" and becomes a less efficient template for the (thin) platelet formation.
  • (irregular) polyhedral particles form more often, although this process does not appear to be strong.
  • FIG. 9 illustrates SEM images of Pt nanoparticles formed at 130 °C (top) and 200 °C (bottom) after 20 hours of heating. Pt nanoparticles have been obtained that are only a few nanometers in size. The results for Pd and Ag are similar.
  • XRD confirms the electron microscopy data
  • Figure 10 shows XRD pattern of Pd grown with the thermochemical approach at 200 °C. The reflections of the metal are barely visible (arrow in panel b) and the most intense signal is from some organic residue (cellulose). Overall, however, the XRD data confirm electron microscopy, because the reflections are so broad (indicative of very small metal particles) that they are barely visible.

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Abstract

La présente invention concerne un procédé de préparation de nano ou microcristaux de Au, Pd, Pt ou Ag comprenant les étapes consistant à : a) préparer un mélange liquide ionique de cellulose et d'au moins un sel métallique sélectionné dans le groupe constitué par Au, Pd, Pt et Ag dans le chlorure de l-butyle-3-méthylimidazolium; et b) (i) provoquer thermiquement une réduction du sel métallique avec la cellulose par chauffage du mélange jusqu'à une température comprise entre 50 et 250 °C; ou (ii) effectuer la photoréduction du sel métallique par irradiation du mélange avec une lumière présentant une longueur d'onde comprise entre 200 et 800 nm.

Claims (5)

  1. Procédé de préparation de nano ou microcristaux de Au, Pd, Pt ou Ag comprenant les étapes suivantes :
    a) préparer un mélange de liquide ionique de cellulose et d'au moins un sel métallique sélectionné dans le groupe constitué par Au, Pd, Pt et Ag dans du chlorure de 1-butyl-3-méthylimidazolium ; et
    b)
    (i) induire thermiquement une réduction du sel métallique avec la cellulose par chauffage du mélange jusqu'à une température comprise dans la plage allant de 50 à 250 °C ; ou
    (ii) effectuer une photoréduction du sel métallique par irradiation du mélange par une lumière présentant une longueur d'onde comprise dans la plage allant de 200 à 800 nm.
  2. Procédé selon la revendication 1, dans lequel le sel métallique est sélectionné dans le groupe constitué par M(NO3)x, MClx, MBrx, MIx, M(OAc)x, M(TfO)x, M(acac)x et HAuCl4 * 3 H2O, M représentant Au, Pd, Pt ou Ag, et x étant un nombre entier de 1 à 4.
  3. Procédé selon l'une des revendications 1 ou 2, dans lequel la cellulose est présente dans le mélange en quantité équimolaire par rapport au sel métallique ou en excès molaire par rapport au sel métallique.
  4. Procédé selon la revendication 3, dans lequel un rapport molaire de la cellulose au sel métallique est de 1:1 à 20:1.
  5. Procédé selon l'une des revendications précédentes, dans lequel le sel métallique est un sel Au, et dans lequel l'étape b) (i) consistant à induire thermiquement la réduction est effectuée à une température comprise dans la plage allant de 180 à 220 °C pour préparer des microcristaux d'or présentant une forme de plaque et une épaisseur de plaque comprise dans la plage allant de 700 à 1000 nm.
EP08865205A 2007-12-19 2008-12-10 Synthèse de nano ou microcristaux de au, pd, pt ou ag par la réduction des sels métalliques par la cellulose dans le liquide ionique chlorure de 1-butyl-3-méthyl-imidazolium Not-in-force EP2222883B1 (fr)

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EP08865205A EP2222883B1 (fr) 2007-12-19 2008-12-10 Synthèse de nano ou microcristaux de au, pd, pt ou ag par la réduction des sels métalliques par la cellulose dans le liquide ionique chlorure de 1-butyl-3-méthyl-imidazolium

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EP07150120 2007-12-19
EP08865205A EP2222883B1 (fr) 2007-12-19 2008-12-10 Synthèse de nano ou microcristaux de au, pd, pt ou ag par la réduction des sels métalliques par la cellulose dans le liquide ionique chlorure de 1-butyl-3-méthyl-imidazolium
PCT/EP2008/067216 WO2009080522A1 (fr) 2007-12-19 2008-12-10 Synthèse de nano ou microcristaux de au, pd, pt ou ag par la réduction des sels métalliques par la cellulose dans le liquide ionique chlorure de 1-butyl-3-méthyl-imidazolium

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US9631101B2 (en) 2011-08-24 2017-04-25 Eckart America Corporation Ionic liquid release coat for use in metal flake manufacture
US8546288B2 (en) 2012-02-15 2013-10-01 Ford Global Technologies, Llc Substrate selection for a catalyst
PL231410B1 (pl) 2013-06-10 2019-02-28 Inst Chemii Fizycznej Polskiej Akademii Nauk Sposób modyfikowania powierzchni nanokompozytami i zastosowanie materiału nanokompozytowego zmodyfikowanego tym sposobem do wytwarzania powierzchni antyseptycznych
EP3141323B1 (fr) * 2014-05-09 2022-02-09 Toppan Printing Co., Ltd. Complexe, procédé de fabrication d'un complexe, dispersion, procédé de fabrication d'une dispersion, et matériau optique
CN106400120B (zh) * 2016-10-14 2020-05-01 中国科学院光电技术研究所 一种三十二面体金纳米晶体及其可控制备方法
CN107699954B (zh) * 2017-09-29 2020-03-20 中国科学院光电技术研究所 一种强耦合的金纳米超晶格结构及其自组装制备方法
CN110340375B (zh) * 2018-04-03 2022-07-19 中国科学院青岛生物能源与过程研究所 一种制备毫米尺度二维单晶金片的方法
CN111203545B (zh) * 2020-01-16 2022-09-13 河南科技大学 一种离子液体调控的菊花状Pd纳米粒子的制备方法

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