WO2020040379A1 - Nanostructures d'alliage fractales produites à l'aide de nanostructures amorphes et leur procédé de production - Google Patents

Nanostructures d'alliage fractales produites à l'aide de nanostructures amorphes et leur procédé de production Download PDF

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WO2020040379A1
WO2020040379A1 PCT/KR2019/001087 KR2019001087W WO2020040379A1 WO 2020040379 A1 WO2020040379 A1 WO 2020040379A1 KR 2019001087 W KR2019001087 W KR 2019001087W WO 2020040379 A1 WO2020040379 A1 WO 2020040379A1
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metal
alloy
amorphous
nanostructure
nanostructures
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Korean (ko)
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허가현
김민석
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한국과학기술연구원
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
    • C07F1/10—Silver compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
    • C07F1/12—Gold compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/006—Palladium compounds
    • 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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  • the present invention relates to a nano-sized alloy and a method for manufacturing the same, and more particularly to an alloy nanostructure and a method for producing the amorphous nanostructure using a chemical template.
  • nanostructures For nanomaterial applications, the implementation of nanostructures with the same large surface area per volume (high surface-to-volume ratio) is important. Large surface areas can enhance physical and chemical reactivity, resulting in good properties in catalysts, sensors, material adsorption and separation, and the like. Fractal shapes commonly found in nature, such as snow and leaves, can have large specific surface areas.
  • the first technical problem to be achieved by the present invention is to provide a high entropy alloy nanostructure having a fractal shape.
  • Another object of the present invention is to provide a method of manufacturing an alloy nanostructure having a fractal shape for achieving the first technical problem.
  • the present invention for achieving the above-described first technical problem, has a fractal structure, including a central metal, a halogen element and elements of the functional group for bonding in the inorganic polymer of the formula (1), higher than the standard metal reduction potential It provides an alloy nanostructure further comprising a second metal element having a.
  • M is the transition metal of oxidation number +1 to the central metal
  • X is the halogen element
  • CF is the bonding functional group containing a hydrogen element and hydrogen bonding element
  • n is a repeating number of 10 to 10 Has a value of 500,000.
  • the present invention for achieving the above-described second technical problem, preparing an amorphous nanostructure hydrogen-bonded inorganic polymer having the formula (2); Mixing a second metal precursor including the second metal element having a standard reduction potential higher than that of the center metal of the inorganic polymer with the amorphous nanostructure; And dismantling the amorphous nanostructure and forming an alloy nanostructure of a fractal structure including the elements of the inorganic polymer and the second metal element.
  • M represents a transition metal
  • X represents a halogen element
  • CF represents a functional group for bonding including a hydrogen element and an element for hydrogen bonding
  • n has a value of 10 to 500,000 as a repetition frequency.
  • the alloy nanostructure of the fractal structure comprises a second metal element having a standard reduction potential higher than that of the center metal of the inorganic polymer, the composition of the center metal, halogen elements and bonding functional groups constituting the inorganic polymer Contains an element.
  • the alloy nanostructures may be composed of two or more kinds of second metal elements, and thus may express various electrochemical properties.
  • forming the alloy structure in the nano size can form a uniform size due to the nature of not using a melting process, it is possible to secure a high specific surface area due to the fractal structure.
  • 1 is a molecular formula showing an inorganic polymer according to a preferred embodiment of the present invention.
  • FIG. 2 is a schematic view showing the inorganic polymer of FIG. 1 according to a preferred embodiment of the present invention.
  • FIG. 3 is a STEM image and an EDS mapping image of Au atoms adsorbed to an amorphous nanostructure at an atomic level according to Preparation Example 1 of the present invention.
  • FIG. 4 is a STEM image and an EDS mapping image in which Au atoms are absorbed or formed into a sphere at an atomic level according to Preparation Example 2 of the present invention.
  • FIG. 5 is a STEM image and an EDS mapping image of a fractal nanostructure including an Au element derived from an amorphous nanostructure according to Preparation Example 3 of the present invention.
  • FIG. 6 is a STEM image and an EDS mapping image of a nanostructure including Au and Pd elements according to Preparation Example 4 of the present invention.
  • FIG. 7 is a SEM image and an EDS mapping image of a fractal nanostructure formed by changing a molar ratio of Au and Pd elements according to Preparation Example 5 of the present invention.
  • FIG. 8 is a STEM image and an EDS mapping image showing a fractal-shaped nanostructure including Au, Pd, and Rh elements according to Preparation Example 6 of the present invention.
  • an amorphous nanostructure formed through hydrogen bonding of inorganic polymers is prepared.
  • the prepared nanostructures serve as templates for chemical synthesis to form alloy nanostructures.
  • the formed alloy nanostructures have a diameter of 30 nm to 300 nm and have a fractal shape.
  • the inorganic polymer constituting the amorphous nanostructure has a main chain and a side chain, the main chain is composed of a bond of a central metal and a halogen element, and the side chain has a functional group for bonding.
  • the bonding functional group is combined with the central metal.
  • a second metal precursor containing a second metal element having a standard reduction potential higher than that of the center metal included in the amorphous nanostructure is added to the polar solvent and mixed with the amorphous nanostructure in the polar solvent, it is separated from the second metal precursor.
  • the ionized second metal element forms a fractal shaped alloy nanostructure with a portion of the amorphous nanostructure.
  • 1 is a molecular formula showing an inorganic polymer according to a preferred embodiment of the present invention.
  • M is a transition metal
  • the oxidation number is 1
  • X means a halogen element
  • CF is a bonding functional group.
  • the functional group for bonding has a hydrogen element and an element for hydrogen bonding.
  • the transition metal M is silver (Ag), gold (Au), platinum (Pt), palladium (Pd), ruthenium (Ru), cobalt (Co), sodium (Na), potassium (K), iron (Fe), cadmium (Cd), nickel (Ni), chromium (Cr), thallium (Tl), rubidium (Rb), zinc (Zn), copper (Cu), manganese (Mn), molybdenum (Mo), indium (In), gallium (Ga), bismuth (Bi), titanium (Ti), lead (Pb), aluminum (Al), magnesium (Mg) or antimony (Sb).
  • halogen element includes fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
  • the functional group for bonding is a compound having a hydrogen element and an element for hydrogen bonding.
  • the bonding functional group is chemically bonded to the transition metal and forms a hydrogen bond with a neighboring inorganic polymer through a hydrogen element.
  • the bonding functional group preferably has a hydrogen element and a hydrogen bonding element at the end of the chemical bond.
  • the hydrogen bonding element is a group 15 or 16 element and oxygen, sulfur, nitrogen, selenium or tellurium may be candidates.
  • the functional group for bonding in the inorganic polymer may form hydrogen bonds with halogen elements of other inorganic polymers.
  • the functional group for binding is preferably thiourea, urea, selenourea, tellurourea or thiol compounds.
  • the hydrogen element of the bonding functional group can form a hydrogen bond with the hydrogen bonding element or halogen element of another inorganic polymer.
  • Inorganic polymers are bonded to each other by hydrogen bonding to form amorphous nanostructures.
  • the transition metal and the halogen element form a main chain, and the bonding functional group bonded to the transition metal forms a side chain.
  • the transition metal has an oxidation number of +1.
  • FIG. 2 is a schematic view showing the inorganic polymer of FIG. 1 according to a preferred embodiment of the present invention.
  • certain inorganic polymers form hydrogen bonds with adjacent inorganic polymers and form nanowires according to hydrogen bonds.
  • the hydrogen bond may be made between the hydrogen element of the bonding functional group and the halogen element of another inorganic polymer or between the hydrogen element of the bonding functional group and the group 15 element or group 16 element of the other inorganic polymer.
  • the inorganic polymer is combined with the adjacent inorganic polymer and forms amorphous nanowires.
  • Cu is used as the transition metal
  • Cl is used as the halogen element
  • thiourea is used as the bonding functional group.
  • the main chain of the inorganic polymer is CuCl
  • thiourea is bonded using Cu as the center metal.
  • Sulfur (S) of thiourea forms a bond with the central metal Cu.
  • the hydrogen atom of the thiourea which forms a side chain hydrogen bonds with Cl which is a halogen element of a main chain.
  • the second is when the hydrogen atom of thiourea is hydrogen bonded to the sulfur of the side chain.
  • the hydrogen bonds cause the inorganic polymers to have a predetermined volume and form agglomerated or uniform form.
  • the amorphous nanostructure formed by the hydrogen bond may have a form of a wire, and may have a form in which a bond between a hydrogen-halogen element and a bond between a hydrogen-16 element / hydrogen-15 element is mixed.
  • Amorphous nanostructures are prepared by the following process.
  • a synthesis solution of the first metal precursor, the bonding functional group, and the polar solvent is prepared.
  • the first metal precursor includes a transition metal which may have various oxidation numbers, and includes a halogen element, which is dissolved in a polar solvent.
  • Transition metals that can be introduced are copper (Cu), manganese (Mn), iron (Fe), cadmium (Cd), cobalt (Co), nickel (Ni), zinc (Zn), mercury (Hg), molybdenum (Mo) ), Titanium (Ti), magnesium (Mg), chromium (Cr) or antimony (Sb).
  • the metal precursors also include the transition metals mentioned, including chlorides, nitrates, sulfates, acetates, acetylacetonates, formates, hydroxides, oxides or hydrates thereof with halogen elements.
  • the functional group for bonding has a hydrogen element and an element for hydrogen bonding, and a suitable functional group for bonding is a thiourea, urea, selenurea, tellurium or thiol compound.
  • the bonding functional group should have a group 15 element or a group 16 element together with a hydrogen element, so that various selections may be made as needed at the level of those skilled in the art in addition to the compounds mentioned.
  • the polar solvent prepared is for dissolving or dispersing the first metal precursor and the functional group for bonding.
  • Polar solvents that can be used include alcohols, glycols, polyglycols or water. Alcohols include methanol, ethanol, propanol or butanol.
  • polyglycols include ethylene glycol, diethylene glycol, triethylene glycol, and the like.
  • a pH adjuster may be added to the polar solvent. This adjusts the polarity of the synthetic solution composed of the dissolved first metal precursor, the bonding functional group and the polar solvent. According to the change in the polarity of the synthesis solution, the diameter or length of the prepared nanostructures may be changed to obtain various nanostructures.
  • the pH adjusting agent has an acid or a base, hydrochloric acid, hydrofluoric acid, formic acid, acetic acid, hydrocyanic acid, sulfuric acid, nitric acid, carbonic acid, amino acid, citric acid, ascorbic acid, potassium hydroxide, lithium hydroxide, sodium hydroxide, barium hydroxide, Strontium hydroxide, copper hydroxide, beryllium hydroxide, methoxylated ions, ammonia, amidated ions, methyl anions, cyanide ions, acetic acid anions or formic acid anions can be used.
  • a synthetic solution including a first metal precursor, a compound including a functional group for binding, and a polar solvent are formed.
  • pH adjusting agents may be added to the synthesis solution.
  • amorphous nanostructures in the synthesis solution through mixing, stirring, sonicating, shaking, vibrating, agitating or flowing the synthesis solution. Is prepared.
  • reaction temperature in the synthesis solution may be set to the boiling point of 0 ° C. to the polar solvent, preferably in the range of 5 ° C. to 50 ° C., and more preferably in the range of 10 ° C. to 40 ° C. Since the temperature range belongs to room temperature, those skilled in the art can induce a reaction without limiting the temperature.
  • the oxidation number of the first metal precursor decreases to have a value of +1, and a main chain of the central metal and the halogen element is formed. That is, in the state before the reaction, the transition metal constituting the first metal precursor may have various oxidation numbers, but the transition metal constituting the first metal precursor through the reaction has an oxidation number of +1, from the inorganic polymer to the center metal. Works.
  • the halogen element included in the first metal precursor is bonded to the transition metal or the center metal to form a main chain of the inorganic polymer. During the formation of the main chain, some halogen elements that do not bond with the central metal may escape and float in the ionic state in the synthesis solution.
  • the bonding functional group forms a chemical bond with the central metal.
  • the bonding group donates a lone pair of electrons to the central metal.
  • the bonding functional group has a group 15 element or a group 16 element in addition to the hydrogen element, and these elements are bonded by donating a lone pair of electrons to the center metal, and the hydrogen element forms a hydrogen bond with another synthesized inorganic polymer.
  • inorganic polymers are synthesized, and amorphous nanostructures are formed by forming hydrogen bonds between inorganic polymers.
  • the amorphous nanostructures described above may be formed of nanowires or spherical nanoparticles.
  • the subsequently formed amorphous nanostructures are mixed with a second metal precursor.
  • the amorphous nanostructures are mixed with the second metal precursor.
  • the molar ratio of the amorphous nanostructure and the second metal precursor in the polar solvent forms a fractal nano alloy structure.
  • the second metal precursor is a chloride, fluoride, bromide, iodide, nitrate, nitrite, sulfate, acetate, carbonate, citrate, cyanide, phosphate, acetylacetonate, formate, hydroxide, oxide, It may include at least one selected from the group consisting of chlorometallic acid and hydrates thereof.
  • the second metal element is required to have a standard reduction potential higher than that of the central metal having an oxidation number of +1.
  • M 1 represents a center metal of the inorganic polymer
  • M 2 represents a second metal element. Since the second metal element in the above formula has a higher reducing power than the center metal, the center metal is dissociated from the main chain with an oxidation number of +2 or more. In addition, electrons generated by dissociation of the center metal are combined with the ionized second metal element, and the ionized second metal element is reduced to the neutral second metal element.
  • the amorphous nanostructures must be completely dissociated in order to reduce the ionized second metal element. That is, the amorphous nanostructures are sufficiently dissociated to produce enough electrons to reduce the ionized second metal element, and nanoparticles composed of only the nano-sized second metal element are formed.
  • the amorphous nanostructures do not need to be completely dissociated to reduce the ionized second metal element, and may maintain the state of the inorganic polymer.
  • the amorphous nanostructures can be disassembled for reduction, at least some of the inorganic polymers are bonded to the reduced second metal element and form nano-sized alloy nanostructures.
  • a fractal structure is formed during the formation of alloy nanostructures.
  • the amount of the second precursor also needs to be prepared accordingly.
  • the second metal element is a metal different from the center metal, and has a standard reduction potential higher than the standard reduction potential of the center metal.
  • the second metal element may include gold (Au), silver (Ag), platinum (Pt), ruthenium (Ru), iridium (Ir), rhodium (Rh), palladium (Pd), osmium (Os), and cobalt ( Co, sodium (Na), potassium (K), iron (Fe), tin (Sn), magnesium (Mg), bismuth (Bi), zinc (Zn), nickel (Ni), aluminum (Al), manganese ( Mn), cadmium (Cd), lead (Pb), molybdenum (Mo), chromium (Cr), thallium (Tl), rubidium (Rb), copper (Cu), manganese (Mn), molybdenum (Mo), indium ( In), gallium (Ga), titanium (Ti) or antimony (Sb).
  • the second metal element tends to be reduced and aggregated in certain regions of the amorphous nanostructures. It is assumed that this is due to the result of the formation of the metal by rapid synthesis in the atomic unit without taking the path of rapid cooling in the molten state.
  • the transition metal is Cu
  • the second metal element is silver (Ag), gold (Au), platinum (Pt), palladium (Pd), ruthenium (Ru), osmium (Os), iridium (Ir) or Preference is given to rhodium (Rh).
  • the reaction between the amorphous nanostructure and the second metal precursor is preferably carried out in a polar solvent.
  • the polar solvent used is used for dissolving and dispersing the second metal precursor, and is preferably water, alcohol, glycol or polyglycol.
  • Alcohol-based polar solvents include methanol, ethanol, propanol or butanol
  • polyglycol-based polar solvents include ethylene glycol, diethylene glycol or triethylene glycol and the like.
  • various materials may be used as the solvent.
  • the amorphous nanostructure and the second metal precursor may be mixed, stirred, sonicated, shaking, vibrating, agitating, or flowing polar solvents. Or a combination thereof.
  • this method it is possible to uniformly disperse the amorphous nanostructure and the second metal element-containing precursor in the solvent and react with each other to form a nanostructure in the form of fractals containing the second metal element simply and quickly.
  • a plurality of second metal precursors may be formed and a high entropy alloy nanostructure in the form of a fractal may be formed. That is, fractal high-entropy alloy nanos are formed by forming second metal precursors containing two or more metals having a standard reduction potential higher than that of the central metal, and mixing two or more second metal elements by mixing and stirring them. The structure can be formed. This allows alloys of various metals to be formed in nanoscale and fractal shapes. When two or more kinds of second metal elements are mixed, the total molar ratio of the second metal elements is preferably 0.5 to 1 relative to the amorphous nanostructure.
  • the fractal high entropy alloy nanostructure is composed of two or more different metal elements and has mutually different reducing power. In addition, they have a high standard reduction potential compared to the center metal of amorphous nanostructures. Since the amorphous nanostructure can absorb two or more kinds of second metal elements on an atomic basis, it is possible to synthesize high-entropy alloy nanostructures in a fractal form in which second metal elements are uniformly mixed. Thermodynamically fractal high entropy alloy nanostructures can be formed amorphous.
  • the molar mass of the copper-chloride amorphous nanowires is 175.12 g / mol and has a yield of 70 wt% relative to the input precursor. 25 mg of CuCl 2 and 25 mg of thiourea were used, resulting in 35 mg of amorphous nanowires. Since the molar mass of the amorphous nanowire is 175.12 g / mol, 0.2 mmol of copper-chloride amorphous nanowire is finally formed.
  • gold (III) chloride solution containing 0.05 mmol of Au was dispersed in 100 ml ethanol, and then added to 100 ml of the solution containing the copper-chloride amorphous nanowire, followed by stirring for 30 minutes. I let you.
  • FIG. 3 is a STEM image and an EDS mapping image of Au atoms adsorbed to an amorphous nanostructure at an atomic level according to Preparation Example 1 of the present invention.
  • Au atoms are absorbed or adsorbed at the atomic level to copper-chloride amorphous nanowires. That is, when the molar ratio of the second metal element to the amorphous nanostructure is low, the second metal element is not sufficiently reduced to form the metal particles, and is absorbed into or inside the amorphous nanostructure in the ionic state or the partially reduced metal state. Appear as adsorbed. Below is the composition of each element in atomic percent.
  • Table 1 the atomic percentage of the structure of FIG. 3 is shown, and it can be seen that Au, the second metal element, has a relatively low atomic percentage compared to the central metal Cu.
  • the amount of Au precursor in Preparation Example 1 was increased to disperse gold (III) chloride solution containing 0.1 mmol in Au in 100 ml ethanol, and then added to the solution containing the copper-chloride amorphous nanowire, followed by stirring for 30 minutes. do.
  • FIG. 4 is a STEM image and an EDS mapping image in which Au atoms are absorbed or formed into a sphere at an atomic level according to Preparation Example 2 of the present invention.
  • the portion labeled “A” represents a state in which Au atoms and components of the inorganic polymer are formed in a fractal sphere in a specific portion of the amorphous nanostructure.
  • the portion labeled “B” shows a state in which Au atoms are absorbed or adsorbed on the pores or surfaces of the amorphous nanostructures.
  • Table 2 discloses the atomic percentage of elements in the fractal shape and the atomic percentage of elements in the absorbed state.
  • the portion indicated by A in Table 2 is the atomic percentage of the fractal structure represented by "A" of FIG. 4, and the portion indicated by B indicates that the second metal element represented by "B" of FIG. 4 is absorbed by the amorphous nanostructure or
  • the inorganic polymer constituting the amorphous nanostructure is released to reduce the Au element, and it is chemically or physically bonded to the Au element in the reduction process.
  • the amorphous nanowires are prepared in a state of 0.2 mmol in the preparation example, when the second metal element having a molar amount of 50% of the amorphous nanowires is added, it can be seen that a fractal shape appears. In the structure, various elements constituting the second metal element and the inorganic polymer appear in an aggregated state.
  • the amount of Au precursor in Preparation Example 1 was increased to disperse gold (III) chloride solution containing 0.15 mmol of Au in 100 ml ethanol, and then added to the solution containing copper-chloride amorphous nanowire, followed by stirring for 30 minutes. do.
  • FIG. 5 is a STEM image and an EDS mapping image of a fractal nanostructure including an Au element derived from an amorphous nanostructure according to Preparation Example 3 of the present invention.
  • the copper-chloride amorphous nanowires are prepared as 0.2 mmol, and the second metal element Au has a molar ratio of 75% to the amorphous nanowires.
  • the amorphous nanowire is dissociated into a form in which the inorganic polymer or the inorganic polymer is partially aggregated, aggregates into the elements constituting the inorganic polymer and the second metal element, and forms a fractal shape.
  • the amorphous nanowire is completely dissociated by oxidation of the center metal, and the elements of the separated inorganic polymers form a fractal structure with the second metal element.
  • Gold (III) chloride solution containing 0.075 mmol of Au and palladium (II) chloride solution containing 0.075 mmol of Pd were dispersed in 100 ml ethanol and stirred with the copper-chloride amorphous nanowire prepared in Preparation Example 1.
  • FIG. 6 is a STEM image and an EDS mapping image of a nanostructure including Au and Pd elements according to Preparation Example 4 of the present invention.
  • Au and Pd are added in the same molar amount, and have a total molar amount of 0.15 mmol.
  • the amorphous nanowires of Preparation Example 1 have a molar amount of 0.2 mmol
  • Au and Pd have a molar amount of 75% compared to the amorphous nanowires.
  • alloy nanostructures of fractal structure can be formed.
  • Table 4 the atomic percentage of the alloy nanostructure of FIG. 6 is disclosed.
  • Table 4 above describes the atomic percentages for the portion indicated by the dotted lines in the first image of FIG. As can be seen from the atomic composition, since the input amount of Pd is almost the same as Au, it can be seen that Au and Pd have similar atomic percentages in the alloy nanostructures.
  • Gold (III) chloride solution containing 0.1125 mmol of Au and palladium (II) chloride solution containing 0.0375 mmol of Pd were dispersed in 100 ml ethanol and stirred with copper-chloride amorphous nanowires prepared in Preparation Example 1. .
  • FIG. 7 is a SEM image and an EDS mapping image of a fractal nanostructure formed by changing a molar ratio of Au and Pd elements according to Preparation Example 5 of the present invention.
  • two kinds of second metal elements include Au and Pd.
  • the total mole number of the second metal element is 0.15 mole, representing a mole ratio of 75% to the amorphous nanowires.
  • the second metal element can form a fractal structure.
  • Au having a relatively high mole number shows a clear fractal structure, and in the case of Pd having a small number of moles, the fractal structure does not appear clearly and is distributed throughout the alloy nanostructure. have.
  • Table 5 the atomic percentage in the alloy nanostructure is disclosed by the molar imbalance introduced between the second metal elements.
  • Pd has a low atomic composition ratio even in the alloy nanostructure formed. That is, when two or more kinds of second metal elements are added, it is proportional to the amount of precursor of the second metal element used. It can form a nanostructure of fractal shape having an atomic molar ratio.
  • Au, Pd and Rh are prepared as the second metal element, and the total amount of the second metal elements is 0.15 mole, and the molar content of 75% of the amorphous nanowire of Preparation Example 1 is shown. Therefore, it is possible to produce a fractal shape.
  • FIG. 8 is a STEM image and an EDS mapping image showing a fractal-shaped nanostructure including Au, Pd, and Rh elements according to Preparation Example 6 of the present invention.
  • the fractal shape is entirely formed in the SREM image.
  • the second metal elements appear to be widely distributed rather than a clear fractal shape. This is presumed to be due to the rather low molar content of each metal element constituting the second metal element. That is, it can be seen that as the molar content of the metal element increases, it is easier to form a fractal structure.
  • the second metal element in the present embodiment, three metal elements are used as the second metal element, but more metal elements may be used as necessary. However, it is preferable that the total molar total amount of the second metal element is 50% to 100% of the amorphous nanostructure. If less than 50%, the alloy nanostructures of the fractal structure is not formed, and if it exceeds 100%, the alloy nanostructures of the fractal structure are not formed, and nanoparticles composed of only the second metal element are formed.
  • the inorganic polymer having a main metal and a halogen element as a main chain forms an amorphous nanostructure through hydrogen bonding.
  • the second metal element which has a higher standard reduction potential compared to the center metal, forms alloy nanostructures of fractal structure at a specific molar ratio.
  • the alloy nanostructure formed includes elements of a central metal, a halogen element and a bonding functional group forming an inorganic polymer.
  • the total molar amount of the second metal element exceeds a certain upper limit than the amorphous nanostructure, more electrons must be produced and consumed for the reduction of the second metal element. Thus, a phenomenon in which the inorganic polymer itself is completely dissociated occurs, and nanoparticles of only the reduced second metal elements are formed.
  • the second metal element when the total molar amount of the second metal element is less than a certain lower limit than the amorphous nanostructure, the second metal element is absorbed or adsorbed to the amorphous nanostructure in an ionized state.
  • the second metal element may be partially reduced, but the amount thereof is insignificant so that the amorphous nanostructure is not disassembled.
  • the second metal element When the total molar amount of the second metal element is greater than a certain lower limit than the amorphous nanostructure, the second metal element is reduced in earnest, and is combined with a partially disintegrated inorganic polymer on the surface of the amorphous nanostructure to form the alloy nanostructure of the fractal structure. It starts. In addition, when the total molar amount increases, the amorphous nanostructure is completely disintegrated, and a part of the disintegrated inorganic polymer is combined with the reduced second metal element to form a fractal structure.
  • the alloy nanostructure of the fractal structure includes a second metal element having a standard reduction potential higher than that of the center metal of the inorganic polymer, and includes a center metal, a halogen element, and a constituent element of the functional group for bonding.
  • the alloy nanostructures may be composed of two or more kinds of second metal elements, and thus may express various electrochemical properties.
  • forming the alloy structure in the nano size can form a uniform size due to the nature of not using a melting process, it is possible to secure a high specific surface area due to the fractal structure.

Abstract

L'invention concerne des nanostructures d'alliage à structure fractale et leur procédé de production. La structure fractale en forme de flocon de neige est formée en utilisant des nanostructures amorphes comme modèle chimique. L'invention permet d'ajouter un second élément métallique ayant un potentiel de réduction standard supérieur à celui du métal central constituant les nanostructures amorphes, ce qui permet de réduire le second élément métallique ionique, et d'augmenter le nombre d'oxydation du métal central. De plus, les nanostructures amorphes sont dissociées, et les éléments constituant le polymère inorganique forment la structure fractale conjointement avec les seconds éléments métalliques.
PCT/KR2019/001087 2018-08-21 2019-01-25 Nanostructures d'alliage fractales produites à l'aide de nanostructures amorphes et leur procédé de production WO2020040379A1 (fr)

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US20120034550A1 (en) * 2009-04-21 2012-02-09 Washington University In St. Louis Palladium-Platinum Nanostructures And Methods For Their Preparation
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