WO2019066466A1 - Nanostructure amorphe composée d'un polymère inorganique et procédé de préparation associé - Google Patents

Nanostructure amorphe composée d'un polymère inorganique et procédé de préparation associé Download PDF

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WO2019066466A1
WO2019066466A1 PCT/KR2018/011382 KR2018011382W WO2019066466A1 WO 2019066466 A1 WO2019066466 A1 WO 2019066466A1 KR 2018011382 W KR2018011382 W KR 2018011382W WO 2019066466 A1 WO2019066466 A1 WO 2019066466A1
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bonding
amorphous
hydrogen
amorphous nanostructure
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Korean (ko)
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허가현
김민석
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한국과학기술연구원
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Priority to US16/646,144 priority Critical patent/US11167262B2/en
Priority to CN201880058437.7A priority patent/CN111051390B/zh
Publication of WO2019066466A1 publication Critical patent/WO2019066466A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B01J20/28007—Sorbent size or size distribution, e.g. particle size with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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

Definitions

  • the present invention relates to an inorganic polymer, and more particularly, to an amorphous nanostructure composed of an inorganic polymer and a method for producing the same.
  • Nanomaterials having amorphous properties can be applied to various fields such as bio-field, catalyst, thermoelectric material field, electrochemical device such as secondary cell, absorber of toxic substance, and serum separation.
  • thermoelectric material such as Cu 2-x S or Cu 2-x Se may have a sudden change in the figure of merit (ZT) of the thermoelectric material depending on the fine composition change (x change).
  • the composition adjustment method is to dissolve the Cu, S or Se element to the desired composition and sinter it again, which makes it difficult to localize the composition uniformly. Further, the process of melting each of the components of the thermoelectric material consumes much time and cost. For Cu, S or Se, a melting temperature of 1400 K or more is required. In addition, it takes more time than several hours for the melting to take place over time.
  • Another method is to compound Cu with S or Se through high-energy ball milling, which is also time consuming and costly. This method is also difficult to induce a change in the local composition.
  • a first object of the present invention is to provide an amorphous nanostructure formed of an inorganic polymer and capable of local crystallization.
  • a method for fabricating an amorphous nanostructure to achieve the first technical object According to a second aspect of the present invention, there is provided a method for fabricating an amorphous nanostructure to achieve the first technical object.
  • an amorphous nanostructure comprising an inorganic polymer represented by the following general formula (1).
  • M represents a transition metal
  • X represents a halogen element
  • CF represents a bonding functional group containing a hydrogen element and a hydrogen bonding element
  • n has a value of 10 to 500,000 as the number of repetitions.
  • a method of manufacturing a semiconductor device comprising: preparing a metal precursor, a functional group for bonding, and a polar solvent; And mixing the metal precursor, the functional group for bonding and the polar solvent to form an amorphous nanostructure formed by hydrogen bonding between the inorganic polymers of Formula 1.
  • amorphous nanowires or spherical nanoparticles can be formed through a simple manufacturing method.
  • the amorphous nanostructure is formed through hydrogen bonding between inorganic polymers, and the inorganic polymer has a compound having a bonding structure of a transition metal and a halogen element in a main chain and an element capable of hydrogen and hydrogen bonding in a side chain.
  • the hydrogen contained in the side chain forms a hydrogen bond with an element capable of hydrogen bonding or a halogen element through which the inorganic polymer is combined with each other to form an amorphous nanowire.
  • the inorganic polymer may be formed into spherical nanoparticles.
  • the halogen element is excluded, and the functional group for binding having the hydrogen element and the hydrogen bonding element and the transition metal are mutually bonded.
  • the amorphous nanowires formed exhibit excellent adsorption capacity for metal ions and exhibit different crystallization behavior depending on the method of energy application.
  • the amorphous nanowires have a function of absorbing light in a specific wavelength band such as an ultraviolet region. As a result, it can be utilized as various functional materials.
  • 1 is a molecular formula for describing 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 flowchart illustrating a method of fabricating an amorphous nanostructure according to a preferred embodiment of the present invention.
  • FIG. 5 is a graph showing DSC and TGA results for the amorphous nanowires produced according to Production Example 1 of the present invention.
  • FIG. 6 is a graph showing the results of XRD analysis of the amorphous nanowires according to Production Example 1 of the present invention after heat treatment and annealing temperature.
  • 11 and 12 are EDS mapping images before and after electron beam irradiation according to Production Example 3 of the present invention.
  • 1 is a molecular formula for describing an inorganic polymer according to a preferred embodiment of the present invention.
  • M is a transition metal, the oxidation number is 1, and X means a halogen element.
  • CF is a compound having a hydrogen bonding element as a functional group for bonding and having a hydrogen bonding element capable of forming a hydrogen bond with another inorganic polymer.
  • n is 10 to 500,000 in terms of repeating units.
  • the transition metal is selected from the group consisting of copper, manganese, iron, cadmium, cobalt, nickel, zinc, mercury, molybdenum, Ti), magnesium (Mg), chromium (Cr), and antimony (Sb).
  • the halogen element may include fluorine (F), chlorine (Cl), bromine (Br), iodine (I) or a combination thereof.
  • the halogen element is bonded to the transition metal and forms a main chain in the inorganic polymer.
  • the functional group for bonding is composed of a compound having an element capable of forming a hydrogen bond with a hydrogen element and other inorganic polymer.
  • the functional group for bonding must have a hydrogen element at the end of the chemical bond.
  • This hydrogen element is bound to an element such as nitrogen (N), oxygen (O), or fluorine (F), which has a higher electronegativity than a hydrogen atom.
  • the functional group for bonding has another element which forms a hydrogen bond. Possible elements are a group 15 element or a group 16 element. They have a non-covalent electron pair and are chemically bonded to the transition metal.
  • the group 15 element or the group 16 element which can be used for the functional group for bonding includes at least one element selected from the group consisting of oxygen (O), sulfur (S), nitrogen (N), selenium (Se) and tellurium .
  • a hydrogen atom attached to an element having a high electronegativity can hydrogen bond with a non-covalent electron pair of a group 15 element or a group 16 element of another adjacent inorganic polymer. This process forms an amorphous nanostructure.
  • the functional group for bonding is preferably thiourea, urea, selenourea, tellurourea or a thiol compound.
  • the transition metal and the halogen element form a main chain, and the functional group for bonding which is 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.
  • a specific inorganic polymer forms a hydrogen bond with an adjacent inorganic polymer and forms a nanowire according to a hydrogen bond.
  • the hydrogen bond is formed by a hydrogen element present in the functional group for bonding, which is bonded to an element whose electronegativity is larger than hydrogen. That is, the hydrogen element becomes a positive charge and bonds with the non-covalent electron pair of the other inorganic polymer.
  • the hydrogen bond may be formed between a hydrogen element of a functional group for binding an inorganic polymer and a halogen element of another inorganic polymer, or may be formed between a hydrogen element of a functional group for bonding and a Group 15 element or a Group 16 element of another inorganic polymer .
  • the inorganic polymer binds to the adjacent inorganic polymer and forms an amorphous nanowire.
  • Cu is used as a transition metal
  • Cl is used as a halogen element
  • thiourea is used as a functional group for bonding. Therefore, the main chain of the inorganic polymer is CuCl, and thiourea is bound with Cu as a central metal. The sulfur (S) of thiourea forms bonds with the central metal Cu.
  • the hydrogen element has a capability of hydrogen bonding because it is bonded to a nitrogen element having a higher electronegativity.
  • the first is the case where the hydrogen atom of the thiourea forming the side chain is hydrogen-bonded to the halogen element Cl of the main chain.
  • the hydrogen atom of thiourea is hydrogen bonded to the sulfur of the side chain.
  • the inorganic polymers are aggregated or form a certain volume with a predetermined volume by hydrogen bonding.
  • the amorphous nanostructure formed by hydrogen bonding has a form of a wire, and may have a form in which a hydrogen-halogen element bond and a hydrogen-16 group element / hydrogen-15 group element bond are mixed.
  • FIG. 3 is a flowchart illustrating a method of fabricating an amorphous nanostructure according to a preferred embodiment of the present invention.
  • a metal precursor, a functional group for bonding, and a polar solvent are prepared (S100).
  • the metal precursor comprises a transition metal, and the transition metal should be capable of having multiple oxidation states.
  • the transition metals used are copper, manganese, iron, cadmium, cobalt, nickel, zinc, mercury, molybdenum, , At least one element selected from the group consisting of titanium (Ti), magnesium (Mg), chromium (Cr) and antimony (Sb).
  • the metal precursor includes the metal element and the halogen element mentioned, and has a property of dissolving in a polar solvent.
  • the metal precursor may include at least one selected from the group consisting of chloride, nitrate, sulfate, acetate, acetylacetonate, formate, hydroxide, oxide and hydrates thereof containing the transition metal, do.
  • the functional group for bonding needs to have a hydrogen element capable of hydrogen bonding and an element capable of forming a hydrogen bond with the hydrogen element.
  • Suitable functional groups for bonding are preferably thiourea, urea, selenium urea, tellurium urea or a thiol compound.
  • the functional group for bonding is most preferably a group 15 element or a group 16 element, but may include all elements of an environment capable of having a non-covalent electron pair. That is, a wide variety of choices may be possible as required by those skilled in the art besides the compounds mentioned.
  • the polar solvent to be prepared is for dissolving or dispersing the metal precursor and the functional group for bonding.
  • Polar solvents that can be used include alcoholic, glycolic, polyglycolic, or water. Alcohols include methanol, ethanol, propanol or butanol. Examples of the polyglycol system include ethylene glycol, diethylene glycol, triethylene glycol, and the like.
  • a pH adjuster may be added to the polar solvent. This controls the polarity of the synthesis solution consisting of the dissolved metal precursor, the functional group for bonding and the polar solvent. The diameter or length of the nanostructure produced according to the change of the polarity of the synthesis solution may be changed to obtain various types of nanostructures.
  • Examples of the pH regulator include acids or bases and include acids and bases such as hydrochloric acid, hydrofluoric acid, formic acid, acetic acid, hydrogensic acid, sulfuric acid, nitric acid, carbonic acid, amino acid, citric acid, ascorbic acid, potassium hydroxide, lithium hydroxide, Strontium hydroxide, copper hydroxide, beryllium hydroxide, methoxylated ion, ammonia, amidated ion, methyl anion, cyanide ion, acetic acid anion or formic acid anion may be used.
  • acids or bases include acids and bases such as hydrochloric acid, hydrofluoric acid, formic acid, acetic acid, hydrogensic acid, sulfuric acid, nitric acid, carbonic acid, amino acid, citric acid, ascorbic acid, potassium hydroxide, lithium hydroxide, Strontium hydroxide, copper hydroxide, beryllium hydroxide, methoxylated ion, ammonia, amidated
  • a synthesis solution containing a metal precursor, a functional group-containing compound for bonding and a polar solvent is formed. Also, as mentioned, a pH adjusting agent may be added to the synthesis solution.
  • the amorphous nanostructures in the synthesis solution may be prepared by mixing, stirring, sonicating, shaking, vibrating, agitating or flowing the synthesis solution. .
  • reaction temperature in the synthesis solution may be set from 0 ° C to the boiling point of the polar solvent, preferably from 5 ° C to 50 ° C, and more preferably from 10 ° C to 40 ° C. Since the temperature range is at room temperature, a person skilled in the art can induce the reaction without limit of temperature.
  • the oxidation number of the metal precursor decreases to have a value of +1, and the main chain of the center metal and the halogen element is formed. That is, the transition metal constituting the metal precursor in the state before the reaction may have various oxidation numbers of 1 or more, but the transition metal constituting the metal precursor through the reaction has an oxidation number of +1 and acts as a center metal in the inorganic polymer do. Further, the halogen element contained in the metal precursor is bonded to the transition metal or the center metal to form the main chain of the inorganic polymer. During the formation of the main chain, some halogen elements that do not bind to the center metal may be released and suspended in the ionic state in the synthesis solution.
  • the functional group for bonding also forms a chemical bond with the center metal.
  • the bonding functional group donates a non-covalent electron pair to the center metal.
  • the functional group for bonding has a group 15 element or a group 16 element in addition to a hydrogen element. These elements are bonded by donating a pair of non-covalent electrons to a central metal, and the hydrogen element forms a hydrogen bond with other synthesized inorganic polymer.
  • inorganic polymers are synthesized and amorphous nanostructures are formed by forming hydrogen bonds between inorganic polymers.
  • nanowires formed using ethanol as a polar solvent according to Production Example 1 are composed of Cu, S, N and Cl. Further, the hydrogen atom can not be identified as the XPS phase, so a description thereof is omitted.
  • the binding energy of p orbital of Cu is started in the graph of FIG. 4 (a), and since there is no distinct peak between Cu 2p 1/2 and Cu 2p 3/2 , the oxidation number of Cu is + 1. That is, Cu forms a main chain by a single bond with Cl, which is a halogen element in the periphery.
  • Graph (b) shows the state in which thiourea is bound to Cu with the detection peak of sulfur (S).
  • the graph (c) shows the presence of nitrogen, which can confirm the state of the hydrogen bonded with nitrogen in the state that the nitrogen atom of thiourea is bonded to the inorganic polymer without releasing.
  • Graph (d) shows the presence of the halogen element Cl, and graph (e) shows the state where Cu and thiourea are directly bonded.
  • the molecular formula of the inorganic polymer of FIG. 1 can be confirmed, and formation of amorphous nanowires by hydrogen bonding can be confirmed.
  • the oxidation number of Cu is mainly +1, and it can be seen that there exists a valence of Cu +1 . That is, the oxidation number of Cu in CuCl 2 is +2, but when it is synthesized with an amorphous nanostructure, the oxidation number of Cu decreases and has a value of +1, which indicates that Cu-Cl bonds are formed in the main chain of the inorganic polymer .
  • FIG. 5 is a graph showing DSC and TGA results for the amorphous nanowires produced according to Production Example 1 of the present invention.
  • DSC Different Scanning Calorimetry analysis is a function of the temperature difference between the energy of the sample and the reference material. 5
  • an exothermic reaction is observed in the vicinity of 200 ° C. This indicates that the amorphous nanowire starts crystallization at around 200 ° C.
  • the nanowire exhibits a strong endothermic reaction at around 250 ° C. This indicates that decomposition occurs according to the endothermic reaction in the synthesized amorphous nanowires. That is, some thiourea in the amorphous nanowire is separated from the main chain.
  • a TGA (Thermogravimetry) analysis is performed, which is a measurement of the mass change of the sample as a function of temperature while changing the temperature of the sample to be measured.
  • the weight is rapidly reduced at a temperature of 250 ° C. It is interpreted that the amorphous nanowire separates thiourea through endothermic action. At a temperature exceeding 250 ° C, the weight of the sample decreases gradually, and it is understood that the elements that are attached to the surface are slowly separated.
  • the amorphous nanowire of Production Example 1 has a crystallization process at 200 ° C, and the thiourea constituting the side chain of the inorganic polymer is separated by the endothermic reaction at a temperature of about 250 ° C, and the weight is rapidly reduced. There is no meaningful change in the change of the composition in the range of other temperatures.
  • FIG. 6 is a graph showing the results of XRD analysis of the amorphous nanowires according to Production Example 1 of the present invention after heat treatment and annealing temperature.
  • the amorphous nanowires of the present invention are collected by a centrifugal separator and heat-treated at 150 ° C, 200 ° C, 300 ° C, 400 ° C, and 500 ° C, respectively. Respectively. And does not have a distinct peak corresponding to the crystallized material at a temperature lower than 200 ° C.
  • distinct peaks associated with crystallization begin to appear, which is linked to the crystallization process at around 200 ° C in the DSC results of FIG. From this time, peaks corresponding to CuS 2 and Cu 2 S start to appear. This indicates that some of the inorganic polymer structures were locally crystallized into CuS 2 and Cu 2 S, respectively, with progress of crystallization.
  • FIG. 7 shows images before and after the heat treatment of amorphous nanowires according to Production Example 1 of the present invention.
  • amorphous nanowires are disclosed before heat treatment. Further, after the heat treatment is performed at 200 ⁇ ⁇ , the shape of the nanowire disappears, and the structure in which the plate-shaped structures cohere with each other is disclosed. That is, part of the Cu-Cl bonds forming the main chain are destroyed, and the nanowires are separated from each other or combined with the adjacent nanowires to form a plate-like coagulated form. However, it is considered that the coagulated form of the plate forms crystallinity, but this crystallinity does not form a perfect single crystal.
  • crystalline phases appear in a part or a substantial region of the plate-like shape, and they can be judged as polycrystals depending on the observation, or it can be judged that some crystal grains are formed in the bulk of the amorphous state. Since these are not entirely single crystals, they are referred to as amorphous nanostructures for convenience of explanation in this embodiment.
  • nanowires synthesized by using ethylene glycol (polarity 0.790), diethylene glycol (polarity 0.713) and triethylene glycol (polarity 0.704) in place of ethanol as the polar solvent in Production Example 1 are compared and observed.
  • the diameter and length of the synthesized nanowires decrease. This is due to the fact that highly polar solvents interfere with the hydrogen bonding between the inorganic polymers synthesized and prevent the bonding functional groups from participating in the synthesis. That is, it can be seen that the diameter and length of the nanostructure can be controlled by adjusting the polarity of the solvent.
  • a nano structure is synthesized by using water (polarity 1.0) instead of ethanol in Example 1 as a polar solvent. It is also compared with the nanostructures produced by Example 1.
  • ethanol polarity 1.0
  • nanowires are synthesized.
  • spherical nanoparticles having a uniform size are formed instead of the nanowire.
  • the spherical nanoparticles have a diameter of 10 nm or less. This is due to the phenomenon that a large polar solvent interferes with the bonding or formation of the polymer main chain and the bonding functional group is bonded to the central metal. For the reasons described, spherical nanoparticles are formed.
  • Table 1 shows the data of the nanowires and spherical nanoparticles prepared in FIG. 9 measured by EDS, and has an error range of ⁇ 10% due to the nature of the measurement.
  • the hydrogen atom is excluded from the measurement object.
  • the nanostructure using ethanol as a polar solvent is a nanowire type
  • Cu-Cl forms a main chain
  • S as a group 16 element is bound to Cu, which is a central metal.
  • thiourea acts as a functional group for bonding because N of thiourea has a composition ratio of 2.
  • an amorphous nanowire formed according to Production Example 1 is used as the amorphous nanowire.
  • the amorphous state is reformed locally to crystalline.
  • grain boundaries appear in the form of crystal grains.
  • the crystallized grain boundary is identified as CuCl. That is, the crystal grains are bound to CuCl, and thiourea, which contributes to the formation of amorphous nanowires, is separated from Cu, which is a center metal.
  • 11 and 12 are EDS mapping images before and after electron beam irradiation according to Production Example 3 of the present invention.
  • an EDS mapping image of an amorphous nanowire formed according to Preparation Example 1 in a state before electron beam irradiation is disclosed. Referring to FIG. 11, it can be seen that Cu, S, N and Cl are evenly distributed throughout the nanowire before the electron beam is irradiated.
  • the crystallization progresses in the local region of the nanowire after the electron beam irradiation.
  • Cl appears intensely in the crystallization region, which is a local region.
  • Cu, N and S are evenly distributed in the nanowire.
  • Cu and Cl preferentially crystallize by the irradiation of the electron beam.
  • the oxidation number of Cu keeps monovalent because the crystallized part is CuCl.
  • the halogen element Cl forming the main chain of the inorganic polymer in the amorphous nanowire synthesized in Production Example 1 is replaced with another halogen element Br, and the thiourea forming the side chain is replaced with selenium urea.
  • the production conditions of the nanowires are the same as those described in Production Example 1. [ That is, CuBr 2 and selenium urea are mixed, and ethanol is used as a polar solvent.
  • the molar concentration of the precursor used in each of the mixtures was the same as in Preparation Example 1. For example, in the experiment in which Cl in the main chain was replaced with Br, 84.6 mg of CuBr 2 and 50 mg of thiourea were mixed with 80 ml of ethanol.
  • FIG 13 shows EDS mapping images of the nanowires produced by the elements substituted according to Production Example 4 of the present invention.
  • Evaluation Example 1 Evaluation of adsorption capacity of nanowires
  • the nanowire produced according to Preparation Example 1 was confirmed to have adsorption ability to other elements or chemicals. Particularly, the adsorption capacity for a heterogeneous material is achieved by mixing a solution in which metal ions or toxic anion molecules are dissolved, with the amorphous nanowires of Production Example 1 above.
  • an adsorption EDS mapping image is shown in a solution in which 5 wt% of Pt atoms is dissolved in the nanowires prepared in Production Example 1.
  • An aqueous solution containing PtCl 4 is used to evaluate the ability of the nanowire to adsorb to the Pt atom, and nanowires are mixed in the aqueous solution.
  • the Pt atoms in the aqueous solution are dissolved in the cation at 5 wt%.
  • the EDS mapping image it can be seen that the Pt atoms are evenly adsorbed on the nanowires.
  • an EDS mapping image adsorbed on the nanowire of Production Example 1 is disclosed in a solution in which 10 wt% of Pt atoms is dissolved in the nanowire produced in Production Example 1.
  • FIG. In the EDS mapping image it can be seen that Pt atoms are evenly adsorbed on the nanowires.
  • the solution in which Pt atoms are dissolved is a solution in which PtCl 4 is dissolved in an aqueous solution.
  • 16 is a STEM image and an EDS mapping image containing Ag elements at 2.4 at.% (A), 16.1 at.%, 30.1 at.% And 85.6 at.%, Respectively.
  • the element is doped to the atomic level as shown in (A), and as the amount of the Ag precursor is increased, the island shape is formed in the nanowire like (B). If the amount of the Ag precursor is further increased, the nanowire will have a nanowire shape containing nanoparticles of several tens nanometers at the edge of the nanowire (C). If the absorption amount exceeds 40 at.%, The original shape of the nanowire disappears D).
  • 17 is an image showing the result of mixing amorphous nanowires of Production Example 1 with an aqueous solution (116 mg / l) in which K 2 CrO 4 was dissolved. 17 that molecular compounds such as chromate are well adsorbed on the nanowires.
  • the nanowire used is the amorphous nanowire according to Preparation Example 1 above.
  • Table 2 below adsorbed metals and solvents included in the materials used and the materials used are disclosed.
  • the 16 metal elements are uniformly adsorbed to the amorphous nanowires at the atomic level.
  • the amorphous nanowire can easily adsorb metal or metal ion at an atomic unit, and has adsorbability to the form of metal salt.
  • the amorphous nanowire uses the nanowire according to Production Example 1 above.
  • the absorbance is evaluated while changing the wavelength of the incident light.
  • the nanowire strongly absorbs incident light. Accordingly, it can be seen that the amorphous nanowire of the present invention can be used as an optical filter that absorbs or blocks light of a specific band.
  • amorphous nanowires or spherical nanoparticles can be formed by a simple manufacturing method.
  • a nanostructure is formed through the formed inorganic polymer.
  • the inorganic polymer has a hydrogen element attached to an element having a binding structure of a transition metal and a halogen element in the main chain and an electronegativity higher than hydrogen having a hydrogen bonding ability in the side chain . It also has Group 15 and Group 16 elements used for hydrogen bonding.
  • the hydrogen contained in the side chain forms a hydrogen bond with an element capable of hydrogen bonding or a halogen element through which the inorganic polymer is combined with each other to form an amorphous nanowire.
  • the inorganic polymer may be formed into spherical nanoparticles.
  • the halogen element is excluded, and the functional group for binding having the hydrogen element and the hydrogen bonding element and the transition metal are mutually bonded.
  • the amorphous nanowires formed exhibit excellent adsorption ability to metal ions and crystallize into other phases upon application of energy.
  • the amorphous nanowires have a function of absorbing light in a specific wavelength band such as an ultraviolet region. As a result, it can be utilized as various functional materials.

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Abstract

L'invention concerne une nanostructure amorphe et un procédé de préparation de la nanostructure amorphe. La nanostructure amorphe présente un métal de transition et un atome d'halogène dans sa chaîne principale et le métal de transition présente un nombre d'oxydation de +1. De plus, un polymère inorganique formant la nanostructure amorphe forme une liaison hydrogène avec un polymère inorganique adjacent. Le polymère inorganique présente, dans sa chaîne latérale, de l'hydrogène et un élément pour une liaison hydrogène afin de former une liaison hydrogène. Diverses caractéristiques peuvent ainsi être identifiées.
PCT/KR2018/011382 2017-09-29 2018-09-27 Nanostructure amorphe composée d'un polymère inorganique et procédé de préparation associé WO2019066466A1 (fr)

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