WO2019066466A1 - Amorphous nanostructure composed of inorganic polymer, and preparation method therefor - Google Patents

Abstract

An amorphous nanostructure and a method for preparing the amorphous nanostructure are disclosed. The amorphous nanostructure has a transition metal and a halogen atom in the main chain thereof, and the transition metal has an oxidation number of +1. In addition, an inorganic polymer forming the amorphous nanostructure forms a hydrogen bond with an adjacent inorganic polymer. The inorganic polymer has, in the side chain thereof, hydrogen and an element for a hydrogen bond in order to form a hydrogen bond. Various characteristics can be identified thereby.

Description

Amorphous nanostructure comprising inorganic polymer and method for producing the same

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.

In the field of thermoelectric materials, the 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).

Currently, 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.

Therefore, it is required to develop an amorphous nano structure that can be applied to various application fields and can control the composition of the crystallization material.

A first object of the present invention is to provide an amorphous nanostructure formed of an inorganic polymer and capable of local crystallization.

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.

According to an aspect of the present invention, there is provided an amorphous nanostructure comprising an inorganic polymer represented by the following general formula (1).

[Chemical Formula 1]

In the above 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, and n has a value of 10 to 500,000 as the number of repetitions.

According to another aspect of the present invention, there is provided 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.

According to the present invention described above, 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. In addition, depending on the polarity of the polar solvent introduced in the formation process, the inorganic polymer may be formed into spherical nanoparticles. When formed of 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. In addition, 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.

2 is a schematic view showing the inorganic polymer of FIG. 1 according to a preferred embodiment of the present invention.

3 is a flowchart illustrating a method of fabricating an amorphous nanostructure according to a preferred embodiment of the present invention.

4 is XPS analysis graphs of amorphous nanowires according to Production Example 1 of the present invention.

5 is a graph showing DSC and TGA results for the amorphous nanowires produced according to Production Example 1 of the present invention.

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.

7 is SEM images showing the amorphous nanowires before and after the heat treatment according to Production Example 1 of the present invention.

8 is an SEM image of the nanowires produced in Production Example 2 of the present invention at the same magnification.

9 is an image showing the produced nanostructure using ethanol and water as a polar solvent according to Production Example 2 of the present invention.

10 is an image showing a state of crystallization in an amorphous nanowire according to Production Example 3 of the present invention.

11 and 12 are EDS mapping images before and after electron beam irradiation according to Production Example 3 of the present invention.

13 is EDS mapping images of nanowires made by the elements substituted according to Production Example 4 of the present invention.

14 to 17 are images showing the adsorption capability of nanowires of Production Example 1 according to Evaluation Example 1 of the present invention.

18 is images showing nanowires adsorbing various metals according to Evaluation Example 1 of the present invention.

19 is a graph showing the results of UV-Vis absorption analysis of amorphous nanowires according to Evaluation Example 2 of the present invention.

The present invention is capable of various modifications and various forms, and specific embodiments are illustrated in the drawings and described in detail in the text. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. Like reference numerals are used for like elements in describing each drawing.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Example

1 is a molecular formula for describing an inorganic polymer according to a preferred embodiment of the present invention.

Referring to FIG. 1, 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).

Further, 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.

In particular, 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. For this purpose, 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. In addition, 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.

In the inorganic polymer, 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. In particular, the transition metal has an oxidation number of +1.

2 is a schematic view showing the inorganic polymer of FIG. 1 according to a preferred embodiment of the present invention.

Referring to FIG. 2, 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. Specifically, 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 . Through this, the inorganic polymer binds to the adjacent inorganic polymer and forms an amorphous nanowire.

More specifically, in FIG. 1, Cu is used as a transition metal, Cl is used as a halogen element, and 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.

2, two kinds of hydrogen bonds for forming an amorphous nanostructure are formed. In FIG. 2, 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. Secondly, the hydrogen atom of thiourea is hydrogen bonded to the sulfur of the side chain. In either case, the inorganic polymers are aggregated or form a certain volume with a predetermined volume by hydrogen bonding. In addition, 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.

3 is a flowchart illustrating a method of fabricating an amorphous nanostructure according to a preferred embodiment of the present invention.

First, 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).

In addition, the metal precursor includes the metal element and the halogen element mentioned, and has a property of dissolving in a polar solvent. For example, 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. However, 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.

In addition, 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.

Through the above-described process, 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.

Next, a process for producing an amorphous nanostructure using a synthesis solution is disclosed (S200).

For example, the amorphous nanostructures in the synthesis solution may be prepared by mixing, stirring, sonicating, shaking, vibrating, agitating or flowing the synthesis solution. .

Also, the 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.

In the present reaction, 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. In the bonding process, the bonding functional group donates a non-covalent electron pair to the center metal. Particularly, 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.

In this way, inorganic polymers are synthesized and amorphous nanostructures are formed by forming hydrogen bonds between inorganic polymers.

Production Example 1: Synthesis of amorphous nanowire

Captured the 50 mg of CuCl ₂ and 50 mg of thiourea powder in a beaker. CuCl ₂ is used as a metal precursor, and the oxidation number of Cu is +2. Further, thiourea is used as a functional group for bonding. Add 80 ml to the beaker using ethanol as a polar solvent. The synthesis solution in which CuCl ₂ , thiourea and ethanol are mixed is ultrasonically dispersed at room temperature. Ultrasonic dispersion is performed for 1 minute to 2 minutes, through which amorphous nanowires are synthesized.

4 is XPS analysis graphs of amorphous nanowires according to Production Example 1 of the present invention.

Referring to FIG. 4, it can be seen that 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. First, 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.

As a result, the molecular formula of the inorganic polymer of FIG. 1 can be confirmed, and formation of amorphous nanowires by hydrogen bonding can be confirmed.

In particular, it can be seen that Cu and Cl form a chemical bond and a bond exists between Cu and thiourea. In addition, 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 .

5 is a graph showing DSC and TGA results for the amorphous nanowires produced according to Production Example 1 of the present invention.

Referring to FIG. 5, DSC (Differential 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. In addition, 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.

Also, referring to FIG. 5, 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. In FIG. 5, 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. That is, 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.

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.

Referring to FIG. 6, 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. At 200 ° C and above, 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. In this process, however, there are no distinct peaks corresponding to the two crystal phases. It was found that the thiourea was decomposed at about 250 ° C in FIG. 5 to cause a sudden change in mass, which simultaneously means loss of sulfur (S) atoms. That is, it means that the original consumption of Cu is larger than that of S. In fact, when the heat treatment is performed at 300 ° C, the peak of CuS _{2 with} a large amount of sulfur disappears and only a peak corresponding to Cu _7.2 S ₄ appears. In addition, a stable crystallization bond between Cu and S appears due to the apparent crystallization peak. In addition, it can be seen that the original consumption of Cu is finer than that of S in the heat treatment at 400 ° C and 500 ° C. In FIG. 5, it was found that the weight was gradually decreased at a temperature exceeding 250 ° C, which seems to be due to loss in S. In other words, S is slightly lost and the phase change is made to Cu ₂ S with a large fraction of Cu in Cu _7.2 S ₄ . That is, the amorphous nanowire of Production Example 1 is crystallized through heat treatment, and the original consumption between Cu and S can be controlled by changing the crystallization temperature.

FIG. 7 shows images before and after the heat treatment of amorphous nanowires according to Production Example 1 of the present invention.

Referring to FIG. 7, amorphous nanowires are disclosed before heat treatment. Further, after the heat treatment is performed at 200 占 폚, 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. That is, 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.

Production Example 2: Change in shape and composition of nanostructure according to polarity of solvent

The length and diameter of 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.

8 is an SEM image of the nanowires produced in Production Example 2 of the present invention at the same magnification.

Referring to FIG. 8, it can be seen that as the polarity of the solvent increases, 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.

9 is an image showing the produced nanostructure using ethanol and water as a polar solvent according to Production Example 2 of the present invention.

Referring to FIG. 9, 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. As shown in the left image of FIG. 9, when ethanol is used as a polar solvent, nanowires are synthesized. On the other hand, when looking at the image on the right side where water having a large polarity is used as a polar solvent, 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 below 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. For convenience of explanation, the hydrogen atom is excluded from the measurement object.

Kinds Atomic composition ratio of Cu: S: N: Cl The nanowires synthesized in ethanol 1: 1: 2: 1 Spherical nanoparticles synthesized in water 6: 3: 1: 0

Referring to Table 1, it can be seen that the nanostructure using ethanol as a polar solvent is a nanowire type, Cu-Cl forms a main chain, and S as a group 16 element is bound to Cu, which is a central metal. Further, it can be seen that thiourea acts as a functional group for bonding because N of thiourea has a composition ratio of 2.

In the case of spherical nanoparticles synthesized in water, Cl is not detected. This is a very unusual phenomenon, meaning that the main chain of Cu-Cl is not formed, and that Cl acts as a bridge for nanowire synthesis. That is, it can be seen that Cl dominates longitudinal growth. In addition, it can be seen that the spherical nanoparticles are formed in a form in which the transition metal and the group 16 element are bonded to each other.

Production Example 3: Crystallization by nanowire electron beam

In this production example, local crystallization of the amorphous nanowire formed in Production Example 1 is performed. An electron beam is irradiated for crystallization, and the crystallization state is confirmed.

10 is an image showing a state of crystallization in an amorphous nanowire according to Production Example 3 of the present invention.

Referring to FIG. 10, an amorphous nanowire formed according to Production Example 1 is used as the amorphous nanowire. When an electron beam is incident on an amorphous nanowire and energized, the amorphous state is reformed locally to crystalline. In the image of FIG. 10, grain boundaries appear in the form of crystal grains. Also, 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.

Referring to FIG. 11, 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.

Referring to FIG. 12, it can be seen that the crystallization progresses in the local region of the nanowire after the electron beam irradiation. In particular, Cl appears intensely in the crystallization region, which is a local region. It can also be seen that Cu, N and S are evenly distributed in the nanowire. It can be seen that Cu and Cl preferentially crystallize by the irradiation of the electron beam. It can be seen that the oxidation number of Cu keeps monovalent because the crystallized part is CuCl.

In Fig. 6, local crystallization takes place in the form of CuCl by the electron beam in case the crystallization occurs between Cu and S by heat. It is a peculiar phenomenon to be able to crystallize in different forms as the source of energy is varied and it can be used for various applications.

Production Example 4: Elemental substitution of amorphous nanowires

In this production example, 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.

13 shows EDS mapping images of the nanowires produced by the elements substituted according to Production Example 4 of the present invention.

Referring to FIG. 13, it can be seen that Br is used instead of Cl as a halogen element and is uniformly distributed in the nanowire together with Cu. It can also be seen that the element Se in the selenium urea is evenly distributed in the nanowire as a group 16 element. The transition metal and the halogen element are chemically bonded to form a main chain. The transition metal is bonded to the transition metal through a bond sharing a non-covalent electron pair, and a group 16 element is bonded to the transition metal. It is possible to form a nanostructure through the nanostructure.

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.

14 to 17 are images showing the adsorption capability of nanowires of Production Example 1 according to Evaluation Example 1 of the present invention.

Referring to Fig. 14, 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%. In the EDS mapping image, it can be seen that the Pt atoms are evenly adsorbed on the nanowires.

Referring to FIG. 15, 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. When the amount of the Ag precursor is less than 5 at.%, 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.

18 is images showing nanowires adsorbing various metals according to Evaluation Example 1 of the present invention.

Referring to FIG. 18, the nanowire used is the amorphous nanowire according to Preparation Example 1 above. In addition, in Table 2 below, adsorbed metals and solvents included in the materials used and the materials used are disclosed.

Adsorption metal Substances used amount Used solvent Ag Silver nitrate (≥99.0%) 4 mg Ethanol 30 ml Au Gold (III) chloride (99%) 8 mg Ethanol 30 ml Bi Bismuth (III) chloride (≥98%) 8 mg Ethanol 30 ml CD Cadmium nitrate tetrahydrate (98%) 8 mg Ethanol 30 ml Ce Cerium chloride heptahydrate (≥98%) 9 mg Ethanol 30 ml Cs Cesium chloride (99.9%) 4 mg Ethanol 30 ml Fe Iron (III) chloride (97%) 4 mg Ethanol 30 ml Gd Gadolinium (III) chloride (99.99%) 7 mg Ethanol 30 ml Ir Iridium (III) chloride hydrate (99.9%) 9 mg Ethanol 25 ml + Water 5 ml Mg Magnesium acetate tetrahydrate (≥98%) 5 mg Ethanol 30 ml Na Sodium nitrate (≥99%) 2 mg Ethanol 25 ml + Water 5 ml Pb Lead (II) nitrate (≥99%) 8 mg Ethanol 25 ml + Water 5 ml Pd Palladium (II) chloride (99%) 4 mg Ethanol 25 ml + Water 5 ml Pt Chloroplatinic acid solution (8 wt.% In H2O) 0.12 ml Ethanol 30 ml Ru Ruthenium chloride hydrate (99.98%) 7 mg Ethanol 30 ml Te Telluric acid (98%) 6 mg Ethanol 25 ml + Water 5 ml

Referring to FIG. 18 and Table 2, it can be seen that the 16 metal elements are uniformly adsorbed to the amorphous nanowires at the atomic level. As a result, the amorphous nanowire can easily adsorb metal or metal ion at an atomic unit, and has adsorbability to the form of metal salt.

Evaluation Example 2: UV-Vis absorbance analysis of synthesized nanowires

In this evaluation example, the absorbance of the amorphous nanowire according to Production Example 1 is analyzed.

19 is a graph showing the results of UV-Vis absorption analysis of amorphous nanowires according to Evaluation Example 2 of the present invention.

Referring to FIG. 19, the amorphous nanowire uses the nanowire according to Production Example 1 above. The absorbance is evaluated while changing the wavelength of the incident light. At 250 to 400 nm of 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.

In the present invention, 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. In addition, depending on the polarity of the polar solvent introduced in the formation process, the inorganic polymer may be formed into spherical nanoparticles. When formed of 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. In addition, 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.

Claims (20)

An amorphous nanostructure comprising an inorganic polymer represented by the following formula (1). [Chemical Formula 1]

In the above 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, and n has a value of 10 to 500,000 as the number of repetitions. The method of claim 1, wherein the transition metal is selected from the group consisting of copper, manganese, iron, cadmium, cobalt, nickel, zinc, mercury, Wherein the amorphous nanostructure is at least one selected from the group consisting of molybdenum (Mo), titanium (Ti), magnesium (Mg), chromium (Cr) and antimony (Sb). The amorphous nanostructure according to claim 1, wherein the halogen element is fluorine (F), chlorine (Cl), bromine (Br), iodine (I) or a combination thereof. The amorphous nanostructure according to claim 1, wherein the functional group for bonding has the hydrogen element and the hydrogen bonding element, and the hydrogen bonding element donates a non-covalent electron pair to the transition metal. The hydrogen-bonding element according to claim 4, wherein the element for hydrogen bonding has a group 15 element or a group 16 element and is composed of oxygen (O), sulfur (S), nitrogen (N), selenium (Se), and tellurium Wherein the amorphous nanostructure is at least one element selected from the group consisting of amorphous and amorphous. The amorphous nanostructure according to claim 4, wherein the functional group for bonding has thiourea, urea, selenourea, tellurourea or a thiol compound. The amorphous nanostructure according to claim 1, wherein the hydrogen of the functional group for bonding forms a hydrogen bond with a hydrogen bonding element or a halogen element of a bonding functional group of another adjacent inorganic polymer. Preparing a metal precursor, a functional group for bonding, and a polar solvent; And And forming an amorphous nanostructure formed by hydrogen bonding between the inorganic polymers of the following formula (2) through a synthesis solution in which the metal precursor, the functional group for bonding, and the polar solvent are mixed. (2)

In Formula 2, M represents a transition metal, X represents a halogen element, CF represents a functional group for binding including a hydrogen element and a hydrogen bonding element, and n has a value of 10 to 500,000 in terms of repetition number. 9. The method of claim 8, wherein the metal precursor comprises a transition metal and a halogen element. The method of claim 9, wherein the transition metal is selected from the group consisting of copper (Cu), manganese (Mn), iron (Fe), cadmium (Cd), cobalt (Co), nickel (Ni), zinc (Zn) Wherein at least one element selected from the group consisting of molybdenum (Mo), titanium (Ti), magnesium (Mg), chromium (Cr) and antimony (Sb) is contained. 11. The method of claim 10, wherein the metal precursor comprises at least a transition metal selected from the group consisting of chloride, nitrate, sulfate, acetate, acetylacetonate, formate, hydroxide, oxide and hydrates thereof, Wherein the amorphous nanostructure is formed on the surface of the amorphous nanostructure. The method according to claim 8, wherein the element for hydrogen bonding of the functional group for bonding is at least one element selected from the group consisting of oxygen (O), sulfur (S), nitrogen (N), selenium (Se) Wherein the amorphous nanostructure is an element. 13. The amorphous nanostructure according to claim 12, wherein the functional group for bonding is selected from the group consisting of thiourea, urea, selenourea, tellurourea, or a thiol compound. Gt; The method according to claim 8, wherein the hydrogen of the functional group for bonding forms a hydrogen bond with a hydrogen bonding element or a halogen element of a bonding functional group of another adjacent inorganic polymer. The method for producing an amorphous nanostructure according to claim 8, wherein the polar solvent comprises an alcohol-based solvent, a glycol-based solvent, a polyglycol-based solvent or water. The amorphous nanostructure according to claim 15, wherein as the polarity of the polar solvent increases, the bond between the halogen element and the transition metal breaks and the spherical nanoparticles in which the halogen element is removed are formed Way. The method for producing an amorphous nanostructure according to claim 8, wherein the transition metal of the metal precursor has a multivalent oxidation number, and the oxidation number is reduced by synthesis of the inorganic polymer to have an oxidation number of +1. 9. The method of claim 8, further comprising the step of forming a plate-like crystal phase by breaking bonds of the main chain of the inorganic polymer through heat treatment of the amorphous nanostructure after the step of forming the amorphous nanostructure A method for producing an amorphous nanostructure. The method of claim 8, further comprising the step of irradiating the amorphous nanostructure with an electron beam to crystallize the irradiated region after forming the amorphous nanostructure. 20. The method of claim 19, wherein the synthesis of the amorphous nanostructure comprises mixing, stirring, sonicating, shaking, vibrating, stirring (stirring), stirring agitating < / RTI > or flowing of the amorphous nanostructure.

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