KR102052533B1 - Oxide or hydroxide nanostructure on metal surface and synthesis method of the same - Google Patents

Abstract

The present invention relates to a method for synthesizing an oxide or hydroxide nanostructure on a metal surface using corrosion and to an oxide or hydroxide nanostructure synthesized by the method.

Description

Oxide or hydroxide nanostructures on metal surfaces and methods for their synthesis {OXIDE OR HYDROXIDE NANOSTRUCTURE ON METAL SURFACE AND SYNTHESIS METHOD OF THE SAME}

The present application relates to a method for synthesizing an oxide or hydroxide nanostructure on a metal surface using corrosion, and to an oxide or hydroxide nanostructure synthesized by the method.

Nanostructure generally refers to an architecture in which nanoparticles, nanorods, or nanoplates with a size ranging from about 1 nm to about 1 μm are combined. These nanostructures can be widely used in various fields such as catalysts, pharmaceuticals, paint industry, self-assembly materials, and nonlinear optical materials. In addition, when the nanostructure is formed, it is easy to handle because its size is increased to about several hundred nm to several micrometers, and it is very useful because it retains various properties exhibited when it is a nanoparticle. Accordingly, research on nanostructures is being actively conducted.

However, in order to prepare a nanostructure consisting of these nano-size particles are combined, complex processes such as a surfactant and a support are not only necessary, but also easy to control the shape and additional washing process is inevitable. Therefore, a lot of studies on the synthesis of nanostructures have been reported, but the amount produced is about several milligrams, there are many problems to use in the actual industry.

One of the existing synthetic methods for forming nanostructures, urea-based synthesis has a problem in that environmentally friendly elements are inferior in that organic solvents are used. In order to solve the above problems, it is required to develop a nanostructure synthesis method of hydroxide on the surface of the metal through a simple process as an environmentally friendly condition that does not use organic solvents, organic stabilizers, binders and the like.

On the other hand, Korean Patent Laid-Open Publication No. 10-2009-0091571 relates to "three-dimensional nanostructures of phosphate-based hydroxides and a method for producing the same," wherein the three-dimensional nanostructures are weighed and mixed with a metal compound and a phosphorous compound, the mixed compound It discloses about the compound produced by adjusting the pH (pH) of 3-9, and reacting the compound which pH controlled.

The present application is to provide a method for synthesizing an oxide or hydroxide nanostructure on a metal surface using corrosion and an oxide or hydroxide nanostructure synthesized by the method.

However, the problem to be solved by the present application is not limited to the above-mentioned problem, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

One aspect of the present application, the step of reducing the surface of the metal formed on the substrate to corrode; And growing an oxide or hydroxide nanostructure on the corroded metal surface in a solvent.

Another aspect of the present disclosure provides a hydroxide nanostructure synthesized by the method according to one aspect of the disclosure on a substrate surface.

According to one embodiment of the present invention, oxides on the metal surface using an easy manufacturing method using only water or deionized water without the use of additional organic solvents, organic stabilizers, and binders and corrosion occurring on the metal surface at low cost Alternatively, a synthesis method of growing a hydroxide nanostructure may be provided, and when a corrosion additive is used, the synthesis time of the hydroxide nanostructure may be shortened.

According to one embodiment of the present application, ethanol, binder, urea, organic solvent, and the like, which are widely used in a synthesis method of growing hydroxide nanostructures on a conventional metal surface, do not use water, Alternatively, a new synthetic method using deionized water as a solvent may be provided.

When using the synthesis method according to an embodiment of the present application, it is possible to grow the oxide or hydroxide nanostructures in the form of nanowalls (rods) or the like on the metal surface, there is no environmental pollution, in the conventional method The manufacturing cost is much lower than that of the commercialization limit, and can be used in fields such as supercapacitors and oxygen revolution catalysts.

Figure 1 (a) is a schematic diagram of a hydroxide nanostructure synthesized by the method according to an embodiment of the present application, Figure 1 (b) is a scanning electron microscope (SEM) of the hydroxide nanostructure according to an embodiment of the present application ) Image.
2 is a schematic diagram showing the synthesis of hydroxide nanostructures using corrosion in one embodiment of the present application.
3 is a surface SEM image before synthesis of various metals, in one embodiment of the present disclosure.
FIG. 4 is a SEM image of a hydroxide nanostructure synthesized using only ultrapure water over time according to one embodiment of the present disclosure.
FIG. 5 is an SEM image of hydroxide nanostructures of nickel foam synthesized using various corrosion additives in one embodiment of the present disclosure.
FIG. 6A is an SEM image of hydroxide nanostructures of (a) nickel foil and (b) aluminum foil synthesized using a chloride based corrosion additive, in one embodiment of the present disclosure.
FIG. 6B is an SEM image of the hydroxide nanostructures synthesized using acetate based corrosion additives, in one embodiment of the present disclosure. FIG.
Figure 7 is a spectrum showing the X-ray diffraction (XRD) pattern of the hydroxide nanostructures synthesized according to an embodiment of the present application.
8 is a graph of oxidation / reduction reaction CV (cyclic voltammogram) of Ni (OH) ₂ in one embodiment of the present application.

Hereinafter, with reference to the accompanying drawings will be described in detail the embodiments and embodiments of the present application to be easily carried out by those of ordinary skill in the art. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and like reference numerals designate like parts throughout the specification.

Throughout this specification, when a portion is "connected" to another portion, this includes not only "directly connected" but also "electrically connected" with another element in between. do.

Throughout this specification, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

Throughout this specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding the other components unless specifically stated otherwise.

As used herein, the terms "about", "substantially", and the like, are used at, or in close proximity to, numerical values when manufacturing and material tolerances inherent in the meanings indicated are provided to aid the understanding herein. In order to prevent the unfair use of unscrupulous infringers.

As used throughout this specification, the term “step to” or “step of” does not mean “step for”.

Throughout this specification, the term "combination (s) thereof" included in the representation of a makushi form refers to one or more mixtures or combinations selected from the group consisting of the components described in the representation of makushi form, It means to include one or more selected from the group consisting of the above components.

Throughout this specification, the description of "A and / or B" means "A or B, or A and B."

Hereinafter, embodiments of the present disclosure have been described in detail, but the present disclosure may not be limited thereto.

One aspect of the present application, the step of reducing the surface of the metal formed on the substrate to corrode; And growing an oxide or hydroxide nanostructure on the corroded metal surface in a solvent.

In one embodiment of the present application, the metal is Ni, Al, Cu, Co, Mn, Fe, Na, K, Ru, Au, Pt, Sn, Pd, Zn, Ti, Ir, Ce, and combinations thereof It may be to include one selected from the group consisting of, but is not limited thereto.

In one embodiment of the present application, the solvent may include water, but is not limited thereto. For example, the water may include ultrapure water, but is not limited thereto. The method of synthesizing the oxide or hydroxide nanostructure may be to form an oxide or hydroxide nanostructure on the surface of the metal by corroding the metal using only water or ultrapure water without using a reducing agent. Since the synthesis method uses only water or ultrapure water without using organic materials and precursors, it is an environmentally friendly synthetic condition. Particularly, in the conventional synthetic method, the organic solvent, organic stabilizer, and binder are synthesized using environmentally harmful substances. However, the synthetic method according to the exemplary embodiment of the present application does not use the substances and is harmless to the environment without water or ultrapure water. By using only and / or corrosion additives, it can be synthesized by growing oxide or hydroxide nanostructures on the metal surface through corrosion of the metal in an environmentally friendly, inexpensive, and easy manner.

In one embodiment of the present application, the substrate may include any material capable of corrosion reaction by the water or the ultrapure water and can give a cation. For example, the substrate may be in the form of a foil, a foam, or a deposition film, but is not limited thereto.

In one embodiment of the present application, the step of reducing the surface of the metal to corrode, may further include adding a halogen-based precursor or acetate-based precursor containing a metal ion as a corrosion additive, but is not limited thereto. no. The halogen-based precursor or acetate-based precursor containing the metal ion may be represented by the formula MX _n (M may be a metal, for example, Ni, Al, Cu, Co, Mn, Fe, Na, K, Ru, Au, Pt , Sn, Pd, Zn, Ti, Ir, or Ce, X can be halogen or acetate, for example, can be F, Cl, Br, I, or OCOCH ₃ , n is 1, 2 , Or 3), but is not limited thereto. For example, in the above formula, M may be used without limitation so long as it is a substance capable of bonding with halogen or acetate.

For example, the corrosion additive is NaCl, KCl, CoCl, MnCl, FeCl, CoCl ₂ , MnCl ₂ , FeCl ₂ , CuCl ₂ , AlCl ₃ , FeCl ₃ , FeCl ₂ , RuCl ₂ , PtCl, Na ₂ PtCl ₆ H ₂ O, AuCl, HAuCl ₄ , ZnCl ₂ , SnCl ₂ , PdCl ₂ , Ni (OCOCH ₃ ) ₂ , Co (OCOCH ₃ ) ₂ , Mn (OCOCH ₃ ) ₂ , CeCl ₃ , mixtures thereof, and combinations thereof It may be a material selected from the group consisting of, but is not limited thereto. As the corrosion additive, any precursor capable of corrosion such as a halogen-based precursor or an acetate-based precursor containing metal ions may be used without limitation. The halogen-based precursor may be one containing F, Cl, Br, or I.

The corrosion additive may promote corrosion of the metal to reduce the synthesis time of the oxide or hydroxide nanostructure. The hydroxide nanostructures may be synthesized by reacting metal ions with water or deionized water as in Scheme 1 or 2 below:

Scheme 1

2M + O ₂ + 2H ₂ O → 2M (OH) ₂ ;

Scheme 2

4M + 3O ₂ + 6H ₂ O → 4M (OH) ₃ ;

In Schemes 1 and 2, M is a divalent or trivalent metal, respectively.

In one embodiment of the present application, the oxide or hydroxide nanostructures may include, but are not limited to, growth in a 0-dimensional, 1-dimensional, 2-dimensional, or 3-dimensional structure.

In one embodiment of the present application, the oxide or hydroxide nanostructures are nanoparticles (nanoparticle), nanorod (nanorod), nanosheet (nanosheet), nanowall (nanowall), nanocube (nanocube), nanoflower (nanoflower) It may include, but is not limited to, growth in a form selected from the group consisting of, and combinations thereof, Preferably, the oxide or hydroxide nanostructures are nanowalls (nanowall) or nanorods (nanorod) ) May be grown in the form, but is not limited thereto. For example, the 0-dimensional structure may mean the nanoparticle (nanoparticle) form, the one-dimensional structure may mean the nanorod (nanorod) form, the two-dimensional structure is the nanosheet (Nanosheet) or nanowall (nanowall) may mean the form, the three-dimensional structure may mean the nanocube (nanocube) or nanoflower (nanoflower) form, but is not limited thereto.

FIG. 2 illustrates a schematic diagram of a hydroxide nanostructure according to an exemplary embodiment of the present disclosure, and specifically illustrates a process of forming hydroxide nanowalls on a metal substrate.

For example, the hydroxide may include layered double hydroxide, but is not limited thereto.

In one embodiment of the present application, the oxide or hydroxide may be synthesized by reacting the metal and the solvent, but is not limited thereto.

In one embodiment of the present application, the step of growing the oxide or hydroxide nanostructures, may be performed at a temperature in the range of about 0 ℃ to about 100 ℃, but is not limited thereto. For example, the temperature may be about 0 ° C. to about 100 ° C., about 0 ° C. to about 95 ° C., about 0 ° C. to about 85 ° C., about 0 ° C. to about 75 ° C., about 0 ° C. to about 65 ° C., about 0 ° C. To about 55 ° C, about 0 ° C to about 45 ° C, about 0 ° C to about 35 ° C, about 0 ° C to about 25 ° C, about 0 ° C to about 15 ° C, about 15 ° C to about 100 ° C, about 25 ° C to about 100 ° C., about 50 ° C. to about 100 ° C., or about 75 ° C. to about 100 ° C., but is not limited thereto.

Another aspect of the present disclosure provides an oxide or hydroxide nanostructure synthesized by the method according to one aspect of the disclosure on a substrate surface. Another aspect of the present application may apply all the contents described with respect to the above-described aspect.

Figure 1 (a) is a schematic diagram of the nano-wall hydroxide nanostructures according to an embodiment of the present application, Figure 1 (b) is a scanning electron microscope (SEM) of the hydroxide nanostructures synthesized according to an embodiment of the present application ) Image.

In one embodiment of the present application, the substrate may include any material capable of corrosion reaction by the water or ultrapure water and the cation. For example, the substrate may be in the form of a foil, a foam, or a deposition film, but is not limited thereto.

In one embodiment of the present disclosure, the substrate is Ni, Al, Cu, Co, Mn, Fe, Na, K, Ru, Au, Pt, Sn, Pd, Zn, Ti, Ir, Ce, and combinations thereof It may be to include a metal selected from the group consisting of, but is not limited thereto.

In one embodiment of the present application, the oxide or hydroxide nanostructures may be grown to include a structure of 0 to 3 dimensions, but is not limited thereto.

In one embodiment of the present application, the oxide or hydroxide nanostructures include growing in the form selected from the group consisting of nanoparticles, nanorods, nanosheets, nanowalls, nanocubes, nanoflowers, and combinations thereof. This may be, but is not limited thereto. Preferably, the growth may be performed in the form of nanowalls or nanorods, but is not limited thereto. For example, the 0-dimensional structure may mean the nanoparticle form, the one-dimensional structure may mean the nanorod form, and the two-dimensional structure means the nanosheet or nanowall form. The three-dimensional structure may mean the nanocube or nanoflower form, but is not limited thereto.

The oxide or hydroxide nanostructures according to one embodiment of the present application may be utilized in the field of supercapacitors or oxygen reduction catalysts.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

[ Example ]

[ Example  One]

Synthesis of Hydroxide Nanostructures

Nickel foam (Ni foam, Welcos Co., Ltd.) (0.8 mm x 400 mm x 500 mm), nickel foil (Ni foil, Niraco Co., Ltd.), and aluminum foil (Al foil) were used as the metal substrate of this example. 3 shows a metal surface SEM image before synthesis of the metals. (A) and (b) of FIG. 3 are surface SEM images of nickel foam, (c) and (d) of FIG. 3 are surface SEM images of nickel foil, and (e) and (f) of FIG. Surface SEM image of the foil.

The metal was supported in 30 mL of deionized water, and then stirred at a speed of 300 rpm at a temperature of 95 ° C., which was maintained for 7 days and reacted. The surface of the stirred metal was washed with ultrapure water and dried to synthesize a hydroxide nanostructure.

FIG. 4 is an SEM image of a hydroxide nanostructure synthesized using nickel foam as the metal, and specifically, (a), (b), (c), and (d) of FIG. 4 are 1 day and 3 days, respectively. SEM images of the hydroxide nanostructures are shown when stirred for 5 days, and 7 days.

[ Example  2]

Synthesis of Hydroxide Nanostructures Using Chloride Corrosion Additives

Nickel foam (Ni foam), nickel foil (Ni foil), and aluminum foil (Al foil) was used as the metal substrate of this embodiment. The metal was supported in an aqueous solution in which 10 mmol of NaCl (samchun) was dispersed as a corrosion additive in 30 mL of deionized water, and then stirred at a speed of 300 rpm at a temperature of 95 ° C., which was maintained for 24 hours. I was. The surface of the stirred metal was washed with ultrapure water and dried to synthesize a hydroxide nanostructure.

5 (a) to 5 (c) show SEM images of hydroxide nanostructures synthesized using nickel foam in this embodiment, and FIG. 6a (a) shows hydroxides synthesized using nickel foil in this embodiment. An SEM image of the nanostructure is shown, and FIG. 6A (b) shows an SEM image of the hydroxide nanostructure synthesized using aluminum foil in this embodiment.

[ Example  3]

Chloride Synthesis of Hydroxide Nanostructures with Corrosion Additives 2

Nickel foam (Ni foam), nickel foil (Ni foil), and aluminum foil (Al foil) was used as the metal substrate of this embodiment. The metal was supported in an aqueous solution in which 10 mmol of KCl (samchun) was dispersed as a corrosion additive in 30 mL of deionized water, and then stirred at a speed of 300 rpm at a temperature of 95 ° C., and maintained for 24 hours. I was. The surface of the stirred metal was washed with ultrapure water and dried to synthesize a hydroxide nanostructure.

5 (d) to (f) show SEM images of the hydroxide nanostructures synthesized using the nickel foam in this example.

[ Example  4]

Acetate  Synthesis of Hydroxide Nanostructures Using Corrosion Additives

Aluminum foil (Al foil) was used as the metal substrate of this embodiment. The metal was supported in an aqueous solution in which 0.06 mmol of Ni (OCOCH ₃ ) ₂ was dispersed as a corrosion additive in 10 mL of deionized water, and stirred at a speed of 300 rpm at a temperature of 95 ° C., which was maintained for 24 hours. Reacted. The surface of the stirred metal was washed with ultrapure water and dried to synthesize a hydroxide nanostructure.

6B shows an SEM image of the hydroxide nanostructures synthesized in this example.

Characterization

The oxidation and reduction reaction was measured using CHI660D (CH Instruments, Inc.). A three-electrode system was used, and electrochemical measurements were performed using Ag / AgCl (saturated NaCl solution) as the reference electrode, Pt wire as the counter electrode, and 1 M KOH as the electrolyte. In order to confirm the availability of the supercapacitor and oxygen reduction catalyst of the hydroxide nanostructure synthesized by the method according to Example 2 on the nickel foam substrate, the oxidation and reduction reaction was confirmed by measuring the CV curve. 8 is shown.

7 shows the XRD pattern of the hydroxide nanostructures synthesized according to the present embodiment. The hydroxide nanostructure was separated from the substrate by sonication. Figure 7 (a) is a XRD pattern of the Ni (OH) ₂ nanostructures synthesized according to Example 2 using a nickel foam, α-Ni (OH) ₂ is an anion and water molecules between the formed hydroxide layer Β-Ni (OH) ₂ means a structure in which no anion and water molecules exist between the hydroxide layers. Figure 7 (b) shows the XRD pattern of Al (OH) ₃ nanostructures synthesized according to Example 2 using aluminum foil.

The above description of the present application is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present application is indicated by the following claims rather than the above description, and it should be construed that all changes or modifications derived from the meaning and scope of the claims and their equivalents are included in the scope of the present application. .

Claims (11)

Reducing the surface of the metal formed on the substrate to corrode it; And
Growing an oxide or hydroxide nanostructure on the corroded metal surface in a solvent
Including,
Corrosion by reducing the surface of the metal further comprises adding as a corrosion additive comprising a halogen-based precursor or an acetate-based precursor containing metal ions,
Method for the synthesis of oxide or hydroxide nanostructures.
The method of claim 1,
The metal includes one selected from the group consisting of Ni, Al, Cu, Co, Mn, Fe, Na, K, Ru, Au, Pt, Sn, Pd, Zn, Ti, Ir, Ce, and combinations thereof. That is, the synthesis method of the oxide or hydroxide nanostructure.
The method of claim 1,
The solvent is water, the synthesis method of the oxide or hydroxide nanostructures.
The method of claim 3, wherein
The water comprises ultra pure water (deionized water), method of synthesizing oxide or hydroxide nanostructures.
delete The method of claim 1,
The oxide or hydroxide nanostructures comprising the growth in a structure of 0 to 3 dimensions, oxide or hydroxide nanostructures synthesis method.
The method of claim 6,
The oxide or hydroxide nanostructure is selected from the group consisting of nanoparticles, nanorods, nanosheets, nanowalls, nanocubes, nanoflowers, and combinations thereof. Method of synthesizing an oxide or hydroxide nanostructure, comprising growing in the form of.
The method of claim 1,
The step of growing the oxide or hydroxide nanostructures, is carried out at a temperature in the range of 0 ℃ to 100 ℃, the synthesis method of the oxide or hydroxide nanostructures.
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