CN109715317B - Metal nanowire - Google Patents
Metal nanowire Download PDFInfo
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- CN109715317B CN109715317B CN201780055604.8A CN201780055604A CN109715317B CN 109715317 B CN109715317 B CN 109715317B CN 201780055604 A CN201780055604 A CN 201780055604A CN 109715317 B CN109715317 B CN 109715317B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/15—Nickel or cobalt
Abstract
The invention provides a metal nanowire with a sufficiently large specific surface area. The invention relates to a metal nanowire, which is characterized in that the specific surface area measured by a nitrogen adsorption method is 15m2More than g.
Description
Technical Field
The present invention relates to a metal nanowire, and more particularly, to a metal nanowire having a large specific surface area.
Background
There are technologies having a catalytic function, a deodorizing function, an antibacterial function, and the like in metals, and in recent years, their use as catalysts, deodorants, antibacterial agents, and the like has been studied. In addition, since metals have redox ability and conductivity, the use of metal nanomaterials as electrodes, sensors, and the like has been studied. In these applications, a large specific surface area is required for improving the function.
Nickel is known as a metal having a catalytic function, and as a nickel nanomaterial, for example, patent documents 1 to 3 disclose a nickel nanowire obtained by reducing metal ions while applying a magnetic field. However, the nickel nanowires of cited documents 1 to 3 have insufficient specific surface area and are limited in use.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2014/147885 pamphlet
Patent document 2: international publication No. 2015/163258 pamphlet
Patent document 3: japanese patent laid-open publication No. 2016-135920
Disclosure of Invention
The invention aims to provide a metal nanowire with a sufficiently large specific surface area.
The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that a metal nanowire having a large specific surface area can be obtained by reducing metal ions in water containing carboxymethyl cellulose having a specific viscosity at a specific concentration while applying a magnetic field, thereby completing the present invention.
The gist of the present invention is as follows.
Less than 1 is a metal nanowire, which is characterized in that the specific surface area measured by a nitrogen adsorption method is 15m2More than g.
< 2 > the metal nanowire according to < 1 > wherein the metal is nickel.
< 3 > the metal nanowire according to < 1 > or < 2 > characterized in that the metal nanowire has an average fiber diameter of 50 to 300 nm.
< 4 > the metal nanowire according to any one of < 1 > to < 3 >, wherein the metal nanowire has an average length of 5 to 100 μm.
< 5 > a dispersion comprising the metal nanowire described in any one of < 1 > to < 4 >.
< 6 > a structure comprising the metal nanowire described in any one of < 1 > to < 4 >.
< 7 > A method for producing a metal nanowire as defined in any one of < 1 > to < 4 >, wherein metal ions are reduced in an aqueous solution of a carboxymethyl cellulose salt.
< 8 > the method for producing a metal nanowire according to < 7 >, wherein the carboxymethyl cellulose salt is a carboxymethyl cellulose salt having a viscosity of 1000 to 9000 mPas in a 1 mass% aqueous solution.
< 9 > the method for producing a metal nanowire according to < 7 > or < 8 >, wherein the concentration of the carboxymethyl cellulose salt is 0.5% by mass or more and less than 1.0% by mass.
< 10 > A metal nanowire obtained by a method for producing a metal nanowire, which comprises reducing metal ions while applying a magnetic field to an aqueous solution containing a carboxymethyl cellulose salt at a concentration of 0.5 mass% or more and less than 1.0 mass%, wherein the carboxymethyl cellulose salt is a 1 mass% aqueous solution having a viscosity of 1000 to 9000 mPas.
According to the present invention, a metal nanowire having a large specific surface area can be provided. The metal nanowire of the present invention can be suitably used as a catalyst, a deodorant, an antibacterial agent, and also can be suitably used as a sensor or a battery electrode.
Drawings
Fig. 1 is an image obtained by photographing the metal nanowire obtained in example 1 using a scanning electron microscope.
Detailed Description
[ Metal nanowires ]
The metal nanowire of the present invention has a protruding structure having a plurality of protruding portions on the surface thereof, and thus has a large specific surface area. The protruding direction of the plurality of protrusions is not particularly limited. The protruding direction of each of the plurality of projections may be, for example, a substantially radial direction of the metal nanowire in a cross section perpendicular to the longitudinal direction of the metal nanowire, or may be a resultant force direction of the substantially radial direction and the longitudinal direction of the metal nanowire. The protruding length of the plurality of protrusions is not particularly limited. When the average fiber diameter described later is r (nm), the projection lengths of the plurality of protrusions are usually r (nm) or less independently of each other.
The metal nanowire of the present inventionHas a specific surface area of 15m2A ratio of at least 20 m/g, preferably2A value of 30m or more, more preferably2A total of 40m or more, preferably 40m2More than g, most preferably 50m2More than g. The specific surface area can be measured by an analysis method described later. If the specific surface area is 50m2The specific surface area of the catalyst is equal to or larger than that of the adsorbent such as magnesium oxide or titanium dioxide, and therefore, the catalyst can be used preferably as a catalyst. The upper limit of the specific surface area of the metal nanowire of the present invention is not particularly limited, and the specific surface area is usually 200m2A ratio of less than g, in particular 100m2The ratio of the carbon atoms to the carbon atoms is less than g.
The average fiber diameter of the metal nanowire of the present invention is usually 50 to 300nm, preferably 50 to 200nm, more preferably 60 to 150nm, further preferably 65 to 150nm, particularly preferably 65 to 100nm, and most preferably 65 to 95 μm. When the average fiber diameter is less than 50nm, the fibers are easily broken, and therefore, the length is not constant, and various properties are sometimes affected. The metal nanowires of the present invention have an average length of usually about 5 to 100. mu.m, preferably 5 to 50 μm, more preferably 6 to 50 μm, still more preferably 6 to 40 μm, and most preferably 6 to 30 μm. When the average length is less than 5 μm, the strength may be weakened when a molded article (particularly, a nonwoven fabric) is produced. The average fiber diameter and the average length of the metal nanowires can be measured by the analysis method described later.
The fiber diameter in the present invention means the diameter of the nanowire including the protrusion height of the protrusion, that is, the diameter of a cross section perpendicular to the longitudinal direction of the nanowire, and can be read in an SEM image (scanning electron microscope image (photograph)) of the nanowire. The protrusion height of the protrusion is the height of the protrusion in a cross section perpendicular to the longitudinal direction of the nanowire. Since the metal nanowire of the present invention has a plurality of projections on the surface thereof without any gap, the 2 points defining the line segment having the diameter on the image are usually points on the contour line of the projections. Specifically, the minimum value of the diameters was measured at a position other than the end of 1 nanowire as the minimum fiber diameter, and the average value of the minimum fiber diameters of 300 arbitrary nanowires was defined as the average fiber diameter. The end portion refers to a position within 100nm from one end of the nanowire.
The metal constituting the metal nanowire of the present invention is not particularly limited, but since the metal nanowire is produced in a magnetic field in the present invention, ferromagnetic metals such as nickel, iron, cobalt, and gadolinium are preferable, and nickel is more preferable in terms of being inexpensive and having high practicability.
[ method for producing Metal nanowire ]
The metal nanowire of the present invention can be produced by reducing metal ions in an aqueous solution containing a carboxymethyl cellulose salt having a specific viscosity at a specific concentration while applying a magnetic field (magnetic circuit).
The exemplary manufacturing method is realized by three steps of generating metal particles, growing nanowires, and constructing a bump structure. The metal particles are produced by natural generation of metal particle cores based on a reducing agent or particle formation using palladium cores or platinum cores. The generated metal particles grow into nanowires while being linked by an external factor such as a magnetic field. Then, a reduction reaction of metal ions occurs on the surface of the nanowire to construct a protrusion structure. The difference from patent documents 1 to 3 is the third stage process. In the present invention, in order to construct the protruding structure, a complexing technique that delays the reduction reaction of a part of the metal ions and viscosity control of a reaction solvent that suppresses binding and aggregation between nanowires are important. Therefore, a reaction solvent containing a specific carboxymethyl cellulose salt at a specific concentration is required.
The carboxymethyl cellulose salt has a lower limit of viscosity of 1000 mPas or more when an aqueous solution obtained by dissolving the carboxymethyl cellulose salt in water at a concentration of 1 mass% is measured at 25 ℃ using a B-type viscometer. From the viewpoint of further increasing the specific surface area of the metal nanowire, the viscosity of the carboxymethyl cellulose salt is preferably 2000mPa · s or more, more preferably 2500mPa · s or more, and even more preferably 3000mPa · s or more. When the viscosity is less than 1000 mPas, the metal nanowires having a large specific surface area may not be produced. On the other hand, the upper limit of the viscosity of an aqueous solution obtained by dissolving the carboxymethyl cellulose salt in water at a concentration of 1 mass% is 9000mPa · s or less when measured at 25 ℃ using a B-type viscometer, and from the viewpoint of further increasing the specific surface area of the metal nanowire, the upper limit is preferably 8500mPa · s or less, more preferably 8000mPa · s or less, and still more preferably 5000mPa · s or less. When the viscosity exceeds 9000 mPas, nanowires may not be formed.
The concentration of the carboxymethyl cellulose salt is 0.5 mass% or more and less than 1.0 mass% with respect to the total amount of the reaction solution, and is preferably 0.5 to 0.98 mass%, more preferably 0.6 to 0.98 mass%, even more preferably 0.7 to 0.98 mass%, and most preferably 0.7 to 0.8 mass%, from the viewpoint of further increasing the specific surface area of the metal nanowire. When the concentration of the carboxymethyl cellulose salt is less than 0.5% by mass or 1% by mass or more, the metal nanowire having a large specific surface area may not be produced.
Examples of the carboxymethyl cellulose salt include a sodium salt and a calcium salt, and among them, the sodium salt is more preferable in terms of being inexpensive and highly practical and easily causing salt exchange.
As the source of the metal ion, a metal salt is preferable in terms of being easily dissolved in the water solvent. Examples of the metal salt include chlorides, sulfates, nitrates, and acetates of metals.
The concentration of the metal ion varies depending on the kind of the metal, and is usually 10 to 50. mu. mol/g based on the total amount of the reaction solution. In the case where the metal is nickel in particular, the concentration of the metal ions is preferably 20 to 30. mu. mol/g, more preferably 23 to 27. mu. mol/g, based on the total amount of the reaction solution, from the viewpoint of further increasing the specific surface area of the metal nanowire. When the metal is nickel, it is difficult to form a metal nanowire having a large specific surface area both when the concentration of the metal ion is less than 20. mu. mol/g and when the concentration of the metal ion exceeds 30. mu. mol/g. "μmol/g" means the number of moles per 1g of the reaction solution (the same applies hereinafter).
Although the kind and/or concentration of the reducing agent described later may be used for control, it is preferable to add a complexing agent that forms a complex with the metal ion in addition to the carboxymethyl cellulose salt in order to control the amount of the metal ion used for growing the nanowire. The addition of the complexing agent forms 3 components, namely, metal ions to become metal particles, a metal complex to be consumed for growing nanowires, and a metal complex with carboxymethyl cellulose to be used for constructing a protrusion structure, and thus each step is further appropriately performed.
Examples of the complexing agent include citric acid, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, nitrilotriacetic acid, hydroxyethyliminodiacetic acid, hydroxyiminodisuccinic acid, aminotrimethylenephosphonic acid, hydroxyethanephosphonic acid, and salts thereof. Among these, trisodium citrate dihydrate is more preferable in view of solubility in the reaction solution and the like. When the complexing agent is used, the concentration thereof is preferably 0.001. mu. mol/g or more, more preferably 0.001 to 50. mu. mol/g, and still more preferably 1 to 20. mu. mol/g, relative to the total amount of the reaction solution, from the viewpoint of further increasing the specific surface area of the metal nanowire.
The nucleating agent may be contained in the reaction solution at less than 0.07. mu. mol/g relative to the total amount of the reaction solution. The nucleating agent generates a noble metal nanoparticle core with the diameter of about several nm and promotes the generation of metal particles. Examples of the nucleating agent include salts of noble metals such as gold, silver, platinum, palladium, rhodium, iridium, ruthenium, and osmium. Examples of the noble metal salt include chloroplatinic acid, chloroauric acid, and palladium chloride. For example, when nickel ions are reduced, palladium chloride which produces palladium nanoparticles, chloroplatinic acid which produces platinum nanoparticles, and the like are preferable. Among them, chloroplatinic acid is preferable in terms of easy formation of a core suitable for the generation of the metal nanowire. When the nucleating agent is used, the concentration thereof is preferably 0.01. mu. mol/g or more, and more preferably 0.01 to 0.06. mu. mol/g, relative to the total amount of the reaction solution, from the viewpoint of further increasing the specific surface area of the metal nanowire.
As a method for reducing the metal ion, a reducing agent is preferably used. Examples of the reducing agent include hydrazine, hydrazine monohydrate, ferrous chloride, hypophosphorous acid, borohydride salts, aminoboranes, lithium aluminum hydride, sulfites, hydroxylamines (e.g., diethylhydroxylamine), zincamalgate, diisobutylaluminum hydride, hydroiodic acid, ascorbic acid, oxalic acid, formic acid, ferrous chloride, hypophosphorous acid, borohydride salts, aminoboranes, ascorbic acid, oxalic acid, and formic acid. When the metal ion is a nickel ion, hydrazine or hydrazine monohydrate is preferable in view of high reducing ability.
The concentration of the reducing agent varies depending on the kind of the reducing agent used and/or the metal to be reduced, and for example, in the case of reducing nickel ions using hydrazine monohydrate, it is preferably 1 to 500. mu. mol/g, more preferably 1 to 300. mu. mol/g, and still more preferably 200 to 300. mu. mol/g, based on the total amount of the reaction solution, from the viewpoint of further increasing the specific surface area of the metal nanowire.
The reaction solvent preferably contains water as a main component. When water is not the main component, the carboxymethyl cellulose salt may not be dissolved. In the present invention, "water is used as a main component" means that water is 80 mass% or more in the reaction solvent. An alcohol such as methanol or isopropanol may be added to the reaction solvent as necessary.
When the metal ion is reduced, it is preferable to control the pH and the reaction temperature. The preferable pH and reaction temperature vary depending on the reducing agent used, and for example, when hydrazine monohydrate is used, the pH is preferably 11 to 12, and the reaction temperature is preferably 70 to 100 ℃, particularly preferably 75 to 90 ℃ from the viewpoint of further increasing the specific surface area of the metal nanowire.
The time required for the reduction of the metal ion is not particularly limited, but is usually about 10 minutes to 1 hour, and preferably 15 to 30 minutes from the viewpoint of further increasing the specific surface area of the metal nanowire.
The magnetic field (magnetic flux density) applied when the metal ions are reduced is preferably 10mT or more, more preferably 10mT to 1T, and still more preferably 50 to 180mT, in terms of further increasing the specific surface area of the metal nanowire, as the central magnetic field of the reaction vessel. When the central magnetic field of the reaction vessel is less than 10mT, the metal nanowires may not be produced.
After the reduction reaction is completed, the metal nanowires can be obtained by purifying and recovering the metal nanowires by centrifugal separation, filtration, adsorption with a magnet, or the like.
[ use ]
The purified and recovered metal nanowires can be added to a solvent containing a highly polar solvent such as water as a main component and stirred to obtain a dispersion liquid in which the metal nanowires are dispersed. The solvent of the dispersion is preferably an aqueous solvent containing water as a main component. "mainly consisting of water" means that water is 80 mass% or more in the total solvent. An alcohol such as methanol or isopropyl alcohol may be added to the aqueous solvent as necessary. The concentration of the metal nanowires in the dispersion is not particularly limited, but is preferably 0.01 to 2.0 mass% from the viewpoint of dispersibility.
The metal nanowire dispersion liquid of the present invention may contain additives such as a binder, an antioxidant, a wetting agent, a leveling agent, and the like.
The metal nanowire dispersion liquid of the present invention can be filtered and/or dried to produce a nonwoven fabric-like structure. The nonwoven fabric-like structure may be a nonwoven fabric composed of metal nanowires. The metal nanowire dispersion liquid of the present invention may be applied to a molded article to produce a two-dimensional or three-dimensional structure. The molded article is a molded article made of a polymer, and may be a so-called support or a substrate. In this case, the two-dimensional or three-dimensional structure may be a composite body including a molded body and a metal nanowire-containing layer formed on the surface of the molded body. The metal nanowire-containing layer may be a non-woven fabric layer composed of metal nanowires, a polymer layer in which metal nanowires are dispersed, or a polymer layer containing a non-woven fabric of metal nanowires. In addition, the metal nanowire of the present invention may be compounded with a resin. "composite" means containing, dispersed in, a resin polymer.
The metal nanowire of the present invention has a large specific surface area, and therefore is useful for applications in which the performance is improved as the specific surface area is larger. For example, the metal nanowires of the present invention can be suitably used as a catalyst, a catalyst support, a deodorant, and an antibacterial agent, and can also be suitably used for a sensor and a battery electrode.
When the metal nanowire of the present invention is used as a catalyst, a catalyst support, a deodorant, and an antibacterial agent, the metal nanowire of the present invention may be surface-plated with another metal different from the metal constituting the metal nanowire, or the metal nanowire may be supported with the other metal. Further, semiconductivity may be added by oxidation or the like. For example, a catalyst having a promoter function can be produced by supporting nanoparticles of iron, chromium, molybdenum, or the like on the metal nanowire of the present invention.
When the metal nanowire of the present invention is used as a battery electrode, the battery electrode can be obtained by the following method using the above-mentioned metal nanowire dispersion, for example. Firstly, filtering and drying the metal nanowire dispersion liquid to obtain the metal nanowire non-woven fabric. After obtaining the metal nanowire nonwoven fabric, the thickness of the nonwoven fabric can be adjusted by pressing the metal nanowire nonwoven fabric as desired. Next, an electrode active material layer is formed on the surface of the metal nanowire nonwoven fabric (the surface of each metal nanowire), whereby a battery electrode can be obtained. Such a battery electrode can be used as a flexible electrode.
The method for forming the electrode active material layer is not particularly limited, and a known method for forming the electrode active material layer can be used. For example, the surface of the metal nanowire nonwoven fabric may be oxidized to form a metal oxide coating, which is used as an electrode active material layer. It is known that oxides of metals constituting the metal nanowire of the present invention, for example, oxides of nickel, iron, cobalt, and gadolinium, react with lithium in a higher capacity than conventional carbon raw materials. Since the metal nanowire of the present invention has a sufficiently large specific surface area, a battery electrode using the metal nanowire (nonwoven fabric) of the present invention can more efficiently perform a redox reaction. The battery electrode using the metal nanowire (nonwoven fabric) of the present invention is useful, for example, as a negative electrode or a positive electrode (particularly, a negative electrode) of a lithium ion secondary battery.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
1. Evaluation method
(1) Average fiber diameter of metal nanowires
The metal nanowires obtained in each of the examples and comparative examples were photographed at 50000 times the observation magnification using a scanning electron microscope.
From the obtained image, the minimum fiber diameter of each metal nanowire was measured for 300 metal nanowires randomly selected in any 10 visual fields of 3 μm × 3 μm, and the minimum fiber diameter was averaged to obtain the average fiber diameter. Fig. 1 shows a scanning electron microscope image of the metal nanowire obtained in example 1.
(2) Average length of metal nanowires
The metal nanowires obtained in each of the examples and comparative examples were photographed at 1000 to 4000 times using a scanning electron microscope.
From the obtained image, the lengths of 200 randomly selected metal nanowires were measured, and the lengths were averaged to obtain an average length.
(3) Specific surface area of metal nanowire
Using about 100mg of the metal nanowires obtained in each of examples and comparative examples, the amount of nitrogen adsorbed was measured by a nitrogen adsorption method, and the specific surface area was calculated from the adsorbed amount by the BET formula.
2. Raw materials
(1) Sodium carboxymethyl cellulose
·Cellogen MP-60
First Industrial pharmaceutical Co., Ltd, and a solution obtained by dissolving the compound in water at a concentration of 1 mass% was measured at 25 ℃ using a B-type viscometer, and the viscosity was 10000 to 15000 mPas
·Cellogen BSH-12
First Industrial pharmaceutical Co., Ltd, and a solution obtained by dissolving a compound in water at a concentration of 1 mass% was measured at 25 ℃ using a B-type viscometer, and the viscosity was 6000 to 8000 mPas
·Cellogen BSH-6
A solution obtained by dissolving a compound in water at a concentration of 1 mass% was measured at 25 ℃ with a B-type viscometer, manufactured by first Industrial pharmaceutical Co., Ltd., and had a viscosity of 3000 to 4000 mPas
·Cellogen BS
A solution obtained by dissolving a compound in water at a concentration of 1% by mass was measured at 25 ℃ with a B-type viscometer, manufactured by first Industrial pharmaceutical Co., Ltd., and had a viscosity of 350 to 500 mPas
Example 1
0.59g (2.48mmol) of nickel chloride hexahydrate, 0.28g (0.93mmol) of trisodium citrate dihydrate, 0.29mg (5.00. mu. mol) of chloroplatinic acid hexahydrate and 60.75 g of Cellogen BSH-60.75 g were dissolved in water. Further, a 5% aqueous solution of sodium hydroxide was added dropwise to adjust the pH to 11.5, and water was added to make the total amount to 75g, thereby preparing a nickel ion solution.
On the other hand, 1.25g (25.0mmol) of hydrazine monohydrate was mixed with water, and a 5% aqueous solution of sodium hydroxide was further added dropwise to adjust the pH to 11.5, and water was added to make the total amount to 25g to prepare a reducing agent solution.
The nickel ion solution and the reducing agent solution are both heated to 80-85 ℃, mixed in a state of maintaining the temperature, and subjected to a reduction reaction for 20 minutes by applying a magnetic field of 100 mT.
Then, the nickel nanowire is obtained by filtering, cleaning, recovering and vacuum drying.
Examples 2 to 3 and comparative examples 2 to 3, 5 and 7 to 9
Nickel nanowires were obtained in the same manner as in example 1, except that the kind and concentration of the carboxymethyl cellulose salt were changed as shown in table 1.
Comparative example 1
1.19g (5.00mmol) of nickel chloride hexahydrate, 0.55g (1.86mmol) of trisodium citrate dihydrate, and 5.18mg (0.01mmol) of chloroplatinic acid hexahydrate were dissolved in water. Further, a 5% aqueous solution of sodium hydroxide was added dropwise to adjust the pH to 12.5, and water was added to make the total amount to 75g, thereby preparing a nickel ion solution.
On the other hand, 2.50g (50.0mmol) of hydrazine monohydrate was mixed with water, and a 5% aqueous solution of sodium hydroxide was further added dropwise to adjust the pH to 12.5, and water was added to make the total amount to 25g to prepare a reducing agent solution.
The nickel ion solution and the reducing agent solution are both heated to 80-85 ℃, mixed in a state of maintaining the temperature, and subjected to a reduction reaction for 15 minutes by applying a magnetic field of 100 mT.
Then, the nickel nanowire is obtained by filtering, cleaning, recovering and vacuum drying.
Comparative examples 4 and 6
The same operation as in example 1 was carried out except that the kind and concentration of the carboxymethyl cellulose salt were changed as shown in table 1, but since the reaction field had a high viscosity, the movement of the produced nickel particles was restricted, and nickel nanowires could not be obtained.
Table 1 shows the production conditions and evaluation results of the metal nanowires obtained in each of examples and comparative examples.
[ Table 1]
The nickel nanowires of examples 1 to 3 had a plurality of protrusions on the surface thereof and a specific surface area of 15m2More than g. Therefore, it is considered that the present invention can be applied to a catalyst, a deodorant, an antibacterial agent, a sensor, a battery electrode, and the like. Further, the specific surface area of example 1 was 50m2The nanowires have a sufficient fiber length, and a nonwoven fabric made of nanowires is less likely to be detached even when immersed in water, and has excellent strength.
Comparative example 1 is an additional test of example 1 of patent document 1. Because no carboxymethyl cellulose salt is added, the specific surface area is less than 15m2/g。
Comparative examples 2 and 3 are additional tests of examples 1 and 2 of patent document 3, respectively.
Comparative examples 2, 5 and 7 had specific surface areas of less than 15m, since the viscosity of the carboxymethyl cellulose salt added was too low2/g。
Comparative example 3 since the carboxymethyl cellulose salt was added at a high concentration, the growth of the nanowire was inhibited by the viscosity, the formation of the protruding structure was insufficient, and the specific surface area was less than 15m2/g。
In comparative example 8, since the carboxymethyl cellulose salt was added at a low concentration, it is considered that the nickel ion was insufficient in the formation of the protrusion structure, and the specific surface area was less than 15m2/g。
Comparative example 9 the viscosity of the carboxymethyl cellulose salt added was too high, and the specific surface area was less than 15m2The average length of the nanowires is short.
Industrial applicability
The metal nanowires of the present invention are useful in, for example, the production of catalysts, catalyst supports, deodorants, and antibacterial agents.
Claims (25)
1. A metal nanowire characterized in that the specific surface area measured by a nitrogen adsorption method is 15m2More than g, the metal nanowires have an average fiber diameter of 50 to 300nm, and the metal nanowires have an average length of 5 to 100 [ mu ] m.
2. The metal nanowires of claim 1, wherein the metal is nickel.
3. A dispersion liquid comprising the metal nanowires according to claim 1 or 2.
4. A structure comprising the metal nanowire according to claim 1 or 2.
5. A method for producing metal nanowires according to claim 1 or 2, characterized in that metal ions are reduced in an aqueous solution of a carboxymethyl cellulose salt.
6. The method for producing metal nanowires according to claim 5, wherein the carboxymethyl cellulose salt is a carboxymethyl cellulose salt having a viscosity of 1000 to 9000 mPas in a 1 mass% aqueous solution.
7. The method for producing metal nanowires according to claim 5, wherein a concentration of the carboxymethyl cellulose salt is 0.5 mass% or more and less than 1.0 mass%.
8. The method for producing metal nanowires according to claim 6, wherein a concentration of the carboxymethyl cellulose salt is 0.5 mass% or more and less than 1.0 mass%.
9. A method for manufacturing metal nanowires is characterized in that the specific surface area of the metal nanowires is 15m measured by a nitrogen adsorption method2The method for producing metal nanowires of the aforementioned concentration comprises reducing metal ions in an aqueous solution of a carboxymethyl cellulose salt.
10. The method of manufacturing metal nanowires of claim 9, wherein the metal is nickel.
11. The method of manufacturing metal nanowires according to claim 9 or 10, wherein the metal nanowires have an average length of 5 to 100 μm.
12. The method for producing metal nanowires according to claim 9 or 10, wherein the carboxymethyl cellulose salt is a carboxymethyl cellulose salt having a viscosity of 1000 to 9000mPa · s in a 1 mass% aqueous solution.
13. The method for producing metal nanowires according to claim 11, wherein the carboxymethyl cellulose salt is a carboxymethyl cellulose salt having a viscosity of 1000 to 9000 mPa-s in a 1 mass% aqueous solution.
14. The method of producing metal nanowires according to claim 9 or 10, wherein the concentration of the carboxymethyl cellulose salt is 0.5 mass% or more and less than 1.0 mass%.
15. The method of manufacturing a metal nanowire according to claim 11, wherein a concentration of the carboxymethyl cellulose salt is 0.5% by mass or more and less than 1.0% by mass.
16. The method of manufacturing a metal nanowire according to claim 12, wherein a concentration of the carboxymethyl cellulose salt is 0.5% by mass or more and less than 1.0% by mass.
17. A method for manufacturing a metal nanowire, characterized in that the specific surface area of the metal nanowire measured by a nitrogen adsorption method is 15m2(ii)/g or more, the metal nanowires have an average fiber diameter of 50 to 300nm,
the metal ions are reduced in an aqueous solution of a salt of carboxymethyl cellulose.
18. The method of manufacturing metal nanowires of claim 17, wherein the metal is nickel.
19. The method of manufacturing metal nanowires according to claim 17 or 18, wherein the metal nanowires have an average length of 5 to 100 μm.
20. The method for producing metal nanowires according to claim 17 or 18, wherein the carboxymethyl cellulose salt is a carboxymethyl cellulose salt having a viscosity of 1000 to 9000mPa · s in a 1 mass% aqueous solution.
21. The method for producing metal nanowires according to claim 19, wherein the carboxymethyl cellulose salt is a carboxymethyl cellulose salt having a viscosity of 1000 to 9000 mPa-s in a 1 mass% aqueous solution.
22. The method of producing metal nanowires according to claim 17 or 18, wherein the concentration of the carboxymethyl cellulose salt is 0.5 mass% or more and less than 1.0 mass%.
23. The method of manufacturing a metal nanowire according to claim 19, wherein a concentration of the carboxymethyl cellulose salt is 0.5% by mass or more and less than 1.0% by mass.
24. The method of manufacturing a metal nanowire according to claim 20, wherein a concentration of the carboxymethyl cellulose salt is 0.5% by mass or more and less than 1.0% by mass.
25. A metal nanowire obtained by a method for producing a metal nanowire, wherein a metal ion is reduced while applying a magnetic field to an aqueous solution containing a carboxymethyl cellulose salt at a concentration of 0.5 mass% or more and less than 1.0 mass%, and the carboxymethyl cellulose salt is a carboxymethyl cellulose salt having a viscosity of 1000 to 9000 mPas in a 1 mass% aqueous solution.
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