JP5017017B2 - Nanoparticle carrying device and coaxial carrying method with coaxial vacuum arc deposition source - Google Patents

Description

  The present invention relates to a catalyst nanoparticle support apparatus and a catalyst nanoparticle support apparatus using a coaxial vacuum arc deposition source, and more specifically, in vacuum arc deposition in which catalyst nanoparticles are supported on a particulate carrier. The present invention relates to a catalyst nanoparticle supporting apparatus and a catalyst nanoparticle supporting method in which a particulate carrier accommodated in a container is not scattered outside the container.

  Conventionally, fuel cells have been used in which platinum is supported as an active metal having catalytic action on powdered carbon black. As a method for supporting platinum on carbon black, platinum colloidal liquid containing carbon black is used. Mixing with an aqueous solution is performed. For example, sodium dithionate is added to an aqueous solution containing chloroplatinate ions, preferably hydrogen peroxide is allowed to coexist to produce platinum colloid, and carbon black is added thereto to convert platinum ultrafine particles into carbon black. A method of carrying is known (see Patent Document 1). Further, by mixing a divalent platinum compound (for example, potassium tetrachloroplatinate) and an amine compound (for example, dimethylaminoethanol) in an aqueous solution of a high molecular weight pigment dispersant, the divalent platinum compound is reduced to form a platinum colloid. And a method of immersing activated carbon powder in the platinum colloid is shown as one of many supporting methods (see Patent Document 2).

JP 54-92588 A JP 2002-285207 A

  However, as described above, the method of loading carbon black into platinum colloid in which platinum ultrafine particles are dispersed in water and supporting platinum on carbon black is supported on carbon black among the ultrafine platinum particles. There is a problem in that the amount that is not easily increased tends to increase and the amount of platinum used becomes excessive.

  On the other hand, the present inventors have developed a method in which platinum is supported on carbon particles by a vacuum arc deposition method which is a dry system, rather than by a conventional wet system. That is, it is a method of carrying by the carrying device provided with the coaxial vacuum arc evaporation source as shown below.

  FIG. 1 is a cross-sectional view showing a catalyst nanoparticle support apparatus 1 equipped with the coaxial vacuum arc deposition source. That is, a coaxial type vacuum arc vapor deposition source 21 for evaporating platinum is attached to the upper part of the vacuum chamber 11, and a container for containing and stirring carbon black C as a carrier to be deposited on the bottom of the vacuum chamber 11. 31 is arranged. Further, a rotary pump 12 and a turbo molecular pump 13 which are vacuum exhaust systems for exhausting the inside of the vacuum chamber 11 are attached to the side wall of the vacuum chamber 11.

  The coaxial vacuum arc evaporation source 21 includes a cylindrical cathode electrode 22 made of platinum (Pt) as an evaporation material, a hat-shaped insulator 23 coaxially provided in contact with the outer peripheral surface of the cathode electrode 22, and an insulator. A cylindrical trigger electrode 24 that is in contact with the outer peripheral surface of the cylindrical portion of the hat 23 and is in contact with the upper end of the hat's collar and coaxially, and coaxially spaced from the outer peripheral surface of the trigger electrode 24 The cylindrical electrode is provided, the lower end side is opened into the vacuum chamber 11, and the upper end side is composed of an anode electrode 25 which is closed at a position spaced from the upper end of the cathode electrode 22.

  Further, a trigger power source 26 is provided between the trigger electrode 24 and the cathode electrode 22, and a DC power source 27 for generating an arc is provided between the cathode electrode 22 and the anode electrode 25. The positive terminal of the trigger power supply 26 is connected to the trigger electrode 24, and the negative terminal is connected to the cathode electrode 22 at the same potential as the negative terminal of the DC power supply 27. The trigger power source 26 is composed of a pulse transformer, and boosts and outputs a pulse voltage in units of 200 V and a pulse width of μsec to 3.4 kV (several μA), which is 17 times.

  As described above, an arc generating DC power supply 27 having a voltage of 100 V and a current of several A is provided between the anode electrode 25 and the cathode electrode 22, and the positive terminal of the DC power supply 27 is grounded. It is at ground potential and is connected to the anode electrode 25. An arc generating capacitor unit 28 having a capacity of 8800 μF is provided in parallel with the arc generating DC power supply 27, and one terminal of the capacitor unit 28 is connected to the plus terminal side of the DC power supply 27, and the other The terminal is connected to the negative terminal side of the DC power supply 27. The capacitor unit 28 is a unit in which four capacitors having a capacity of 2200 μF and a withstand voltage of 100 V are connected in parallel. The capacitor unit 28 is charged at any time by the DC power source 27. Since the charging takes about 1 second, the discharge cycle when the discharge from the capacitor unit 28 is repeated is about 1 Hz.

  The carbon black C container 31 is rotated by a rotational drive source 32 provided outside the vacuum chamber 11. That is, the rotary shaft 33 of the rotary drive source 32 is inserted into the vacuum chamber 11 through a vacuum seal mechanism (not shown), and further, a fixed base 34 provided in the vacuum chamber 11 is rotatably inserted. A container 31 is attached to the upper end of the rotating shaft 33. The fixed blade 36 supported by the support column 35 attached to the fixed base 34 is positioned at a depth close to the bottom surface of the container 31. The carbon black accommodated inside the container 31 by rotating the container 31. C is stirred.

Subsequently, by using the nanoparticle carrying device 1 shown in FIG. 1, the material of the cathode electrode 22 of the coaxial vacuum arc evaporation source 21 on the surface of the carbon black C as the carrier in the container 31 is used as the evaporation material. A supporting method for forming a certain platinum nanoparticle will be described. A predetermined amount of carbon black C is accommodated in the container 31, and the container 31 is rotated by the rotational drive source 32 and stirring is started, and the rotary pump 12 and then the turbo molecular pump 13 are activated to perform vacuum. The inside of the chamber 11 is evacuated to a predetermined degree of vacuum, and if necessary, an inert gas is introduced from a supply source (not shown) and maintained at a degree of vacuum of 10 ⁻⁵ Pa. The capacitor unit 28 is used for arc generation. It is assumed that the battery is charged by the direct current power source 27. In this state, first, a pulse voltage of 3.4 kV is output from the trigger power source 26 to the trigger electrode 24, and creeping discharge occurs on the lower end surface of the insulator 23 between the lower end of the cathode electrode 22 and the lower end of the trigger electrode 24, that is, Causes a trigger discharge.

  An arc discharge is generated between the cathode electrode 22 and the anode electrode 25 by being induced by the trigger discharge. That is, the electric charge stored in the capacitor unit 28 is subjected to vacuum arc discharge, and a large amount of arc current (2000 A to 5000 A) flows into the cathode electrode 22 during 200 μsec to 550 μsec. Due to this arc current, plasma is formed in the vicinity of the lower end of the cathode electrode 22 and platinum constituting the cathode electrode 22 is partially melted at the lower end surface to evaporate, but the evaporated platinum is converted into plasma. Dissociated into electrons and platinum ions. When the arc current flows through the cathode electrode 22, a magnetic field is formed in a concentric cylindrical shape with the cathode electrode 22 as the center. Therefore, electrons and platinum ions emitted from the cathode electrode 22 receive Lorentz force from the magnetic field, electrons are caused by Lorentz force, and atomic platinum ions having a large (charge / mass) ratio are between Lorentz force and electrons. The Coulomb force is accelerated in the axial direction of the cathode electrode 22 and flies, collides with and adheres to the carbon black C stirred in the container 31.

  In this way, platinum nanoparticles (particle diameter: 1 nm to 10 nm) can be uniformly supported on the surface of the carbon black C. However, during the vacuum arc deposition, the carbon black C rises from the container 31 in a smoke shape. The phenomenon of scattering occurred. On the other hand, the height of the peripheral wall of the container 31 is somewhat improved, but the height is increased too much, for example, the upper end of the container 31 is the same as the lower end of the coaxial vacuum arc deposition source 21. Increasing to the extent caused the coaxial vacuum arc evaporation source 21 to become dirty and short-circuited with the carbon black C.

  The present invention has been made in view of the above-mentioned problems. When a metal nanoparticle is supported on a particulate carrier by a catalyst nanoparticle carrier equipped with a coaxial vacuum arc evaporation source, the particulate carrier contained in the container is outside the container. It is an object of the present invention to provide a nanoparticle carrying device and a nanoparticle carrying method that do not scatter.

  The above problem can be solved by the structure of the first or fourth aspect. The means for solving the problem will be described as follows.

A nanoparticle carrying device according to the present invention includes a vacuum chamber, a cathode electrode made of a metal having a catalytic activity as a deposition material, a trigger electrode, an anode electrode, a trigger power source, and a DC power source provided in parallel for generating an arc. In a nanoparticle carrying device comprising a coaxial vacuum arc evaporation source having a capacitor and a container for storing carbon black as a particulate carrier as a material to be deposited, it is evaporated from the cathode electrode during vacuum arc deposition, By adjusting the amount of charge of the metal nanoparticles flying toward the carbon black , a means for adjusting the amount of charge of the metal nanoparticles is provided to prevent the carbon black in the container from scattering outside the container. It is a device.

  Such a nanoparticle support device suppresses the charge-up of the particulate carrier in the container by suppressing the charge amount of the metal nanoparticles flying from the cathode electrode toward the particulate carrier.

  The nanoparticle carrying device according to claim 2 is a device in which the charge amount adjusting means adjusts at least one of the capacitance of the capacitor and the discharge voltage of the DC power supply. Such a nanoparticle carrying | support apparatus can suppress the electric charge amount of the metal nanoparticle which flies toward a particulate support from a cathode electrode.

  4. The nanoparticle carrying device according to claim 3, wherein the charge amount adjusting means is an electron emission source that is installed in a vacuum chamber and emits electrons for neutralizing at least part of the charge of the metal nanoparticles. It is. Such a nanoparticle carrying | support apparatus can suppress the electric charge amount of the metal nanoparticle which flies toward a particulate support from a cathode electrode.

The nanoparticle carrying method according to the present invention includes a cathode electrode, a trigger electrode, an anode electrode, a trigger power source, and a DC power source provided in parallel for generating an arc, in a vacuum chamber, made of a metal having a catalytic activity as a deposition material. A nanoparticle carrying method for carrying metal nanoparticles on carbon black as a particulate carrier , which is a material to be deposited, contained in a container, using a coaxial vacuum arc evaporation source equipped with a capacitor and vacuum arc deposition This is a method in which metal nanoparticles are evaporated onto carbon black while adjusting the amount of charge of metal nanoparticles that are sometimes evaporated from the cathode electrode and suppressing the carbon black in the container from scattering outside the container .

  Such a nanoparticle carrying | support method suppresses that the particulate support in a container charges up by adjusting the electric charge amount which the metal nanoparticle which flies toward a particulate support from a cathode electrode.

  In the nanoparticle carrying method of claim 5, the method of adjusting the charge amount is a method of adjusting at least one of the electrostatic capacity of the capacitor and the discharge voltage of the DC power supply. Such a nanoparticle carrying method can suppress the charge amount of the metal nanoparticles flying from the cathode electrode toward the particulate carrier.

  The nanoparticle carrying method according to claim 6 is a method in which at least a part of the electric charge of the metal nanoparticles is neutralized by electrons supplied from an electron emission source. Such a nanoparticle carrying | support method can suppress the electric charge amount which the metal nanoparticle which flies toward a particulate support from a cathode electrode has.

  According to the nanoparticle carrying device of claim 1, since the means for adjusting the charge amount of the metal nanoparticles that evaporate from the cathode electrode and fly toward the particulate carrier during vacuum arc deposition is provided, The amount of charge to be charged up to the particulate carrier is reduced, and the particulate carrier in the container is prevented from scattering outside the container during the vacuum arc deposition, thereby increasing the productivity of the nanoparticle carrier.

  According to the nanoparticle carrying device of claim 2, the metal nanoparticles flying from the cathode electrode toward the particulate carrier by adjusting at least one of the capacitance of the capacitor and the discharge voltage of the DC power supply are included. Since the amount of charge can be reduced, the amount of charge that is charged up to the particulate carrier can be suppressed, and the particulate carrier in the container is prevented from being charged up and scattered outside the container.

  According to the nanoparticle carrying device of claim 3, since at least a part of the electric charge of the metal nanoparticles flying from the cathode electrode toward the particulate carrier is neutralized by the electrons emitted from the electron emission source, The amount of charge that charges the carrier can be suppressed, and the particulate carrier in the container is prevented from being charged up and scattered outside the container.

  According to the catalyst nanoparticle supporting method of claim 4, the amount of charge of the metal nanoparticles that evaporate from the cathode electrode and fly toward the particulate carrier during vacuum arc deposition is adjusted. Since it suppresses the charge-up, the amount of charge to be charged to the particulate carrier, which is the deposition target, is reduced, and the particulate carrier in the container is prevented from scattering outside the container during vacuum arc deposition. The yield of the particulate carrier carrying the particles is increased.

  According to the catalyst nanoparticle supporting method of claim 5, by adjusting at least one of the capacitance of the capacitor and the discharge voltage of the DC power supply, the metal nanoparticle that flies from the cathode electrode toward the particulate carrier. Since the amount of charge of the particles is suppressed, the amount of charge to be charged to the particulate carrier that is the deposition target is reduced, and the particulate carrier in the container is prevented from being scattered outside the container during the vacuum arc deposition.

  According to the catalyst nanoparticle supporting method of claim 6, at least a part of the charge of the metal nanoparticles flying from the cathode electrode toward the particulate carrier by the electrons emitted from the electron emission source installed in the vacuum chamber. Therefore, the amount of charge to be charged to the particulate carrier, which is the deposition target, is reduced, and the particulate carrier in the container is prevented from being scattered outside the container during the vacuum arc deposition.

  When the platinum nanoparticles are supported on the carbon black C by the catalyst nanoparticle support apparatus 1 having the coaxial vacuum arc evaporation source 21 described above, the cause of the carbon black C in the container 31 being scattered outside the container 31 is searched. The cause of this was thought to be that carbon black C was charged up to (+) because a large amount of platinum ions dropped onto carbon black C during vacuum arc deposition.

Based on the above idea, the capacity of the arc discharge capacitor unit 28 in the coaxial vacuum arc deposition source 21 is set to 8800 μF as described above, using the catalyst nanoparticle support device 1 shown in FIG. When the discharge voltage of the DC power source 27 was changed, and the amount of carbon black C discharged was measured when the discharge cycle was 1 Hz and the number of discharges was 20000, the results shown in Table 1 were obtained. In addition, 2g of the product (brand name; VulcanXC-72) of a Cabot company was used for carbon black C.

  As is clear from Table 1, the higher the discharge voltage, in other words, the greater the energy of the plasma formed by a single discharge, and the greater the amount of charge generated in the platinum nanoparticles passing through the plasma. It can be said that the amount of carbon black C scattered increases rapidly as the value becomes.

  Based on the results of Example 1, the capacity of the arc generating capacitor unit 28 is set to 4400 μF or less, the discharge voltage of the arc generating DC power supply 27 is set to 100 V or less, the discharge cycle is set to 2 Hz or more, and the number of discharges is the same deposition amount. Table 2 shows the amount of carbon black C scattered according to the discharge conditions when discharged as the number of times obtained.

  The test number 2 of Table 1 is compared with the test number 6 of Table 2, and the capacity 8800 μF of the capacitor unit 28 in the test number 2 is set to 4400 μF of (1/2) in the test number 6, and the DC power source 27 in the test number 2 In order to obtain the same deposition rate as in test number 2 with a discharge period of 1 Hz, which is twice as high as in test number 6, the discharge number of 20000 in test number 2 was discharged as 40000 in test number 6, but carbon was discharged. The scattering amount of Black C was 200 mg in Test No. 2 and 50 mg in Test No. 6, which was reduced to (1/4).

As shown in the following formula (1), the film formation amount R as an index of the amount of vapor deposition is proportional to the discharge energy E.
^{R α E (= CV 2/} 2) ( Equation 1)
In the formula (1), the film formation amount R is the thickness of the deposited film per unit area / unit time. C is the capacity of the capacitor unit 28, and V is the discharge voltage of the DC power supply 27.

  Since Test No. 2 and Test No. 6 have the same discharge energy E, it is considered that the carbon black C is similarly charged up and the scattering amount thereof is also the same. However, the scattering amount of the carbon black C in test number 6 is small because the discharge voltage is the same and the discharge interval is (1/2) by setting the capacity of the capacitor unit 28 to (1/2). Even if it is doubled, the energy of the plasma formed for each discharge is small, for example, the plasma density is lowered, so that the degree of dissociation of platinum nanoparticles passing through the plasma into platinum ions and electrons It is assumed that the charge-up (surface potential, charge amount) of carbon black C by platinum ions is reduced and the repulsive force between the carbon blacks C is reduced.

  Further, in test number 8 in Table 2, the capacity of the capacitor unit 28 is set to 1100 μF of (1/8) of test number 2 so that the same vapor deposition amount as in test number 2 in Table 1 is obtained, and the discharge cycle is set. When discharging was performed at 8 Hz, which is 8 times the test number 2, and thus the number of discharges was 16000, the amount of carbon black C scattered in test number 8 was 20 mg of (1/10) of test number 2.

  In Example 1 and Example 2, it is shown that the charge-up of the carbon black C can be suppressed by limiting the discharge conditions, and as a result, the carbon black C can suppress scattering from the container 31 to the outside. However, an electron emission source is installed in the vicinity of the coaxial vacuum arc deposition source in the vacuum chamber 11 or in the vicinity of the container for storing the particulate carrier, and platinum ions flying from the cathode electrode 22 toward the carbon black C The charge-up of the carbon black C can also be suppressed by neutralizing at least a part with electrons emitted from the electron emission source.

  FIG. 2 is a cross-sectional view showing the nanoparticle support device 2 in which a thermionic emitter 41 is installed as an electron emission source in the vacuum chamber 11 of the nanoparticle support device 1 of FIG. That is, the thermoelectron emitter 41 includes a tungsten (W) filament 42 which is a thermoelectron emitting material, and a DC power supply 43 for energizing and heating the filament 42. The filament 42 has a wire diameter of 1 mm and a length of 80 mm and is formed into a spiral spring shape by being energized with a DC power supply 43 of, for example, about 6 V and 25 A (= 150 W). The filament 42 becomes red hot and emits thermoelectrons. Using the nanoparticle carrier device 2 provided with such a thermionic emitter 41, the discharge conditions identical to the test number 2 in Table 1 of Example 1, that is, the capacity of the arc discharge capacitor unit 28 is 8800 μF. The discharge voltage of the arc discharge DC power supply 27 is 100 V, the discharge cycle is 1 Hz, the number of discharges is 20000, and the amount of scattering of the carbon black C when the thermoelectrons are emitted from the thermoelectron emitter 41 is 30 mg. there were. That is, most of the platinum ions flying from the cathode electrode 22 toward the carbon black C are neutralized by thermionic electrons, so that the amount of carbon black C scattered is approximately (1) compared to test number 2 in Table 1. / 7).

  As mentioned above, although the nanoparticle carrying | support apparatus and the nanoparticle carrying | support method using the coaxial vacuum arc vapor deposition source of this invention were demonstrated by the Example, of course, this invention is not limited to these, The technical idea of this invention Various modifications are possible based on the above.

For example, in Example 3, the filament 42 made of tungsten was used for the thermoelectron emission device 41, but a thermoelectron emission material other than tungsten, such as thallium (Ta), molybdenum (Mo), or lanthanum hexaboride (LaB _6). ) Can be used in a suitable shape. As the heating method, the filament 42 is energized by the DC power supply 43 and resistance-heated, but a method other than resistance heating, for example, a thermoelectron emission material may be formed into a cylindrical shape and a cylindrical heating element may be provided in contact with the outer periphery.

  In the third embodiment, the thermionic emission device 41 is employed as the electron emission source. However, a device that introduces a rare gas into the discharge tube, ignites plasma, and extracts electrons can be used.

  In the embodiment, the present invention has been described by exemplifying a catalyst used in a fuel cell. However, the present invention is similarly applied to a catalyst for an exhaust gas purification device of an automobile and a catalyst for a base film when manufacturing a carbon nanotube. Applied.

It is sectional drawing which shows the nanoparticle carrying | support apparatus used in Example 1 and Example 2. FIG. It is sectional drawing which shows the nanoparticle support apparatus provided with the thermoelectron emitter used in Example 3.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Vacuum arc evaporation apparatus, 11 ... Vacuum chamber,
21 ... Coaxial vacuum arc evaporation source, 22 ... Cathode electrode,
23 ... Insulator, 24 ... Trigger electrode,
25 ... Anode electrode, 26 ... Trigger power supply,
27 ... DC power supply for arc, 28 ... Capacitor unit,
31 ... Container, 32 ... Rotation drive source,
33 ... rotating shaft, 36 ... fixed blade,
41 ... Thermionic emission device, 42 ... Filament,
43 ... DC power supply for heating, 51 ... Electron supply equipment using plasma,
52 ... center electrode, 53 ... outer peripheral electrode,
54 ... cylindrical insulator, 55 ... high frequency AC power supply,
56 ... He gas introduction tube, 57 ... discharge space,
58: Magnet.

Claims (6)

A coaxial vacuum arc evaporation source comprising a vacuum chamber, a cathode electrode made of a metal that is a deposition material and having catalytic activity, a trigger electrode, an anode electrode, a trigger power source, and a DC power source and a capacitor provided in parallel for arc generation And a nanoparticle carrying device comprising a container containing carbon black as a deposition material,
It is possible to prevent the carbon black in the container from scattering outside the container by adjusting the amount of charge of the metal nanoparticles that are evaporated from the cathode electrode and fly toward the carbon black in the container during vacuum arc deposition. Therefore, a means for adjusting the amount of charge of the metal nanoparticles is provided.   2. The nanoparticle carrying device according to claim 1, wherein the charge amount adjusting means is means for adjusting at least one of an electrostatic capacity of the capacitor and a discharge voltage of the DC power supply.   2. The electron emission source according to claim 1, wherein the charge amount adjusting unit is an electron emission source that is installed in the vacuum chamber and emits electrons for neutralizing at least part of the electric charge of the metal nanoparticles. The nanoparticle carrying device as described. In a vacuum chamber, a coaxial type vacuum arc evaporation provided with a cathode electrode, a trigger electrode, an anode electrode, a trigger power source, and a DC power source and a capacitor provided in parallel for generating an arc in a vacuum chamber made of a metal having a catalytic activity. A nanoparticle carrying method in which metal nanoparticles are carried on carbon black , which is a deposition material contained in a container, using a source,
The amount of charge of the metal nanoparticles formed by evaporation from the cathode electrode during vacuum arc deposition is adjusted, and the metal nanoparticles are removed from the carbon while suppressing carbon black in the container from being scattered outside the container. A method for supporting nanoparticles, comprising vapor depositing on black .   5. The nanoparticle carrying method according to claim 4, wherein the method of adjusting the charge amount is a method of adjusting at least one of an electrostatic capacity of the capacitor and a discharge voltage of the DC power supply.   5. The nanoparticle support according to claim 4, wherein the method of adjusting the amount of charge is a method of neutralizing at least part of the charge of the metal nanoparticle by electrons emitted from an electron emission source. Method.

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