JP4958649B2 - Nanoparticle support device for catalyst with coaxial vacuum arc evaporation source - Google Patents

Description

  The present invention relates to a catalyst supporting apparatus for supporting nanosized fine particles having catalytic activity on a particulate carrier using a coaxial vacuum arc evaporation source, and more specifically, for a catalyst capable of reducing the time required for supporting. The present invention relates to a carrier device.

Conventionally, a fuel cell in which platinum is supported as an active metal having catalytic action on powdered carbon particles has been used (see, for example, Patent Document 1 and Patent Document 2). However, in the apparatus for supporting the catalyst nanoparticles using the coaxial vacuum arc evaporation source experimentally developed by the present inventors, the carbon particles have a very large surface area per unit weight and adsorbed moisture. When the platinum nanoparticles are supported on the surface of the carbon particles, the adsorbed moisture is desorbed in advance. However, it takes time for the desorption, and an effective pumping speed of about 300 liters for about 2 g of carbon particles. Even when a vacuum pump having a performance of / sec is used, it takes about one hour to reach a vacuum degree of 10 ⁻³ Pa or less, which is judged to be sufficiently desorbed.

JP-A-10-189003 JP 2000-243406 A

  In addition, after deaeration is completed, when platinum nanoparticles are formed on the surface of carbon particles by a coaxial vacuum arc deposition source, platinum ions collide with the surface of carbon particles with an energy of about 20 eV to 80 eV. Due to the impact, the crystallinity of the surface of the carbon particles is damaged and the conductivity is lowered. And it has been found that the reduced crystallinity is recovered by heat treatment of carbon particles carrying platinum nanoparticles. However, if a separate heat treatment chamber is prepared and heat treated, the carbon particles carrying the platinum nanoparticles are brought into contact with the atmosphere before the heat treatment and adsorb moisture again. Furthermore, when the heat-treated carbon particles are taken out from the vacuum heat treatment chamber, it is necessary to cool to room temperature, but if the cooling takes time and the occupation time of the heat treatment chamber becomes long, The heat treatment applied to the carbon particles carrying the next batch of platinum nanoparticles will be delayed.

  The present invention has been made in view of the above problems, and when carrying active metal nanoparticles having a catalytic action on the surface of the particulate carrier, from the prior deaeration treatment for desorbing the moisture adsorbed on the particulate carrier, It is an object of the present invention to provide a catalyst nanoparticle supporting apparatus capable of shortening the time required for subsequent heat treatment and cooling of a particulate carrier supporting active metal nanoparticles.

  The above problem can be solved by the configuration of claim 1, and the solution means will be described as follows.

The catalyst nanoparticle supporting apparatus having a coaxial vacuum arc vapor deposition source according to claim 1 is a first chamber, and is provided with a carrying-in door for a carrying container containing a particulate carrier, and is carried into the bottom of the first chamber. A deaeration chamber that includes a first support member that supports the transport container, and desorbs moisture adsorbed on the particulate carrier in the transport container supported by the first support member;
A columnar cathode electrode having an active metal as an element, a cylindrical insulator provided coaxially in contact with the outer peripheral surface of the cathode electrode, and an upper portion in the second chamber; A trigger electrode provided coaxially in contact with the outer peripheral surface of the insulator, and a cylindrical shape provided coaxially with a predetermined interval from the outer peripheral surface of the trigger electrode, one end side being opened in the second chamber and the other end side being A coaxial vacuum arc deposition source comprising an anode electrode closed at a position spaced apart from the cathode electrode is provided, and conveyed to a position facing the opening side of the coaxial vacuum arc deposition source at the bottom of the second chamber. A second support member for supporting the transport container is provided, the active metal is evaporated from a coaxial vacuum arc deposition source, and active metal nanoparticles are formed on the surface of the particulate carrier in the transport container supported by the second support member. Forming A bearing chamber for lifting,
A third chamber, a third chamber heat source provided in the third chamber, and a third support for supporting a transport container transported below the third chamber heat source at the bottom of the third chamber A heat treatment chamber for heat treating the particulate carrier carrying the active metal nanoparticles in the transport container supported by the third support member,
It is the fourth chamber, and the particulate carrier on which the active metal nanoparticles supported by the transport container transported into the fourth chamber is placed can be cooled, and the location of the transport container can be moved The movable cooling table and the cooling chamber provided with the carry-out door of the transfer container are connected in order through the gate door between each chamber,
The deaeration chamber is provided with a first transport mechanism for transporting the transport container supported by the first support member to the second support member in the support chamber, and the support chamber is transported by the second support member. A second transport mechanism for transporting the container to the third support member in the heat treatment chamber is provided, and the third transport mechanism for transporting the transport container supported by the third support member to the movable cooling table in the cooling chamber is provided in the heat treatment chamber. It is a device provided.

  The catalyst nanoparticle support device equipped with such a coaxial vacuum arc evaporation source is adsorbed on the particulate carrier in a deaeration chamber arranged upstream of the support chamber for supporting the active metal nanoparticles on the surface of the particulate carrier. In the heat treatment chamber disposed downstream of the loading chamber, the particulate carrier whose crystallinity has decreased during the loading treatment is heat treated to recover the crystallinity, and in the subsequent cooling chamber, the temperature is increased in the heat treatment chamber. By cooling the rising particulate carrier, the time required to carry the catalyst nanoparticles on the particulate carrier as compared with the case where each of the deaeration, loading, heat treatment, and cooling treatment is performed only in the loading chamber. Is greatly shortened.

  The catalyst nanoparticle supporting apparatus having the coaxial vacuum arc deposition source according to claim 2 is such that the first support member in the deaeration chamber, the second support member in the support chamber, and the third support member in the heat treatment chamber all rotate. This is a shaft, and the bottom surface side of the transport container is detachably supported by the upper end portion of the rotation shaft, and the accommodated particulate carrier is agitated by rotating the transport container by the rotation shaft It is a device that has been.

  The catalyst nanoparticle supporting apparatus having such a coaxial vacuum arc deposition source is accommodated inside by rotating the transfer container during each processing operation in the deaeration chamber, the supporting chamber, and the heat treatment chamber. The particulate carrier can be agitated, and the entire particulate carrier is uniformly treated in each of the deaeration chamber, the loading chamber, and the heat treatment chamber.

  The catalyst nanoparticle supporting apparatus having the coaxial vacuum arc vapor deposition source according to claim 3 is a first apparatus for heating the particulate carrier in a transport container that is carried into and supported by the bottom of the deaeration chamber that is the first chamber. The one-chamber heating source is an apparatus provided in the first chamber.

  The catalyst nanoparticle supporting apparatus having such a coaxial vacuum arc deposition source heats the particulate carrier to promote desorption of moisture.

  According to a fourth aspect of the present invention, there is provided a catalyst nanoparticle carrying apparatus having a coaxial vacuum arc vapor deposition source, wherein a glove box is connected to a fourth chamber, surrounding a carry-out door.

  The catalyst nanoparticle supporting apparatus equipped with such a coaxial vacuum arc deposition source can take out the transport container into the glove box that is in an inert gas atmosphere together with the fourth chamber. Do not let the particulate carrier come into contact with the atmosphere.

  According to the catalyst nanoparticle supporting apparatus equipped with the coaxial vacuum arc evaporation source according to claim 1, the deaeration chamber is arranged upstream of the supporting chamber for supporting the active metal nanoparticles on the surface of the particulate support. The particulate carrier requiring degassing is performed independently of the loading chamber, and a heat treatment chamber and a cooling chamber are provided on the downstream side of the loading chamber, so that the heat treatment and cooling of the time-consuming particulate carrier are performed with an active metal. Since the loading of the fine particles is performed independently, the loading chamber can be operated efficiently, and when the deaeration chamber is empty, the next collection container containing the particulate carrier can be loaded. In addition, it is possible to increase the productivity of the catalyst nanoparticle support device. In addition, since the particulate carrier does not come into contact with the atmosphere while the conveyance container is conveyed between the chambers, the particulate carrier does not adsorb moisture in the atmosphere, and waste such as repeated deaeration operations is avoided. Do not generate.

  According to the catalyst nanoparticle supporting apparatus having the coaxial vacuum arc vapor deposition source according to claim 2, supported by the first support member in the deaeration chamber, the second support member in the support chamber, and the third support member in the heat treatment chamber. In the deaeration chamber, the support chamber, and the heat treatment chamber, the processing operation for each chamber can be performed by rotating the transport container that is being rotated by the rotating shaft. It can be applied evenly to the entire carrier and provides a carrier with excellent quality.

  According to the catalyst nanoparticle supporting apparatus equipped with the coaxial vacuum arc vapor deposition source according to claim 3, the particulate carrier is degassed while being heated, so that the moisture adsorbed on the particulate carrier is desorbed and evacuated. This shortens the time required and improves the operating rate of the catalyst nanoparticle support device.

  According to the catalyst nanoparticle carrying apparatus equipped with the coaxial vacuum arc vapor deposition source according to claim 4, the transport container carried out from the cooling chamber to the glove box is covered with a lid, and the contained particulate carrier is sealed. It can be taken out to the atmosphere side.

  The catalyst nanoparticle support apparatus equipped with the coaxial vacuum arc deposition source of the present invention will be described by way of an embodiment. The catalyst nanoparticle support apparatus of the present invention is a coaxial prototype experimentally developed by the present inventors. A support device using a vacuum vacuum evaporation source, that is, a cylindrical cathode electrode having an active metal as an element, and a coaxial cathode in contact with the outer peripheral surface of the cathode electrode at the upper part in a chamber to which a vacuum pump is attached A cylindrical insulator, a trigger electrode coaxially provided in contact with the outer peripheral surface of the insulator, a cylindrical shape coaxially provided at a predetermined interval from the outer peripheral surface of the trigger electrode, and one end side thereof It has a coaxial vacuum arc deposition source that consists of an anode electrode that is opened in the chamber and closed at a position separated from the cathode electrode at the other end, and is opposed to the opening side of the coaxial vacuum arc deposition source at the bottom of the chamber A support member for supporting a transport container containing a particulate carrier that is a deposition target that is transported to a position where the active metal is evaporated from a coaxial vacuum arc deposition source and supported by the support member. A chamber for forming and supporting active metal nanoparticles on the surface of the particulate carrier in the transport container is a loading chamber, and a deaeration chamber for evacuating the adsorbed moisture of the particulate carrier on the upstream side of the loading chamber is provided. And a heat treatment chamber for recovering the crystallinity of the particulate carrier, which has been lowered due to collision of ions in the atomic state of the active metal in the support chamber on the downstream side of the support chamber, and a particulate shape whose temperature has been increased by the heat treatment The catalyst supporting device is arranged in order with a cooling chamber for cooling the carrier.

  The coaxial vacuum arc deposition source in the support chamber is equipped with a power source with a discharge voltage of 100 V to 400 V and a capacitor with a capacity of 1000 μF to 9000 μF, and is set so that the pulse discharge period is 1 Hz to 5 Hz and the discharge time is 1000 μsec or less. Then, a trigger discharge is generated between the trigger electrode and the anode electrode, and an arc discharge is induced between the cathode electrode and the anode electrode by the trigger discharge, so that the active metal that is a component of the cathode electrode is partially The active metal is formed on the surface of the particulate carrier, which is a deposition target, which is melted, evaporated, converted into plasma, and then fly into the chamber, and is transported together with the transport container to a position facing the coaxial vacuum arc deposition source in the chamber. Nanoparticles are formed and supported. The cathode electrode may be entirely composed of an active metal, or the discharge part may be an active metal. Moreover, it is preferable that the support member is provided with a function capable of stirring the particulate carrier in the transport container during arc vapor deposition.

  As active metals, catalysts for fuel cells and automobile exhaust gas purification catalysts are usually palladium (Pd), platinum (Pt), rhodium (Rh), ruthenium (Ru), osmium (Os), iridium ( A noble metal made of Ir) is used, but the base film in the production of carbon nanotubes includes iron (Fe), cobalt (Co), nickel (Ni) iron group metals, as well as cobalt titanium (Co / Ti). The alloy is used. That is, the active metal is appropriately selected depending on the field to which it is applied. As the particulate carrier, a powdery material that can withstand the temperature at which the catalyst is used, for example, conductive carbon particles, insulating alumina particles, silica particles, and the like are appropriately selected.

  The deaeration chamber arranged on the upstream side of the support chamber is a chamber equipped with a vacuum pump, and includes a carry-in door of a transport container containing a particulate carrier, and a support member that supports the transport container, The carrying chamber is connected via a gate door. The particulate carrier in the transport container supported by the support member evaporates the adsorbed water under reduced pressure by a vacuum pump, and the generated water vapor is evacuated, but in order to promote the desorption of water, It is preferable to provide a heating source for raising the temperature of the particulate carrier, for example, an infrared lamp to heat the particulate carrier during deaeration. The support member of the deaeration chamber is preferably capable of stirring the particulate carrier in the transport container during the deaeration process. That is, the carrier may be agitated by vibrating the carrier, or the carrier may be agitated by inserting a fixed blade or baffle into the carrier and rotating the carrier in a horizontal plane. You may do.

  The heat treatment chamber disposed downstream of the support chamber is a chamber equipped with a vacuum pump, and is connected to the support chamber via a gate door. A heat source such as an infrared lamp is provided at the top of the heat treatment chamber, and a support member is provided at the bottom of the heat treatment chamber to support a transport container that is transported below the heat source. By increasing the temperature of the particulate carrier carrying the active metal nanoparticles contained therein to restore the crystallinity of the particulate carrier, for example, its conductivity is restored. The support member is preferably capable of stirring the particulate carrier in the transport container, like the support member of the deaeration chamber and the support chamber.

  The cooling chamber disposed downstream of the heat treatment chamber is a chamber to which a vacuum pump is attached, and is connected to the heat treatment chamber via a gate door. The cooling chamber mounts a transport container transported from the upstream heat treatment chamber, cools the particulate carrier whose temperature in the transport container is rising, together with the active metal nanoparticles, and moves the position of the transport container after cooling. It has a movable cooling stand that can be made to operate. This is to allow two or more transport containers to be simultaneously placed on the movable cooling table because it takes time to cool the particulate carrier whose temperature is rising naturally. You may make it spray the cooled inert gas instead of letting it cool naturally.

EXAMPLES Hereinafter, the catalyst nanoparticle carrying | support apparatus provided with the coaxial type vacuum arc evaporation source of this invention is concretely demonstrated by an Example. FIG. 1 shows a catalyst nanoparticle support of an embodiment in which a platinum nanoparticle as an active metal is formed and supported on the surface of carbon particles (activated carbon powder) as a particulate support using a coaxial vacuum arc deposition source. 2 is a plan view showing the device 1. FIG. That is, the catalyst nanoparticle support device 1 is a vacuum system in which the deaeration chamber 10, the support chamber 20, the heat treatment chamber 30, the cooling chamber 40, and the glove box 50 are connected in order. The deaeration chamber 10 is a cylindrical first chamber, and is a chamber that desorbs moisture adsorbed on carbon particles in a transfer container carried in from the outside as water vapor and evacuates it in advance. The supporting chamber 20 is a cylindrical second chamber, and is a chamber in which platinum (Pt) nanoparticles are supported on the surface of carbon particles using a coaxial vacuum arc evaporation source provided in the chamber. The heat treatment chamber 30 is a cylindrical third chamber, and is a chamber for recovering the crystallinity by heat-treating the carbon particles P whose crystallinity is lowered by the impact caused by the collision of platinum ions in the support chamber 20. The cooling chamber 40 is a rectangular parallelepiped fourth chamber, and is a chamber for cooling the carbon particles P whose temperature is increased by the heat treatment in the heat treatment chamber 30. An inert gas (argon (Ar) gas or nitrogen (N ₂ ) gas supply source) is connected to the glove box 50.

  The deaeration chamber 10, the support chamber 20, the heat treatment chamber 30, and the cooling chamber 40 are integrated with piping serving as a transfer path of the transfer container via gate doors 9A, 9B, and 9C provided between the chambers. It is connected. Further, the deaeration chamber 10 is provided with a loading / unloading door 11 for a transfer container containing carbon particles, the cooling chamber 40 is provided with unloading doors 41A and 41B, and is not used in the carrying chamber 20 during normal operation. A blind lid 31 is provided in the blind lid 21 as well as in the heat treatment chamber 30.

  In addition, the degassing chamber 10 has a mounting portion 12S that can be vacuum-sealed by the first transfer mechanism 12 for transferring the transfer container containing the degassed carbon particles from the degassing chamber 10 to the carrier chamber 20. Is attached to the side wall of the deaeration chamber 10. That is, by moving the end portion 12E of the first transport mechanism 12 to the deaeration chamber 10 side, the inclusion rod 12R shown in FIG. 6 described later holds the transport container at the tip portion, and the opened gate door 9A. It can be conveyed to the inside of the carrying chamber 20 through. Similarly, a second transport mechanism 22 for transporting a transport container from the support chamber 20 to the heat treatment chamber 30 is attached to the support chamber 20 via an attachment portion 22S, and the transport container is transferred from the heat treatment chamber 30 to the heat treatment chamber 30. The 3rd conveyance mechanism 32 conveyed to the cooling chamber 40 is attached via the attachment part 3S.

  The mounting portion 12S is configured such that the first transport mechanism 12 moves in the up and down Y direction and the left and right X directions perpendicular to the first transport mechanism 12 in the Z direction, that is, the first transport mechanism 12. Can be adjusted in the vertical and horizontal directions. The same applies to the attachment portion 22S of the second transfer mechanism 22 in the holding chamber 20 and the attachment portion 32S of the third transfer mechanism 32 in the heat treatment chamber 30.

  FIG. 2 is a schematic longitudinal sectional view of the deaeration chamber 10 shown in FIG. A turbo molecular pump 19T for evacuating the inside of the deaeration chamber 10 is attached to the deaeration chamber 10 as the first chamber via a variable flow valve 19b, and a valve 19b ′ is provided on the exhaust side of the turbo molecular pump 19T. A rotary pump 19R is attached via In FIG. 2, illustration of the carry-in opening and the carry-out opening of the transfer container 61 is omitted.

  And the 1st rotating shaft 14 which supports the conveyance container 61 carried in into the deaeration chamber 10 from the carrying-in door 11 not shown in FIG. 2 in the upper end part is provided in the bottom part of the deaeration chamber 10, The first rotating shaft 14 rotatably passes through a first fixed base 16 that is attached to a member that is not shown, and further, the bottom of the deaeration chamber 10 is opened to the atmosphere via a vacuum seal mechanism that is not shown. The rotary drive source 15 is connected to the lower end portion. The fixed blade 18 is attached to the support column 17 fixed to the first fixed base 16, and the fixed blade 18 is positioned at a depth close to the bottom surface of the transport container 61. Therefore, when the transport container 61 is rotated by the rotating shaft 14, the carbon particles P accommodated therein are agitated. In FIG. 2, illustration of the carry-out opening of the transport container 61 is omitted.

  The support column 17 is extendable in the vertical direction. When the transfer container 61 is carried into the deaeration chamber 10 from the carry-in door 11, or when the transfer container 61 is moved from the deaeration chamber 10 to the carrying chamber by the first transfer mechanism 12. When transporting to 20, the fixed blade 18 can be raised to the upper retreat position indicated by the alternate long and short dash line so as not to interfere. The same applies to the fixed blades 28 in the carrying chamber 20 and the fixed blades 38 in the heat treatment chamber 30, which will be described later. In the embodiment, the support column 17 can be expanded and contracted in the vertical direction, but other operations, for example, the support column 17 together with the fixed blades 18 may be tilted outward.

Furthermore, a heating source 13 for the deaeration chamber is provided in the upper part of the deaeration chamber 10. That is, the moisture adsorbed on the carbon particles P is desorbed as water vapor and evacuated. As described above, the desorption of the moisture is completed and the degree of vacuum reaches 1.3 × 10 ⁻³ Pa or less. Takes a long time. The heat source 13 for the deaeration chamber is intended to promote the desorption of moisture by preventing the temperature and the evaporation rate of the carbon particles P from decreasing due to the evaporation of moisture. The heating source 13 for the deaeration chamber is provided with a heating lamp 13a and a heat ray reflector 13b attached by a hanging tool 13c that penetrates the ceiling of the deaeration chamber 10, and the heating lamp 13a is located outside the deaeration chamber 10. It is connected to a controller 13d having both a power supply and a temperature adjustment mechanism.

  FIG. 3 is a schematic longitudinal sectional view of the carrying chamber 20 shown in FIG. A turbo molecular pump 29T for evacuating the inside of the supporting chamber 20 is attached to the supporting chamber 20 as the second chamber via a variable flow valve, and a rotary pump is connected to the exhaust side of the turbo molecular pump 29T via a valve. 29R is attached. In FIG. 3, the illustration of the carry-in opening and the carry-out opening of the transfer container 61 is omitted.

  A coaxial vacuum arc deposition source 51 is provided above the support chamber 20 to evaporate platinum (Pt) as an active metal and fly it as plasma. That is, the coaxial vacuum arc deposition source 51 includes a cylindrical cathode electrode 52 made of platinum as an evaporation material, and a hat-shaped insulator 53 that is coaxially provided in contact with the outer peripheral surface of the cathode electrode 52 and is upside down. The cylindrical trigger electrode 54 that is in contact with the outer peripheral surface of the cylindrical portion of the hat of the insulator 53 and that is in contact with the upper end of the hat's flange and is coaxially provided with a predetermined distance from the outer peripheral surface of the trigger electrode 54. The anode electrode 55 has a cylindrical shape that is open and coaxially provided, the lower end side is opened toward the inside of the carrier chamber 20, and the upper end side is closed at a position separated from the upper end of the cathode electrode 52.

  A trigger power supply 56 is provided between the trigger electrode 54 and the cathode electrode 52, and an arc DC power supply 57 is provided between the cathode electrode 52 and the anode electrode 55. The trigger power supply 56 has a positive terminal connected to the trigger electrode 54 and a negative terminal connected to the cathode electrode 52 at the same potential as the negative terminal of the DC power supply 57. The trigger power source 56 is composed of a pulse transformer, and boosts and outputs a pulse voltage in units of 200 V and a cycle of μsec to 3.4 kV (several μA), which is 17 times.

  The arc DC power supply 57 has a voltage of 100 V and a current of several A, and its positive terminal is grounded and at the ground potential, and is connected to the anode electrode 55. A capacitor unit 58 having a capacity of 8800 μF is provided in parallel with the DC power supply 57, one terminal is connected to the plus terminal side of the DC power supply 57, and the other terminal is connected to the minus terminal side of the DC power supply 57. Yes. The capacitor unit 58 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 57. Since the charging takes about 1 second, the discharge cycle when the discharge from the capacitor unit 58 is repeated is about 1 Hz.

  The transfer container 61 that stores the degassed carbon particles P transferred from the deaeration chamber 10 is rotated immediately below the opening side of the coaxial vacuum arc deposition source 51 in the first rotation of the deaeration chamber 10. It is supported by the upper end part of the 2nd rotating shaft 24 comprised similarly to the axis | shaft 14. FIG. That is, the second rotating shaft 24 is rotatably penetrated by a second fixing base 26 attached to the carrying chamber 20 by a member not shown in the drawing, similarly to the first rotating shaft 14, and further a vacuum seal not shown in the drawing. A bottom portion of the carrying chamber 20 is penetrated to the atmosphere side through a mechanism, and a rotational drive source 25 is connected to a lower end portion thereof. Then, the stationary blade 28 supported by the extendable column 27 attached to the second fixed base 26 is positioned at a depth close to the bottom surface of the transport container 61, and the transport container 61 is rotated by the rotation drive source 25. The carbon particles P are agitated by the fixed blades 28.

  FIG. 4 is a schematic longitudinal sectional view of the heat treatment chamber 30 shown in FIG. That is, the heat treatment chamber 30 is configured in the same manner as the deaeration chamber 10, and in the heat treatment chamber 30 as the third chamber, a turbo molecular pump 39T for evacuating the heat treatment chamber 30 is provided via a variable flow valve. A rotary pump 39R is attached to the exhaust side of the turbo molecular pump 39T via a valve. In FIG. 4, the illustration of the carry-in opening and the carry-out opening of the transfer container 61 is omitted.

  The carbon particles P transported from the support chamber 20 into the heat treatment chamber 30 are deteriorated in crystallinity due to the impact caused by the collision of platinum ions when the platinum nanoparticles are supported, but the carbon particles P are heat treated. A heat source 33 for heat treatment chamber for recovering the crystallinity is provided in the upper portion of the heat treatment chamber 30. It has been found that this decrease in crystallinity is recovered by heating at about 300 ° C. for about 1 hour. The heat source 33 for heat treatment chamber is provided with a heating lamp 33 a and a heat ray reflector 33 b attached by a suspending tool 33 c that penetrates the ceiling of the heat treatment chamber 30. The heat lamp 33 a is provided outside the heat treatment chamber 30. It is connected to a controller 33d having both a power source and a temperature control mechanism.

  The bottom of the heat treatment chamber 30 is provided with a third rotating shaft 34 that supports the transfer container 61 carried directly under the heat treatment chamber heating source 33 at its upper end. It is the same as in the case of the deaeration chamber 10 and the carrying chamber 20 that the fixed blade 38 supported by the attached stretchable support column 37 is inserted to a position close to the bottom surface of the transport container 61. When the transport container 61 is rotated by the rotational drive source 35 connected to the lower end of the third rotating shaft 34, the carbon particles P carrying platinum nanoparticles accommodated therein are stirred by the fixed blade 38. The

  FIG. 5 is a schematic longitudinal sectional view taken along the line [5]-[5] in the cooling chamber 40 shown in FIG. A turbo molecular pump 49T for evacuating the inside of the cooling chamber 40 is attached to the cooling chamber 40, which is the fourth chamber, via a variable flow valve, and a rotary pump is connected to the exhaust side of the turbo molecular pump 49T via a valve. 49R is attached.

  As shown in FIG. 5, the cooling chamber 40 is provided with a movable cooling table 42 having wheels 44 that run on rails (not shown), and the transfer container 61 transferred from the heat treatment chamber 30 is loaded. It is carried in from the opening 40w and placed on, for example, the support plate 43A provided on the movable cooling table 42. Support plates 43A and 43B are provided on the movable cooling table 42 so that the two transfer containers 61 can be placed thereon. However, when the cooling of the carbon particles P takes time, the movable cooling table 42 is provided. This is because the support plate 43B is positioned in front of the carry-in opening 40w and the transport container 61 ′ of the next batch is placed.

  The transport mechanism of the transport container 61 already briefly described above is attached to the deaeration chamber 10 with reference to FIG. 1 and supported by the upper end portion of the first rotating shaft 14 in the deaeration chamber 10. In addition to the cylindrical first transport mechanism 12 that transports the transport container 61 to the downstream support chamber 20 and supports it on the upper end portion of the second rotation shaft 24, the second transport mechanism provided in the support chamber 20 22 and the third transfer mechanism 32 provided in the heat treatment chamber 30 are all configured in the same manner. Therefore, the first transfer mechanism 12 of the deaeration chamber 10 will be described below, and the description of the other transfer mechanisms will be omitted. To do.

  6A is a partial vertical cross-sectional view showing, in an enlarged manner, a portion where the transport container 61 is supported by the upper end portion of the first rotating shaft 14 of the deaeration chamber 10 in FIG. That is, a state in which the fork 12F attached to the tip of the inclusion rod 12R of the first transport mechanism 12 is being inserted between the transport container 61 and the first fixed base 16 is shown. FIG. 6B is a plan view seen at the level of the surface of the fork 12F, and the bottom surface of the transport container 61 is indicated by a two-dot chain line, but the first fixed base 16 is not shown. The bottom plate of the transport container 61 is provided with a fitting hole 62 for fitting the upper end portion of the first rotating shaft 14 together with the key groove 62w, and the upper end portion where the key 14k of the first rotating shaft 14 is provided in the fitting hole 62. The carrier container 61 is supported by being inserted. Then, after inserting the fork 12F with the first rotating shaft 14 in between, the mounting portion 12S of the first transport mechanism 12 is operated to move the first transport mechanism 12 and the inclusion rod 12R upward, thereby conveying the transport container 61. Is supported by the fork 12 and raised to the position indicated by the alternate long and short dash line, and becomes a height position floating from the tip of the first rotating shaft 14. After the transport container 61 is lifted to its height position, the transport container 61 is transported to the position directly above the second rotating shaft 24 of the carrier chamber 20 by the inclusion rod 12R of the first transport mechanism 12, and then transported by lowering the transport container 61. The container 61 can be supported on the upper end portion of the second rotation shaft 24. Thereafter, the inclusion rod 12 </ b> R is pulled back to the deaeration chamber 10 from directly below the transfer container 61.

The catalyst nanoparticle supporting apparatus 1 having the coaxial vacuum arc evaporation source 51 of the present embodiment is configured as described above. Next, the operation thereof will be described. In FIG. 1, a transport container 61 containing carbon particles P is carried into the deaeration chamber 10 from the carry-in door 11 and supported by the upper end portion of the first rotating shaft 14. The carry-in door 11 is closed, and the deaeration chamber 10, the support chamber 20, the heat treatment chamber 30, and the cooling chamber 40 have gate doors 9A, 9B, and 9C between the chambers. It is assumed that it is closed and already evacuated, inert gas is introduced if necessary, and the degree of vacuum is maintained at 1 × 10 ⁻⁵ Pa or less. Further, the stationary blade 28 of the support chamber 20 and the third rotating shaft 28 of the heat treatment chamber 30 are stopped from being rotated, and the degassing chamber source 13 and the heat treatment chamber heating source 33 are in an operating state. It is assumed that the coaxial vacuum arc evaporation source 51 of the carrying chamber 20 is ready to start operation.

In this state, referring to FIG. 2, when the transport container 61 is rotated by the first rotating shaft 14 in the deaeration chamber 10, the stored carbon particles P are agitated by inserting the fixed blades 18. However, in this state, the heating lamp 13a of the heat source 13 for the deaeration chamber is heated to a temperature of 150 ° C. to 200 ° C. under vacuum. Accordingly, the moisture adsorbed on the carbon particles P is evaporated and evacuated. If the degree of vacuum is 1.3 × 10 ⁻³ Pa or less, it is determined that the desorption of moisture is completed, the fixed blade 18 is raised to the retracted position indicated by the alternate long and short dash line, and the rotation of the first rotating shaft 14 is stopped. . Subsequently, the gate door 9A shown in FIG. 1 is opened, and the fork 12F at the tip of the inner rod 12R of the first transport mechanism 12 is inserted between the transport container 61 and the first fixed base 16 as shown in FIG. Then, the transport container 61 is lifted and floated from the tip of the first rotation shaft 14, and transported to the downstream holding chamber 20 in this state, and the transport container 61 is supported on the upper end portion of the second rotation shaft 24. Thereafter, the inclusion rod 12R is pulled back to the deaeration chamber 10, and the gate door 9A is closed.

  In the carrying chamber 20, referring to FIG. 3, the second rotating shaft 24 is rotated, the fixed blade 28 in the retracted position is lowered to the vicinity of the bottom surface of the transfer container 61, and stirring of the carbon particles P is started. The type vacuum arc evaporation source 51 is activated to carry platinum nanoparticles on the surface of the carbon particles P. First, a pulse voltage of 3.4 kV is output from the trigger power source 56 to the trigger electrode 54 and creeps along the lower end surface of the insulator 53 which is the shortest distance between the lower end of the cathode electrode 52 and the lower end of the trigger electrode 54. Discharge, that is, trigger discharge is caused. Since the capacitor unit 58 is charged at any time by the DC power source 57 for arc, it is induced by the trigger discharge and arc discharge is generated between the cathode electrode 52 and the anode electrode 55.

  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 enters the plasma. Since it is emitted, it is turned into plasma and dissociated into electrons and platinum ions.

  At this time, an arc current flows in the cathode electrode 22, thereby forming a magnetic field concentrically around the cathode electrode 22. Therefore, the electrons and platinum ions emitted from the cathode electrode 22 are subjected to Lorentz force from the magnetic field. The electrons are accelerated by the Lorentz force, and atomic platinum ions having a large (charge / mass) ratio are accelerated in the axial direction of the cathode electrode 22 by the Lorentz force and the Coulomb force between the electrons and fly. It collides with and adheres to the surface of the carbon particles P stirred inside. As a result, platinum nanoparticles (particle diameter: 1 nm to 10 nm) are formed and supported on the surface of the carbon particles P.

  When the carrying operation is completed, the fixed blade 28 shown in FIG. 3 is raised to the retracted position, and the rotation of the second rotating shaft 14 is stopped. Then, the gate door 9B shown in FIG. 1 is opened, and as in the deaeration chamber 10, the transfer container 61 is lifted by the inclusion rod of the second transfer mechanism 22 and floated from the tip of the second rotating shaft 24, and downstream heat treatment is performed. The transport container 61 is supported by the upper end of the third rotating shaft 34 by transporting to the chamber 30. Thereafter, the inclusion rod is pulled back to the carrying chamber 20, and the gate door 9B is closed.

  In the heat treatment chamber 30, referring to FIG. 4, the third rotating shaft 34 is rotated, and the stationary blade 38 in the retracted position is lowered to the vicinity of the bottom surface of the transport container 61 to support the carbon particles P carrying platinum nanoparticles. While stirring is started, the heat lamp 33a of the heat source 33 for heat treatment chamber is heated under vacuum. That is, due to the collision of platinum ions in the support chamber 20, the crystallinity of the surface layer portion of the carbon particles P as a carrier is damaged and the conductivity is reduced, but in order to recover the crystallinity, The carbon particles P carrying the platinum nanoparticles are heat-treated at a temperature range of 350 ° C. to 600 ° C. for 20 minutes to 30 minutes.

  When the heat treatment is finished, the fixed blade 38 is raised to the retracted position, and the rotation of the third rotating shaft 14 is stopped. Then, the gate door 9C shown in FIG. 1 is opened, and similarly to the deaeration chamber 10, the transfer container 61 is lifted by the inclusion rod of the third transfer mechanism 32 and floated from the tip of the third rotating shaft 34, and the downstream cooling is performed. The conveyance container 61 is mounted on the support plate 43A of the movable cooling stand 42 located in front of the carry-in opening 40w of the cooling chamber 40 shown in FIG. Thereafter, the inclusion rod is pulled back to the heat treatment chamber 30, and the gate door 9C is closed.

  In the cooling chamber 40, the carbon particles P carrying platinum nanoparticles contained in the transfer container 61 are allowed to cool to room temperature. Meanwhile, the movable cooling table 42 is moved so that the support plate 43B is positioned in front of the carry-in opening 40w and waits for the carry-in of the subsequent transfer container 61 '. Then, when the cooling of the carbon particles P carrying the platinum nanoparticles in the transport container 61 is completed, as an example, after introducing an inert gas or air from an introduction pipe (not shown) to bring the inside of the cooling chamber 40 to atmospheric pressure, The transport container 61 can be carried out from the carry-out door 41A. Needless to say, other methods of carrying out may be used. The glove box 50 is in an atmosphere of argon gas, and the carrier container 61 is covered with a sealable lid and taken out to the atmosphere.

  As described above, the catalyst nanoparticle supporting apparatus provided with the coaxial vacuum arc evaporation source of the present invention has been described by way of example, but of course, the present invention is not limited to this example, and the technical idea of the present invention is not limited thereto. Various modifications are possible based on this.

  For example, in this embodiment, the cathode electrode 52 in the coaxial vacuum arc evaporation source 51 of the holding chamber 20 is made of platinum, but the portion where platinum is melted and evaporated by arc discharge generated between the cathode electrode 52 and the anode electrode 55. In FIG. 3, the upper end portion of the cathode electrode 52 may be made of a metal other than platinum.

  Further, in this embodiment, for example, the first rotating shaft 14 is illustrated as a support member of the transfer container 61 in the deaeration chamber 10 and is directly supported by the upper end portion of the first rotating shaft 14. The transport container 61 may be supported by a support member that can be rotated at 14. In any of the above, the transport container 61 is rotated, and the carbon particles P are agitated by the fixed blades 18 provided inside the transport container 61. However, the transport container 61 or a support member that supports the transport container 61 is rotated. It is good also as what stirs the carbon particle P in the conveyance container 61 with a stirrer, without it. The same applies to the loading chamber 20 and the heat treatment chamber 30.

  In the present embodiment, for example, in the deaeration chamber 10, the transfer container 61 is transferred to the carrier chamber 20 by the inclusion rod 12 </ b> R of the first transfer mechanism 12, but other transfer means such as a rail is used. The transport container 61 may be transported by a traveling self-propelled vehicle, and the transport means of the transport container 61 is not limited. In the case of laying rails, the gate doors 9A, 9B, and 9C partially lose the rails, so that the self-propelled vehicle needs to consider the arrangement of wheels so that it can travel on such rails.

  In the present embodiment, for example, in the deaeration chamber 10, the attachment portion 12 </ b> S is used for the first transfer in order to lift the transfer container 61 supported by the upper end of the first rotation shaft 14 from the upper end of the first rotation shaft 14. Although the mechanism 12 can be adjusted in the vertical and horizontal directions together with the inclusion rod 12R, the first rotary shaft 14 may be movable in the vertical and horizontal directions together with the rotational drive source 15.

  In the present embodiment, the cooling of the carbon particles P in the cooling chamber 40 was performed by cooling under vacuum, but instead of cooling by radiation under vacuum, an inert gas was introduced and convection of the inert gas was performed. It is good also as cooling, and you may make it cool by spraying the cooled inert gas.

It is a top view which shows arrangement | positioning of the deaeration chamber, a support chamber, a heat processing chamber, and a cooling chamber in the nanoparticle support apparatus for catalysts provided with the coaxial vacuum arc evaporation source of the Example. It is sectional drawing of a deaeration chamber. It is sectional drawing of a carrying chamber. It is sectional drawing of a heat processing chamber. It is sectional drawing of a cooling chamber. It is a figure which shows the effect | action of the support part of the conveyance container by the 1st rotating shaft of a deaeration chamber, and the inclusion rod of a 1st conveyance mechanism.

Explanation of symbols

1 catalyst nanoparticle support device,
9A, 9B, 9C Gate door, 10 Deaeration chamber,
11 carry-in door, 12 first transport mechanism,
12R inclusion rod, 12S mounting part,
13 Heat source for deaeration chamber, 13a Heating lamp,
13b heat ray reflector, 13d controller,
14 1st rotation axis, 14k key,
16 first fixed base, 17 struts,
18 fixed blade, 19R rotary pump,
19T turbo molecular pump, 20 loading chamber,
22 second transport mechanism, 24 second rotating shaft,
30 heat treatment chamber, 32 third transfer mechanism,
33 heat source for heat treatment chamber, 34 third rotating shaft,
40 Cooling chamber, 41A, 41B Unloading door,
42 movable cooling stand, 43A, 43B support plate,
44 wheels, 50 glove box 51 coaxial vacuum arc evaporation source, 52 cathode electrode,
53 Insulator, 54 Trigger electrode,
55 anode electrode, 56 trigger power supply,
57 DC power supply for arc, 58 capacitor unit,
61 transport container, 62 insertion hole,
62w keyway,

Claims (4)

The first chamber is provided with a carrying-in door for a carrying container that contains the particulate carrier, and a first support member that supports the carrying container to be carried is provided at the bottom of the first chamber. A deaeration chamber for desorbing moisture adsorbed on the particulate carrier in the transport container supported by a support member;
A columnar cathode electrode having an active metal as an element, a cylindrical insulator provided coaxially in contact with the outer peripheral surface of the cathode electrode, and an upper portion in the second chamber; A trigger electrode coaxially provided in contact with the outer peripheral surface of the insulator and a cylindrical shape coaxially provided at a predetermined interval from the outer peripheral surface of the trigger electrode, one end side being opened in the second chamber and the other end A coaxial vacuum arc deposition source having an anode electrode closed at a position spaced apart from the cathode electrode, and at the bottom of the second chamber to a position facing the opening side of the coaxial vacuum arc deposition source A second support member for supporting the transport container to be transported; evaporating the active metal from the coaxial vacuum arc deposition source; and the transport container supported by the second support member in the transport container grain A bearing chamber to be supported to form an active metal nanoparticles on the surface of the Jo carrier,
A third chamber, and a third chamber heating source is provided in the third chamber, and the bottom of the third chamber supports the transport container transported below the third chamber heat source. A heat treatment chamber comprising a third support member, and heat-treating the particulate carrier carrying the active metal nanoparticles in the transport container supported by the third support member;
A fourth chamber that cools the particulate carrier on which the active metal nanoparticles supported by the transport container transported into the fourth chamber is placed; A movable cooling stand that can be moved and a cooling chamber provided with a carry-out door of the transfer container are connected in sequence between each chamber via a gate door,
The deaeration chamber is provided with a first transfer mechanism for transferring the transfer container supported by the first support member to the second support member in the support chamber, and the support chamber has the second support. A second transport mechanism configured to transport the transport container supported by a member to the third support member in the heat treatment chamber, wherein the heat treatment chamber includes the transport container supported by the third support member; A catalyst nanoparticle supporting apparatus having a coaxial vacuum arc deposition source, wherein a third transport mechanism for transporting to the movable cooling table in the cooling chamber is provided.   The first support member in the deaeration chamber, the second support member in the carrying chamber, and the third support member in the heat treatment chamber are all rotating shafts, and the bottom surface side of the transfer container is the upper end of the rotating shaft. The coaxial type according to claim 1, wherein the particulate carrier is agitated by rotating the transport container by the rotating shaft so that the particulate carrier is agitated. Catalyst nanoparticle support device equipped with a vacuum arc evaporation source.   A heating source for a first chamber for heating the particulate carrier in the transport container that is carried into and supported by the bottom of the deaeration chamber, which is the first chamber, is provided in the first chamber. A catalyst nanoparticle support apparatus comprising the coaxial vacuum arc deposition source according to claim 1 or 2.   The catalyst nanoparticle supporting apparatus comprising the coaxial vacuum arc evaporation source according to any one of claims 1 to 3, wherein a glove box is connected to the fourth chamber so as to surround the carry-out door.

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