WO2016013245A1 - Matériau de catalyseur et son procédé de production - Google Patents

Matériau de catalyseur et son procédé de production Download PDF

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WO2016013245A1
WO2016013245A1 PCT/JP2015/056440 JP2015056440W WO2016013245A1 WO 2016013245 A1 WO2016013245 A1 WO 2016013245A1 JP 2015056440 W JP2015056440 W JP 2015056440W WO 2016013245 A1 WO2016013245 A1 WO 2016013245A1
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catalyst material
dispersion
carbon
fine particles
carbon nanofibers
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Japanese (ja)
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新井　進
貢 上島
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Zeon Corp
Shinshu University NUC
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Zeon Corp
Shinshu University NUC
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
    • C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/01—Saturated compounds having only one carboxyl group and containing hydroxy or O-metal groups
    • C07C59/10—Polyhydroxy carboxylic acids
    • C07C59/105—Polyhydroxy carboxylic acids having five or more carbon atoms, e.g. aldonic acids

Definitions

  • the present invention relates to a catalyst material and a method for producing the same, and more particularly to a catalyst material containing gold fine particles and a method for producing the catalyst material.
  • Gold can be made into fine particles, such as low-temperature CO oxidation reaction, propylene vapor phase one-step epoxidation reaction, low-temperature water gas shift reaction, direct hydrogen peroxide synthesis reaction from oxygen and hydrogen, and partial oxidation reaction of hydrocarbons. In such reactions, it is known to exhibit excellent catalytic activity.
  • noble metals such as gold are expensive, they are required to be recovered after use as a catalyst.
  • catalytic materials in which gold fine particles are supported on a carrier have been studied, and in addition, technologies for exerting excellent catalytic activity on the catalytic materials have been widely studied. (For example, see Patent Documents 1 and 2).
  • Patent Document 1 discloses a catalyst material in which metal particles such as gold fine particles are supported on a carrier containing carbon, and at least a part of the metal particles has a planar region (for example, a maximum width of 3 to 100 nm), It has been reported that it exhibits excellent surface activity and, for example, exhibits excellent effects as a catalyst for treating nitrate nitrogen.
  • Patent Document 2 as a method for obtaining a catalyst material by dispersing and immobilizing gold fine particles on a support, gold-chalcogen ions formed by adding a chalcogenide to a gold compound solution are brought into contact with the support to form a support.
  • a method is disclosed in which gold chalcogenide is precipitated on the surface of the carrier by adsorbing gold-chalcogen ions, and then gold fine particles are precipitated on the surface of the carrier by separating and heating the carrier.
  • this method makes it possible to support gold fine particles on an acidic carrier, which has been difficult with the conventional method, and that the catalyst material obtained by this method has excellent catalytic activity.
  • Patent Documents 1 and 2 fail to exhibit a sufficiently satisfactory catalytic activity for the catalyst material.
  • Patent Documents 1 and 2 mainly focus on the gold fine particles and the supporting method thereof, and the carrier supporting the gold fine particles has not been sufficiently studied. That is, the above-described conventional technology has room for improvement, particularly in that the catalyst material exhibits excellent catalytic activity by improving the carrier supporting the gold fine particles.
  • an object of this invention is to provide the catalyst material which was carrying
  • Another object of the present invention is to provide a method for producing a catalyst material carrying gold fine particles and having excellent catalytic activity.
  • the inventors of the present invention have made extensive studies to achieve the above object.
  • the inventors of the present invention may further improve the catalytic activity of the catalyst material by using carbon nanofibers having a predetermined average diameter as the support in the catalyst material in which the gold fine particles are supported on the support.
  • the present invention has been completed by finding out what can be done.
  • the present invention aims to advantageously solve the above-mentioned problems, and the catalyst material of the present invention is such that gold fine particles are supported on carbon nanofibers having an average diameter (Av) of 5 nm or less.
  • Av average diameter
  • a catalyst material containing carbon nanofibers having an average diameter of 5 nm or less and gold fine particles supported on the carbon nanofibers has excellent catalytic activity.
  • fiber refers to those having an aspect ratio of 10 or more.
  • the “average diameter of carbon nanofibers” can be determined by measuring the diameter (outer diameter) of 100 carbon nanofibers selected at random using a transmission electron microscope.
  • the average diameter (Av) and the standard deviation ( ⁇ ) of the diameter satisfy the relational expression: 0.20 ⁇ (3 ⁇ / Av) ⁇ 0.60.
  • a carbon nanotube is preferred. This is because the catalytic activity of the catalyst material can be further improved by using carbon nanotubes having 3 ⁇ / Av of more than 0.20 and less than 0.60.
  • “average diameter (Av) of carbon nanotubes” and “standard deviation of carbon nanotube diameter ( ⁇ : sample standard deviation)” are carbons selected at random using a transmission electron microscope, respectively. It can be obtained by measuring the diameter (outer diameter) of 100 nanotubes.
  • the carbon nanofibers are preferably subjected to gas phase plasma treatment. This is because the catalytic activity of the catalyst material can be further improved by using the carbon nanofibers subjected to the gas phase plasma treatment as a carrier.
  • the average particle diameter of the gold fine particles is 2 nm or more and 10 nm or less. This is because if the average particle size of the gold fine particles supported on the carbon nanofibers is 2 to 10 nm, the catalytic activity of the catalyst material can be further improved.
  • the “average particle diameter of gold fine particles” is the particle diameter based on images of 100 gold fine particles carried on carbon nanofibers selected at random using a transmission electron microscope. (The maximum length among the lengths of line segments connecting two points on the outer edge of each particle) can be measured and determined.
  • the manufacturing method of the catalyst material of this invention is a manufacturing method of any of the catalyst materials mentioned above, Comprising: Average diameter (Av ) Is a process of dispersing carbon nanofibers of 5 nm or less in a solvent in the presence of an ionic surfactant and a high molecular weight surfactant in a solvent by a dispersion treatment that provides a cavitation effect or a crushing effect (carbon nanofiber dispersion step ) Is one of the major features.
  • a catalyst material can be obtained.
  • supported the gold fine particle and was excellent in catalyst activity can be provided.
  • supported the gold fine particle and was excellent in catalytic activity can be provided.
  • 4 is a TEM image of the catalyst material of Example 2. 4 is a TEM image of the catalyst material of Example 3.
  • the catalyst material of the present invention is excellent in catalytic activity and can be suitably used as a catalyst material (for example, an oxidation catalyst material) for various reactions.
  • the catalyst material of this invention can be prepared using the manufacturing method of the catalyst material of this invention, for example.
  • the catalyst material of the present invention includes carbon nanofibers having an average diameter of 5 nm or less as a support and gold fine particles present on the surface of the carbon nanofibers.
  • the catalyst material of the present invention is used as a catalyst for a chemical reaction in a state where gold fine particles having a very fine structure are supported on the surface of a carrier, not as they are.
  • the carbon nanofiber surface is excellent in affinity with the gold fine particles, and the gold fine particles are firmly supported on the carbon nanofiber surface, so that the gold fine particles remain supported on the carbon nanofiber surface after the chemical reaction.
  • the catalyst material can be easily recovered.
  • the catalyst material of the present invention is used, the reactivity of a chemical reaction such as an oxidation reaction can be improved, that is, the catalyst material of the present invention is excellent in catalytic activity.
  • the reason why the catalytic activity of the catalyst material is improved by using carbon nanofibers having an average diameter of a specific value or less as a carrier for supporting gold fine particles is not clear, but the above-mentioned carbon nanofiber surface and gold fine particles are good.
  • the average particle diameter of the gold fine particles formed on the carbon nanofiber is also reduced by the small average diameter of the carbon nanofiber.
  • the carbon nanofibers used as a carrier for supporting gold fine particles carbon nanotubes or carbon nanofibers having an average diameter of 5 nm or less can be used, and carbon nanotubes having an average diameter of 5 nm or less should be used. Is preferred.
  • the carbon nanofibers are preferably carbon nanofibers that have been subjected to oxidation treatment, in particular, gas phase plasma treatment. That is, as the carbon nanofiber used for the catalyst material, a carbon nanotube having an average diameter of 5 nm or less and subjected to gas phase plasma treatment is particularly preferable.
  • the CNT used for the catalyst material is not particularly limited as long as the average diameter is 5 nm or less, and single-walled carbon nanotubes and / or multi-walled carbon nanotubes can be used. It is preferably a carbon nanotube of up to 5 layers, and more preferably a single-walled carbon nanotube. This is because if single-walled carbon nanotubes are used, the average particle diameter of the gold fine particles can be made smaller than when multi-walled carbon nanotubes are used, and the catalytic activity of the catalyst material can be improved satisfactorily.
  • a CNT having a ratio (3 ⁇ / Av) of a value (3 ⁇ ) obtained by multiplying the standard deviation ( ⁇ ) of the diameter by 3 with respect to the average diameter (Av) is more than 0.20 and less than 0.60. It is preferable to use CNTs with 3 ⁇ / Av exceeding 0.25, and it is even more preferable to use CNTs with 3 ⁇ / Av exceeding 0.50. This is because if 3CNT / Av is more than 0.20 and less than 0.60, the average particle size of the gold fine particles can be reduced and the catalytic activity of the catalyst material can be further improved.
  • the average diameter (Av) and standard deviation ( ⁇ ) of CNTs may be adjusted by changing the CNT manufacturing method and manufacturing conditions, or by combining multiple types of CNTs obtained by different manufacturing methods. May be.
  • the diameter of 100 carbon nanotubes is measured using a transmission electron microscope, the measured diameter is plotted on the horizontal axis, and the frequency is plotted on the vertical axis, and approximated by Gaussian. In this case, a normal distribution is usually used.
  • the CNT preferably has a peak of Radial Breathing Mode (RBM) when evaluated using Raman spectroscopy. Note that there is no RBM in the Raman spectrum of multi-walled carbon nanotubes of three or more layers.
  • RBM Radial Breathing Mode
  • CNTs preferably have a G-band peak intensity ratio (G / D ratio) of 1 to 20 in the Raman spectrum. This is because if the G / D ratio is 1 or more and 20 or less, the average particle diameter of the gold fine particles can be reduced, and the catalytic activity of the catalyst material can be further improved.
  • G / D ratio G-band peak intensity ratio
  • the average diameter (Av) of the CNTs must be 5 nm or less, preferably 0.5 nm or more, and more preferably 1 nm or more. This is because if the average diameter (Av) of CNT exceeds 5 nm, the average particle diameter of the gold fine particles increases, and the catalytic activity of the catalyst material cannot be ensured. Moreover, if the average diameter (Av) of CNT is 0.5 nm or more, the aggregation of CNTs can be suppressed and the dispersibility of CNTs in a solvent in the production process of the catalyst material can be improved.
  • BET specific surface area of the CNT is preferably at 600 meters 2 / g or more in the unopened state, further preferably 800 m 2 / g or more, is preferably from 2500m 2 / g, 1200m 2 / G or less is more preferable. Furthermore, when the CNTs are mainly opened, the BET specific surface area is preferably 1300 m 2 / g or more. This is because if the BET specific surface area of CNT is 600 m 2 / g or more, the catalytic activity of the catalyst material can be improved satisfactorily.
  • the BET specific surface area of CNT is 2500 m ⁇ 2 > / g or less, aggregation of CNT can be suppressed and the dispersibility of CNT in the solvent in the manufacturing process of a catalyst material can be improved.
  • the “BET specific surface area” refers to a nitrogen adsorption specific surface area measured using the BET method.
  • CNTs are obtained as aggregates (CNT aggregates) oriented in a direction substantially perpendicular to the base material on a base material having a catalyst layer for carbon nanotube growth on the surface according to the super growth method described later.
  • the mass density of the CNTs as the aggregate is preferably 0.002 g / cm 3 or more and 0.2 g / cm 3 or less. If the mass density is 0.2 g / cm 3 or less, the CNTs are weakly bonded, so that the CNTs can be uniformly dispersed. In addition, if the mass density is 0.002 g / cm 3 or more, the integrity of the CNTs can be improved and the variation can be suppressed, so that handling becomes easy.
  • the CNT preferably has a plurality of micropores.
  • the CNT preferably has micropores having a pore diameter smaller than 2 nm, and the abundance thereof is a micropore volume determined by the following method, preferably 0.40 mL / g or more, more preferably 0.43 mL. / G or more, more preferably 0.45 mL / g or more, and the upper limit is usually about 0.65 mL / g. Since the CNTs have the above micropores, the aggregation of the CNTs is suppressed, the dispersibility of the CNTs is increased, and the carbon nanofiber dispersion liquid in which the CNTs are highly dispersed is very efficient in the production process of the catalyst material.
  • micropore volume can be adjusted, for example, by appropriately changing the CNT preparation method and preparation conditions.
  • P is a measurement pressure at the time of adsorption equilibrium
  • P0 is a saturated vapor pressure of liquid nitrogen at the time of measurement
  • M is an adsorbate (nitrogen) molecular weight of 28.010
  • ⁇ is an adsorbate (nitrogen).
  • the micropore volume can be determined using, for example, “BELSORP (registered trademark) -mini” (manufactured by Nippon Bell Co., Ltd.).
  • the CNT having the above-described properties is obtained by, for example, supplying a raw material compound and a carrier gas onto a base material having a catalyst layer for producing carbon nanotubes on the surface, and performing chemical vapor deposition (CVD).
  • CVD chemical vapor deposition
  • a catalyst is synthesized, a method of dramatically improving the catalytic activity of the catalyst layer by making a small amount of an oxidizing agent (catalyst activating substance) present in the system (super growth method; see International Publication No. 2006/011655) ),
  • the catalyst layer is formed on the surface of the substrate by a wet process, and a raw material gas containing acetylene as a main component (for example, a gas containing 50% by volume or more of acetylene) can be used for efficient production. it can.
  • the carbon nanotube obtained by the super growth method may be referred to as “SGCNT”.
  • the carbon nanofibers used for the catalyst material are preferably those subjected to oxidation treatment, particularly gas phase plasma treatment.
  • Surface-treated carbon nanofibers (surface-treated CNTs, etc.) obtained by performing oxidation treatment such as gas phase plasma treatment have defects and functional groups such as carboxyl groups, carbonyl groups, and hydroxyl groups on the surface. Presumed. It is surmised that the contribution of such defects and functional groups improves the affinity between the surface and the gold fine particles, but the surface-treated carbon nanofibers further improve the catalytic activity of the resulting catalyst material. Can be made.
  • the gas phase plasma treatment when CNT is used as the carbon nanofiber will be described in detail.
  • the vapor phase plasma treatment can be performed by, for example, a known low temperature plasma treatment.
  • the processing apparatus is not particularly limited, and a known internal electrode type or external electrode type is used, but an external electrode type is preferable because there is no contamination of the electrodes.
  • Processing conditions such as processing pressure, power supply frequency and processing output are not particularly limited, and may be appropriately selected.
  • Organic or inorganic gas is used individually or in mixture of 2 or more types suitably.
  • the gas include oxygen, nitrogen, hydrogen, ammonia, methane, ethylene, argon, and carbon tetrafluoride. Among these, oxygen, nitrogen, and argon are preferable, and nitrogen is more preferable from the viewpoint of maintaining the cylindrical structure of CNT while suitably introducing defects and functional groups on the surface of CNT.
  • the vapor phase plasma treatment is preferably performed while rolling the CNTs.
  • CNT is usually used as a dry powder, and therefore, when the treatment is performed in a stationary state, there is a risk that plasma will not spread throughout.
  • “rolling CNT” does not keep the CNT stationary during the treatment, but reverses the container in which the CNT is accommodated during the treatment or stirs the CNT.
  • the simplest method is a method in which the gas phase plasma treatment is once performed, then taken out and stirred, and then subjected to the gas phase plasma treatment again. That is, the gas phase plasma treatment may be performed while rolling CNTs continuously or intermittently.
  • the conditions of the gas phase plasma treatment vary depending on the plasma generating gas used and the discharge form and cannot be generally stated.
  • the amount of electric power is 0.05 to 2.0 W in terms of energy per unit area of the plasma irradiation area. / Cm 2 and the gas pressure is preferably 5 to 150 Pa.
  • the treatment time irradiation time, treatment time for each time in the case of intermittent irradiation
  • the plasma exhibits a white color.
  • the plasma exhibiting white means that the carbon-carbon bond constituting CNT is eroded and the structure is destroyed. Therefore, in the vapor phase plasma treatment of CNT, it is preferable to select conditions under which the plasma does not exhibit white.
  • the surface of the CNT as a raw material is subjected to gas phase plasma treatment.
  • the processing conditions by appropriately selecting the processing conditions, only the surface layer of the CNT as a raw material can be processed mildly, and excessive destruction of the structure due to the vapor phase plasma processing can be suppressed.
  • the G / D ratio of the surface-treated CNT is 0.1 or more, preferably 0.5 or more, more preferably 1 or more, and usually the upper limit is about 5. is there.
  • the gold fine particle is a component that can function as a catalytically active component in the catalyst material, and is disposed on the surface of the carbon nanofiber as the support described above, and constitutes the catalyst component together with the carbon nanofiber.
  • the shape of the gold fine particles is not particularly limited, and examples thereof include plate shapes such as a spherical shape, a cubic shape, a rectangular shape and a hexagonal plate shape, and rod shapes such as a columnar shape and a hexagonal rod shape.
  • the average particle diameter of the gold fine particles is preferably 2 nm or more, more preferably 4 nm or more, and usually 15 nm or less, preferably 10 nm or less, and preferably 9 nm or less. More preferred. When the average particle diameter of the gold fine particles is within the above range, the catalytic activity of the catalyst material can be further improved.
  • the method for preparing the catalyst material of the present invention described above is not particularly limited as long as it is a method capable of supporting gold fine particles on carbon nanofibers having an average diameter of 5 nm or less. And it is preferable to use the manufacturing method of the catalyst material of this invention as a method of preparing the catalyst material of this invention.
  • carbon nanofibers having an average diameter (Av) of 5 nm or less are converted into cavitation effect or solution in the presence of an ionic surfactant and a polymeric surfactant.
  • One of the major features is that it includes a step of dispersing in a solvent (carbon nanofiber dispersion step) by a dispersion treatment that provides a crushing effect.
  • the dispersion treatment is performed in the presence of the ionic surfactant and the polymeric surfactant, the synergistic effect of the surfactants having different properties ensures the stability of the dispersion liquid and the carbon nano-particles.
  • the fibers can be dispersed well.
  • the carbon nanofibers are dispersed by a dispersion treatment that provides a cavitation effect or a crushing effect, the carbon nanofibers can be prevented from being damaged during the dispersion treatment. Therefore, by using the carbon nanofibers obtained through the above-mentioned carbon nanofiber dispersion process for the preparation of the catalyst material, a catalyst material capable of exhibiting excellent catalytic activity with gold fine particles uniformly supported on the carbon nanofibers is obtained. be able to.
  • the catalyst material of the present invention is, for example, the following steps (2) to (4) after the above (1) carbon nanofiber dispersion step: (2) A step of preparing a mixed solution containing the carbon nanofiber dispersion obtained in the carbon nanofiber dispersion step and a gold precursor (mixed solution preparation step), (3) adding a reducing agent to the mixed solution and reducing the gold precursor to deposit gold fine particles on the surface of the carbon nanofibers to obtain a catalyst material dispersion (reduction step); (4) a step of separating the catalyst material from the catalyst material dispersion (catalyst material separation step), It can be prepared by going through.
  • steps (1) to (4) will be described in detail.
  • Carbon nanofiber dispersion process In the carbon nanofiber dispersion step, carbon nanofibers having an average diameter of 5 nm or less are dispersed in a solvent by a dispersion treatment that provides a cavitation effect or a disintegration effect in the presence of an ionic surfactant and a polymeric surfactant. To obtain a carbon nanofiber dispersion.
  • the ionic surfactant and the polymeric surfactant can function as a dispersant for assisting the dispersion of the carbon nanofibers in the carbon nanofiber dispersion. And in the manufacturing method of the catalyst material of this invention, in order to disperse
  • the carbon nanofiber dispersion may contain a known dispersant other than the ionic surfactant and the polymeric surfactant.
  • any of a cationic surfactant and an anionic surfactant can be used.
  • the cationic surfactant include quaternary ammonium salts and quaternary phosphonium salts.
  • the anionic surfactant include sodium dodecyl sulfate, sodium deoxycholate, sodium cholate, sodium dodecylbenzenesulfonate, sodium dodecyldiphenyloxide disulfonate, and the like. Among these, sodium dodecyl sulfate and sodium deoxycholate are preferable from the viewpoint of excellent dispersibility of carbon nanofibers.
  • the polymer surfactant examples include polyvinyl pyrrolidone, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polystyrene sulfonic acid, and salts thereof. Among these, hydroxypropylcellulose and polyvinylpyrrolidone are preferable from the viewpoint of excellent dispersibility of the carbon nanofibers. It should be noted that the surfactant corresponding to the polymeric surfactant composed of a polymer is not included in the ionic surfactant described above.
  • the total addition amount of the ionic surfactant and the polymer surfactant may be an amount that is at least the critical micelle concentration or more.
  • the total addition amount of the ionic surfactant and the polymeric surfactant in the carbon nanofiber dispersion is, for example, 1 to 20 times the amount of carbon nanofibers in the carbon nanofiber dispersion. It can be as follows.
  • the ratio of the addition amount of the polymer surfactant to the addition amount of the ionic surfactant is 0.05 or more and 5 or less.
  • the ratio of the addition amount of the polymeric surfactant to the addition amount of the ionic surfactant is within the above range, the effect obtained by using the ionic surfactant and the polymeric surfactant in combination can be obtained. This is because it can be made sufficiently high.
  • the dispersion treatment that provides a cavitation effect is a dispersion method that uses shock waves generated by bursting of vacuum bubbles generated in water when high energy is applied to a liquid. And by using the said dispersion
  • dispersion treatment examples include dispersion treatment using ultrasonic waves, dispersion treatment using a jet mill, and dispersion treatment using high shear stirring. These distributed processes may be performed only one, or may be performed in combination. More specifically, for example, an ultrasonic homogenizer, a jet mill, and a high shear stirrer are suitably used for the dispersion treatment. These devices may be conventionally known devices.
  • the output is preferably 100 W or more and 500 W or less, and the temperature is preferably 15 ° C. or more and 50 ° C. or less.
  • the number of treatments may be appropriately set depending on the amount of carbon nanofibers, and is preferably 2 times or more, more preferably 5 times or more, preferably 100 times or less, and 50 times or less. More preferred.
  • the pressure is preferably 20 MPa to 250 MPa, and the temperature is preferably 15 ° C. to 50 ° C.
  • the coarse dispersion may be treated with a high shear stirring device.
  • the operation time (the time during which the machine is rotating) is preferably 3 minutes to 4 hours
  • the peripheral speed is 5 m / s to 50 m / s
  • the temperature is preferably 15 ° C. to 50 ° C.
  • the dispersion treatment for obtaining the above cavitation effect it is more preferable to perform the dispersion treatment for obtaining the above cavitation effect at a temperature of 50 ° C. or lower. This is because a change in concentration due to the volatilization of the solvent is suppressed.
  • Dispersion treatment that can produce a crushing effect Moreover, in the carbon nanofiber dispersion step, a dispersion treatment capable of obtaining the crushing effect shown below can be applied. Dispersion treatment that provides this crushing effect allows carbon nanofibers to be uniformly dispersed in the solvent, as well as damage to carbon nanofibers caused by shock waves when bubbles disappear, compared to the dispersion treatment that provides the cavitation effect described above. This is more advantageous in this respect.
  • the above-mentioned coarse dispersion is subjected to shearing force to crush and disperse the aggregates of carbon nanofibers in the coarse dispersion, and a back pressure is applied to the obtained dispersion.
  • a back pressure is applied to the dispersion, the back pressure applied to the dispersion may be reduced to atmospheric pressure at a stretch, but it is preferable to reduce the pressure in multiple stages.
  • a dispersion system having a disperser having the following structure may be used.
  • the disperser has a disperser orifice having an inner diameter d1, a dispersion space having an inner diameter d2, and a terminal portion having an inner diameter d3 from the inflow side to the outflow side of the coarse dispersion liquid (where d2>d3> d1)).
  • the inflowing high-pressure (usually 10 to 400 MPa, preferably 50 to 250 MPa) coarse dispersion passes through the disperser orifice, so that the flow rate of the fluid is reduced while the pressure decreases. And flows into the dispersion space. Thereafter, the high-velocity coarse dispersion liquid flowing into the dispersion space flows at high speed in the dispersion space and receives a shearing force at that time. As a result, the flow rate of the coarse dispersion decreases, and the carbon nanofibers in the coarse dispersion are well dispersed. Then, a fluid having a pressure (back pressure) lower than the pressure of the inflowing coarse dispersion liquid flows out from the terminal portion as the dispersion liquid.
  • back pressure back pressure
  • the back pressure of the dispersion can be applied by applying a load to the flow of the dispersion.
  • a multistage step-down device described later can be provided on the downstream side of the disperser to provide a desired dispersion. Back pressure can be applied. By reducing the back pressure of the dispersion in multiple stages using this multistage pressure reducer, it is possible to suppress the generation of bubbles in the dispersion when the dispersion is finally released to atmospheric pressure.
  • the disperser may include a heat exchanger for cooling the dispersion and a coolant supply mechanism. This is because the generation of bubbles in the dispersion can be further suppressed by cooling the dispersion that has been heated to a high temperature by the shearing force applied by the distributor. In addition, it can suppress that a bubble generate
  • the effect of improving dispersibility by suppressing the adhesion of bubbles to the carbon nanofibers is very large in carbon nanofibers having a large BET specific surface area, particularly carbon nanofibers having a BET specific surface area of 600 m 2 / g or more. This is because the larger the specific surface area of the carbon nanofibers and the easier the carbon nanofibers to adhere to the surface, the more easily the dispersibility decreases when bubbles are generated and attached.
  • a distributed system having the above-described configuration for example, there is a distributed system in which a product name “BERYU SYSTEM PRO” (manufactured by Migrain Co., Ltd.) is combined with a multistage step-down device.
  • BERYU SYSTEM PRO manufactured by Migrain Co., Ltd.
  • a carbon nanofiber dispersion and a gold precursor are included by adding a gold precursor to the carbon nanofiber dispersion obtained through the above-described carbon nanofiber dispersion step and mixing by a known mixing method as necessary. Prepare a mixture.
  • the gold precursor a compound capable of generating gold by a reduction reaction is used.
  • a gold precursor that is soluble in the solvent to be used.
  • Such gold precursor H 2 [AuCl 4], (NH 4) 2 [AuCl 4], H [Au (NO 3) 4] ⁇ H 2 O, NaAuCl 2 ⁇ 2H 2 but O, and the like, It is not limited to these. These can be used singly or in combination of two or more. Of these, NaAuCl 2 .2H 2 O is preferable.
  • the addition amount of the gold precursor can be, for example, 50 times or more and 1000 times or less the addition amount of the carbon nanofibers.
  • a reducing agent is added to the liquid mixture containing the carbon nanofiber dispersion and the gold precursor to reduce the gold precursor. Then, by the reduction reaction, gold fine particles are deposited on the surface of the carbon nanofibers to obtain a catalyst material dispersion liquid in which the catalyst material is dispersed in the solvent.
  • the addition method to the liquid mixture of a reducing agent is not specifically limited, The method of adding a reducing agent to a liquid mixture sequentially is preferable. In order to allow the reduction reaction to proceed sufficiently, it is preferable to stir for about 5 to 30 minutes after the addition of the reducing agent.
  • the reducing agent is not particularly limited as long as it can reduce the above-described gold precursor (cation derived from the gold precursor) and deposit gold fine particles on the surface of the carbon nanofiber.
  • the reducing agent include formic acid, formaldehyde, ammonium formate, dimethylamine borane, tertiary butylamine borane, and triethylamine borane. These can be used singly or in combination of two or more. Of these, dimethylamine borane is preferred.
  • the addition amount of a reducing agent can be 0.01 times or more and 1 time or less of the addition amount of a gold precursor, for example.
  • a reduction reaction can be advanced favorable and gold fine particles can be deposited suitably on the surface of carbon nanofiber.
  • a catalyst material can be obtained from the catalyst material dispersion obtained through the reduction step, for example, by filtration or centrifugation, preferably by filtration.
  • the obtained catalyst material may be washed to remove ionic surfactants and polymer surfactants attached to the catalyst material, or dried to remove unnecessary solvents, if necessary. May be.
  • SGCNT-1> CNT (SGCNT-1) was prepared by the super-growth method according to the description in International Publication No. 2006/011655.
  • the catalyst layer iron thin film
  • the obtained SGCNT-1 has a BET specific surface area of 1050 m 2 / g (unopened) and a micropore volume of 0.45 mL / g, and is characteristic of single-walled CNT in measurement with a Raman spectrophotometer.
  • the obtained SGCNT-2 has a BET specific surface area of 860 m 2 / g (unopened) and a micropore volume of 0.41 mL / g, and is characteristic of single-walled CNT in measurement with a Raman spectrophotometer.
  • a spectrum of radial breathing mode (RBM) was observed in the low wavenumber region of ⁇ 300 cm ⁇ 1 .
  • the average diameter (Av) was 4.6 nm and the standard deviation ( ⁇ ) of the diameter was multiplied by 3.
  • the value (3 ⁇ ) was 2.3 nm and the ratio (3 ⁇ / Av) was 0.50.
  • ⁇ Synthesis Example 3 Surface Treatment SGCNT-2>
  • the SGCNT-2 was subjected to gas phase plasma treatment (plasma generating gas: nitrogen, treatment time: 5 minutes) to prepare surface-treated SGCNT-2.
  • the average diameter (Av), the standard deviation of diameter ( ⁇ ), and 3 ⁇ / Av of the surface-treated SGCNT-2 were the same as the values before the surface treatment.
  • the filtrate was adjusted to 80 ° C., and stirred with a stirrer.
  • a Ferring solution (69.2 g / L copper sulfate pentahydrate aqueous solution, 50 mg potassium potassium tartrate at a concentration of 364 g / L, 100 g / L (Prepared by mixing 50 mL of an aqueous solution in which sodium hydroxide was dissolved in each concentration), and stirring was continued for 30 minutes after the addition of the failing solution. Thereafter, cuprous oxide obtained by suction filtration was recovered, and its weight X was measured.
  • reaction rate (%) (1 ⁇ X / Y) ⁇ 100
  • Example 1 An aqueous solution containing 0.01 g of SGCNT-1 as carbon nanofibers, sodium dodecyl sulfate (SDS) as an ionic surfactant, and hydroxypropyl cellulose (HPC) as a polymeric surfactant, each at a concentration of 1 g / L. In addition to 1 L, the mixture was stirred with a stirrer for 30 minutes to obtain a crude dispersion. SGCNT is obtained by subjecting this coarse dispersion to a dispersion process 20 times under the condition of 50 MPa using a jet mill (manufactured by Joko Co., Ltd., product name “JN-20”), which is a dispersion apparatus utilizing the cavitation effect.
  • SGCNT-1 sodium dodecyl sulfate
  • HPC hydroxypropyl cellulose
  • this catalyst material dispersion was subjected to suction filtration, and the catalyst material 1 could be easily separated from the dispersion.
  • the reaction rate (%) of the catalyst material 1 was 27.9%, and it was confirmed that the catalyst material 1 showed high catalytic activity for glucose oxidation.
  • Example 2 SGCNT-2 is used instead of SGCNT-1 as the carbon nanofiber, and the product name “BERYU SYSTEM PRO” (manufactured by Miebu Co., Ltd.) is used instead of the dispersion treatment for obtaining a cavitation effect as the dispersion treatment.
  • a catalyst material 2 was obtained in the same manner as in Example 1 except that a dispersion treatment that can provide a crushing effect was performed using a dispersion system that is a combination of multistage step down devices.
  • TEM transmission electron microscope
  • Example 3 Catalyst material 3 was obtained in the same manner as in Example 2 except that surface-treated SGCNT-2 was used instead of SGCNT-2 as the carbon nanofiber.
  • TEM transmission electron microscope
  • the catalyst material 3 in which gold fine particles (average particle diameter: 6 nm) are supported on a single-walled CNT structure (SWCNT). was observed (see FIG. 2).
  • the reaction rate (%) of the catalyst material 3 was 28.9%, and it was confirmed that the catalyst material 3 showed high catalytic activity for glucose oxidation.
  • Comparative Example 1 instead of SGCNT-1 as the carbon nanofiber, except that multi-walled carbon nanotubes (MWCNT; manufactured by Nanocyl, product name “NC7000”, BET specific surface area: 290 m 2 / g, average diameter: 9.3 nm) were used.
  • Comparative Example Catalyst Material 1 was obtained in the same manner as Example 1. When the catalyst material dispersion containing the comparative catalyst material 1 is observed with a transmission electron microscope (TEM), a comparative catalyst in which gold fine particles (average particle diameter: 18 nm) are supported on a multilayer CNT structure (MWCNT) Material 1 was observed. The reaction rate (%) of the comparative catalyst material 1 was 21.5%, and it was confirmed that the catalytic activity for glucose oxidation was inferior to that of Examples 1 to 3.
  • TEM transmission electron microscope
  • supported the gold fine particle and was excellent in catalyst activity can be provided.
  • supported the gold fine particle and was excellent in catalytic activity can be provided.

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Abstract

L'objectif de la présente invention est de produire : un matériau de catalyseur qui est chargé avec des particules d'or fines et a une excellente activité catalytique ; et un procédé de production de ce matériau de catalyseur. Un matériau de catalyseur selon la présente invention est caractérisé en ce qu'il est obtenu par chargement de nanofibres de carbone ayant un diamètre moyen (Av) de 5 nm ou moins avec des particules d'or fines. Un procédé de production d'un matériau de catalyseur selon la présente invention est caractérisé en ce qu'il comprend une étape dans laquelle des nanofibres de carbone ayant un diamètre moyen (Av) de 5 nm ou moins sont dispersées dans un solvant par un processus de dispersion, par lequel un effet de cavitation ou un effet de broyage peut être obtenu, en présence d'un tensioactif ionique et d'un tensioactif polymère.
PCT/JP2015/056440 2014-07-23 2015-02-26 Matériau de catalyseur et son procédé de production Ceased WO2016013245A1 (fr)

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