JPH1128357A - Manufacture of composite wherein metal oxide is supported on carbon support - Google Patents
Manufacture of composite wherein metal oxide is supported on carbon supportInfo
- Publication number
- JPH1128357A JPH1128357A JP9182086A JP18208697A JPH1128357A JP H1128357 A JPH1128357 A JP H1128357A JP 9182086 A JP9182086 A JP 9182086A JP 18208697 A JP18208697 A JP 18208697A JP H1128357 A JPH1128357 A JP H1128357A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- carbon
- containing compound
- oxide
- plasma
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 41
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 27
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 5
- 150000003624 transition metals Chemical class 0.000 claims abstract description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 3
- 239000004917 carbon fiber Substances 0.000 claims abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000009832 plasma treatment Methods 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 239000003245 coal Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- -1 organic acid salt Chemical class 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910017771 LaFeO Inorganic materials 0.000 description 1
- 241000877463 Lanio Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000010412 oxide-supported catalyst Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical group [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical group [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Physical Or Chemical Processes And Apparatus (AREA)
- Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、炭素系担体に金属
酸化物を担持した複合体を製造する方法に関する。本発
明の製造方法により得られる複合体は、例えば、金属酸
化物担持触媒として有用である。[0001] The present invention relates to a method for producing a composite in which a metal oxide is supported on a carbon-based support. The composite obtained by the production method of the present invention is useful, for example, as a metal oxide-supported catalyst.
【０００２】[0002]
【従来の技術】活性炭のような炭素系担体を担体とする
触媒が知られている。そのような触媒の主なものは、白
金炭及びパラジウム炭として知られる、白金を活性炭に
担持した触媒及びパラジウムを活性炭に担持した触媒で
ある。これらの触媒は、活性炭の高い表面積を利用し
て、その表面に触媒として働く白金及びパラジウムを担
持させることで、反応の場を多くし、単位量当たりの金
属触媒の活性を高めたものである。2. Description of the Related Art Catalysts using a carbon-based carrier such as activated carbon as a carrier are known. The main such catalysts are platinum on activated carbon and palladium on activated carbon, known as platinum and palladium on carbon. These catalysts make use of the high surface area of activated carbon and carry platinum and palladium acting as catalysts on the surface, thereby increasing the number of reaction fields and increasing the activity of the metal catalyst per unit amount. .
【０００３】[0003]
【発明が解決すべき課題】一方、金属酸化物は、石油化
学工業における化成品製造用触媒や自動車の排ガス浄化
用触媒等として利用されている。しかるに、活性炭のよ
うな炭素系担体に担持した触媒はほとんど知られていな
い。これは、触媒調製上の理由による。金属酸化物を担
持する活性炭の調製は、ほとんどの場合、活性炭上に直
接金属酸化物を担持させることでは行えない。まず、水
溶性の金属化合物を活性炭に吸着させた後、金属化合物
を酸化処理する必要がある。この酸化処理には、生成さ
せるべき金属酸化物の種類によるが、酸素を含む雰囲気
中で比較的高温での焼成が必要である。しかるに、その
ような条件下では活性炭が燃焼してしまい、目的とする
金属酸化物担持活性炭は得られない。このため、僅か
に、比較的低温で酸化する鉄、銀、ニッケルの例が知ら
れているに過ぎない。On the other hand, metal oxides are used as catalysts for producing chemical products in the petrochemical industry, as catalysts for purifying exhaust gas from automobiles, and the like. However, catalysts supported on a carbon-based carrier such as activated carbon are hardly known. This is for reasons of catalyst preparation. In most cases, preparation of activated carbon supporting a metal oxide cannot be performed by directly supporting the metal oxide on the activated carbon. First, after a water-soluble metal compound is adsorbed on activated carbon, it is necessary to oxidize the metal compound. This oxidation treatment requires firing at a relatively high temperature in an atmosphere containing oxygen, depending on the type of metal oxide to be generated. However, under such conditions, the activated carbon burns, and the desired activated carbon supporting metal oxide cannot be obtained. For this reason, only a few examples of iron, silver and nickel oxidizing at relatively low temperatures are known.
【０００４】活性炭の高い表面積を利用した高活性の金
属酸化物触媒が得られれば、その利用範囲は広いと考え
られるが、上記製造技術上の理由から、そのような触媒
は実用化さていない。そこで本発明の目的は、活性炭等
の炭素系担体に金属酸化物を担持した触媒等として有用
な複合体を製造する方法を提供することにある。[0004] If a highly active metal oxide catalyst utilizing the high surface area of activated carbon can be obtained, its use range is considered to be wide. However, such a catalyst has not been put into practical use because of the above-mentioned production technology. Therefore, an object of the present invention is to provide a method for producing a composite useful as a catalyst in which a metal oxide is supported on a carbon-based carrier such as activated carbon.
【０００５】[0005]
【課題を解決するための手段】本発明者は、金属含有化
合物を吸着させた炭素系担体をプラズマ処理すること
で、これまでの焼成よりはるかに低い温度で上記金属含
有化合物を金属酸化物に変換でき、目的とする炭素系担
体に金属酸化物を担持した複合体が得られることを見い
だして本発明を完成した。Means for Solving the Problems The present inventors plasma-treat a carbon-based support on which a metal-containing compound has been adsorbed, so that the metal-containing compound can be converted into a metal oxide at a temperature much lower than conventional firing. The present invention has been completed by finding that a composite in which a metal oxide is supported on a target carbon-based carrier can be obtained by conversion.
【０００６】即ち、本発明は、炭素系担体に金属含有化
合物を吸着させ、次いで前記金属含有化合物を吸着させ
た炭素系担体をプラズマ処理することにより、前記金属
含有化合物を金属酸化物に変換させることを含む、炭素
系担体に金属酸化物を担持した複合体の製造方法に関す
る。That is, the present invention converts a metal-containing compound into a metal oxide by adsorbing a metal-containing compound on a carbon-based carrier and then subjecting the carbon-based carrier to which the metal-containing compound has been adsorbed to a plasma treatment. And a method for producing a composite in which a metal oxide is supported on a carbon-based support.
【０００７】[0007]
【発明の実施の形態】本発明の製造方法の製造対象であ
る複合体は、炭素系担体に金属酸化物を担持した複合体
である。炭素系担体は、例えば、活性炭であり、それ以
外の炭素系担体としてカーボンファイバ等を例示でき
る。活性炭としては、従来の活性炭をそのまま用いるこ
とができる。活性炭の原料となる炭素材料は、通常は椰
子殻であるが、椰子殻以外に、木炭、のこくず、亜炭、
石炭、ピッチ、もみ殻、古タイヤ等であっても良い。さ
らに、活性炭製造時の賦活方法にも特に制限はなく、ガ
ス賦活及び薬品賦活のいずれの方法により賦活された活
性炭も用いることができる。さらに、活性炭には、通
常、形状によって造粒炭、破砕炭、顆粒炭、球形炭等が
あるが、本発明では、いずれの形状の活性炭も使用する
ことができる。BEST MODE FOR CARRYING OUT THE INVENTION A composite to be produced by the production method of the present invention is a composite in which a metal oxide is supported on a carbon support. The carbon-based carrier is, for example, activated carbon, and other carbon-based carriers include carbon fibers and the like. As the activated carbon, conventional activated carbon can be used as it is. The carbon material used as the raw material for activated carbon is usually coconut shell, but in addition to coconut shell, charcoal, sawdust, lignite,
Coal, pitch, chaff, old tires and the like may be used. Furthermore, there is no particular limitation on the activation method at the time of producing activated carbon, and activated carbon activated by either gas activation or chemical activation can be used. Further, the activated carbon generally includes granulated coal, crushed coal, granular coal, spherical coal and the like depending on the shape. In the present invention, any shape of activated carbon can be used.
【０００８】金属酸化物は、例えば、遷移金属や希土類
の酸化物及び遷移金属や希土類を含む複合酸化物であ
り、遷移金属の酸化物や希土類の酸化物としては、例え
ば、酸化ニッケル、酸化コバルト、酸化チタン、酸化ジ
ルコニウム、酸化マグネシウム、酸化アルミニウム、酸
化珪素、酸化カルシウム、酸化バナジウム、酸化クロ
ム、酸化マンガン、酸化鉄、酸化銅、酸化亜鉛、酸化ス
トロンチウム、酸化イットリウム、酸化ニオブ、酸化ル
テニウム、酸化カドミウム、酸化インジウム、酸化ス
ズ、酸化バリウム、ランタノイド類の酸化（ＬｎＯｘ）
等を例示することができる。複合酸化物としては、例え
ば、ペロブスカイト型複合酸化物を挙げることができ
る。ペロブスカイト型複合酸化物としては、例えば、Ａ
サイトがランタンである、ＬａＣｏＯ3 、ＬａＴｉ
Ｏ3 、ＬａＭｎＯ3 、ＬａＦｅＯ3 、ＬａＮｉＯ3、Ｌ
ａＣｒＯ3 等や、Ａサイトがストロンチウムである、Ｓ
ｒＭｏＯ3 、ＳｒＴｉＯ3 、さらにＡサイトがイットリ
ウムである、ＹＮｉＯ3 等を挙げることができる。The metal oxide is, for example, a transition metal or rare earth oxide or a composite oxide containing the transition metal or rare earth. Examples of the transition metal oxide or rare earth oxide include nickel oxide and cobalt oxide. , Titanium oxide, zirconium oxide, magnesium oxide, aluminum oxide, silicon oxide, calcium oxide, vanadium oxide, chromium oxide, manganese oxide, iron oxide, copper oxide, zinc oxide, strontium oxide, yttrium oxide, niobium oxide, ruthenium oxide, oxidation Oxidation of cadmium, indium oxide, tin oxide, barium oxide, lanthanoids (LnOx)
And the like. Examples of the composite oxide include a perovskite-type composite oxide. Examples of the perovskite-type composite oxide include A
LaCoO 3 , LaTi whose site is lantern
O 3 , LaMnO 3 , LaFeO 3 , LaNiO 3 , L
aCrO 3 etc., S site where A site is strontium, S
Examples include rMoO 3 , SrTiO 3 , and YNiO 3 in which the A site is yttrium.
【０００９】炭素系担体への金属酸化物の担持量は、特
に制限はなく、本発明の複合体の用途により適宜選択で
きる。本発明の複合体を触媒として利用する場合、例え
ば、炭素系担体100重量部当たり、０．０１〜５０重量
部の範囲とすることができる。但し、この範囲に限定さ
れるものではない。The amount of the metal oxide carried on the carbon-based support is not particularly limited, and can be appropriately selected depending on the use of the composite of the present invention. When the composite of the present invention is used as a catalyst, for example, it can be in the range of 0.01 to 50 parts by weight per 100 parts by weight of the carbon-based carrier. However, it is not limited to this range.
【００１０】本発明の製造方法は、炭素系担体に金属含
有化合物を吸着させ、次いで金属含有化合物を吸着させ
た炭素系担体にプラズマ処理することにより前記金属含
有化合物を金属酸化物に変換させることを含む。In the production method of the present invention, a metal-containing compound is adsorbed on a carbon-based carrier, and the metal-containing compound is converted into a metal oxide by subjecting the carbon-based carrier to which the metal-containing compound has been adsorbed to plasma treatment. including.
【００１１】炭素系担体への金属含有化合物の吸着は、
例えば、炭素系担体を金属含有化合物を含む水溶液に浸
漬し、乾燥することで行うことができる。金属含有化合
物は、炭素系担体への吸着を容易に行うという観点か
ら、水溶液への溶解性が高い化合物であることが適当で
ある。但し、溶解性が低い化合物であっても、水溶液へ
の浸漬及び乾燥を繰り返し行うことで、所望量の金属含
有化合物を吸着させることができる。また、金属含有化
合物の種類は、金属酸化物への変換の容易さ等を考慮し
て選択することができる。金属含有化合物としては、例
えば、金属水酸化物、金属炭酸塩、金属硝酸塩、有機酸
塩、金属アルコキサイド、有機金属錯体等を挙げること
ができる。[0011] The adsorption of the metal-containing compound on the carbon-based support is as follows.
For example, it can be carried out by immersing the carbon-based carrier in an aqueous solution containing a metal-containing compound and drying. The metal-containing compound is suitably a compound having high solubility in an aqueous solution from the viewpoint of facilitating adsorption to a carbon-based carrier. However, even if the compound has low solubility, a desired amount of the metal-containing compound can be adsorbed by repeatedly immersing in an aqueous solution and drying. The type of the metal-containing compound can be selected in consideration of the ease of conversion to a metal oxide and the like. Examples of the metal-containing compound include a metal hydroxide, a metal carbonate, a metal nitrate, an organic acid salt, a metal alkoxide, an organic metal complex, and the like.
【００１２】金属含有化合物を含む水溶液中の金属含有
化合物の濃度や浸漬条件(時間及び温度等)は、金属含有
化合物の種類や吸着させようとする金属含有化合物等を
勘案して適宜決定できる。また、金属含有化合物の活性
炭への吸着を促進する目的で、活性炭を金属含有化合物
を含む水溶液に浸漬した後、これを、例えば、アルカリ
化して、金属の水酸化物として析出させることもでき
る。The concentration of the metal-containing compound in the aqueous solution containing the metal-containing compound and the immersion conditions (time, temperature, etc.) can be appropriately determined in consideration of the type of the metal-containing compound, the metal-containing compound to be adsorbed, and the like. Further, in order to promote adsorption of the metal-containing compound to the activated carbon, the activated carbon can be immersed in an aqueous solution containing the metal-containing compound, and then, for example, alkalized to precipitate as a metal hydroxide.
【００１３】尚、金属含有化合物の吸着前に、処理対象
である活性炭を、例えば、真空下で加熱して脱水するこ
とで、金属含有化合物の吸着を促進することができる。
この真空加熱処理は、例えば温度５０〜６００℃、真空
度１ｔｏｒｒ以下、処理時間１〜５時間の条件で行うこ
とができる。The adsorption of the metal-containing compound can be promoted by, for example, heating and dehydrating the activated carbon to be treated before adsorption of the metal-containing compound under vacuum.
This vacuum heat treatment can be performed, for example, under the conditions of a temperature of 50 to 600 ° C., a degree of vacuum of 1 torr or less, and a treatment time of 1 to 5 hours.
【００１４】金属含有化合物を吸着させた炭素系担体
は、次いで、プラズマ処理される。このプラズマ処理
は、炭素系担体に吸着させた金属含有化合物が金属酸化
物に変換されるように行われる。プラズマ処理の方法自
体は、従来から知られた方法であることができ、例え
ば、特開平５−２２０５３０号や特開平９−５２０４２
号等に記載されたマイクロ波等の電磁波を用いるプラズ
マ処理方法やRFプラズマ処理方法等であることができ
る。また、このようなプラズマ処理は、減圧下及び常圧
下のいずれでも行うことができる。さらに、金属含有化
合物を金属酸化物に変換するという観点からは、プラズ
マ処理は、減圧下で行うか、あるいは減圧下又は常圧下
であって不活性ガスまたは酸素含有ガスの流通下で行わ
れることが適当である。The carbon-based support having the metal-containing compound adsorbed thereon is then subjected to a plasma treatment. This plasma treatment is performed so that the metal-containing compound adsorbed on the carbon-based carrier is converted into a metal oxide. The plasma processing method itself can be a conventionally known method, for example, Japanese Patent Application Laid-Open Nos. 5-220530 and 9-52042.
And a plasma processing method using an electromagnetic wave such as a microwave described in No. 1 or an RF plasma processing method. Such a plasma treatment can be performed either under reduced pressure or normal pressure. Further, from the viewpoint of converting the metal-containing compound into a metal oxide, the plasma treatment is performed under reduced pressure, or performed under reduced pressure or normal pressure and under the flow of an inert gas or an oxygen-containing gas. Is appropriate.
【００１５】電磁波を用いるプラズマ処理は、例えば図
１に示すような装置を用いて行うことができる。図中、
１はマイクロ波発生器、２は導波管、３は石英ガラス製
の処理室、４はアイソレーター、５はスリー・スタブ同
調器（Ｔｈｒｅｅ−ｓｔｕｂｔｕｎｅｒ）、６はマイク
ロ波出力計、７はマイクロ波反射用プランジャである。
マイクロ波反射用プランジャ７はマイクロ波を反射して
処理室３にマイクロ波を集中させるために使用される。
処理室３に金属含有化合物を吸着させた炭素系担体を置
き、これにマイクロ波を照射することでプラズマが発生
し、上記炭素系担体がプラズマ処理される。The plasma processing using an electromagnetic wave can be performed using, for example, an apparatus as shown in FIG. In the figure,
1 is a microwave generator, 2 is a waveguide, 3 is a processing chamber made of quartz glass, 4 is an isolator, 5 is a three-stub tuner (Three-stubtuner), 6 is a microwave power meter, and 7 is a microwave. It is a reflection plunger.
The microwave reflecting plunger 7 is used to reflect the microwave and concentrate the microwave in the processing chamber 3.
A carbon-based carrier on which a metal-containing compound is adsorbed is placed in the processing chamber 3, and a microwave is applied to the carbon-based carrier to generate plasma.
【００１６】プラズマは、励起した分子、原子、イオ
ン、電子など荷電粒子を含み、全体として電気的にほぼ
中性を保つ粒子の集団である。プラズマは、通常は、１
Ｐａ〜１ａｔｍ程度の範囲にある気体を極めて高い高温
状態にするか、あるいは強い磁場又は電磁波のもとにお
くと発生する。本発明においてプラズマ処理とは、この
ような環境中に、対象とする材料を一定時間置くことを
いう。The plasma is a group of particles that contain charged particles such as excited molecules, atoms, ions, and electrons, and that are electrically almost neutral as a whole. The plasma is usually 1
It is generated when a gas in the range of about Pa to 1 atm is brought to an extremely high temperature state or is placed under a strong magnetic field or an electromagnetic wave. In the present invention, plasma processing refers to placing a target material in such an environment for a certain period of time.
【００１７】図１に示す上記装置では、プラズマは、処
理室３を例えば、減圧にし、マイクロ波のような電磁波
を照射することにより、発生させることができる。処理
室３の真空度は、約１トル（Ｔｏｒｒ）以下にすること
が、プラズマの発生を維持するという観点から適当であ
る。また電磁波は、ラジオ波からマイクロ波の範囲が適
当であり、振動数は、おおよそ１ＧＨｚ〜１０００ＧＨ
ｚの範囲、通常は１〜１０ＧＨｚが適当である。 この
プラズマは、減圧下でラジオ波やマイクロ波などの電磁
波を利用するいわゆる低温プラズマである。In the apparatus shown in FIG. 1, the plasma can be generated by, for example, reducing the pressure in the processing chamber 3 and irradiating the processing chamber 3 with an electromagnetic wave such as a microwave. It is appropriate to set the degree of vacuum of the processing chamber 3 to about 1 Torr or less from the viewpoint of maintaining the generation of plasma. The electromagnetic wave is preferably in a range from a radio wave to a microwave, and the frequency is approximately 1 GHz to 1000 GHz.
The range of z, usually 1 to 10 GHz, is appropriate. This plasma is a so-called low-temperature plasma utilizing electromagnetic waves such as radio waves and microwaves under reduced pressure.
【００１８】金属含有化合物を吸着させた炭素系担体
は、金属含有化合物の吸着に使用した薬剤の種類等に応
じて、必要により、プラズマ処理の前に、中和のための
酸性化またはアルカリ化をすることができる。酸性化処
理とは、炭素系担体を酸性水溶液に一定時間浸漬後、適
宜洗浄及び乾燥する処理である。酸性水溶液に含まれる
酸性成分は、塩酸、硝酸、酢酸等であることができる。
酸成分の濃度は、酸の種類等を考慮して適宜決定される
が、通常０．１〜２モル／リットルの範囲とすることが
適当である。The carbon-based carrier to which the metal-containing compound has been adsorbed may be acidified or alkalized for neutralization before the plasma treatment, if necessary, depending on the type of the agent used for adsorbing the metal-containing compound. Can be. The acidification treatment is a treatment in which the carbon-based carrier is immersed in an acidic aqueous solution for a certain period of time, and then appropriately washed and dried. The acidic component contained in the acidic aqueous solution can be hydrochloric acid, nitric acid, acetic acid and the like.
The concentration of the acid component is appropriately determined in consideration of the type of the acid and the like, but is usually preferably in the range of 0.1 to 2 mol / liter.
【００１９】また、アルカリ化処理とは、炭素系担体を
一定時間アルカリ水溶液に浸漬後、適宜洗浄及び乾燥す
る処理である。アルカリ水溶液に含まれるアルカリ成分
としては特に制限はないが、アルカリ金属水酸化物（例
えば、水酸化ナトリウム、水酸化カリウム、水酸化リチ
ウム等）、アルカリ土類金属水酸化物（例えば、水酸化
カルシウム、水酸化バリウム、水酸化ストロンチウム
等）、アンモニア、アミン類等を挙げることができる。
酸成分及びアルカリ成分の濃度は、酸及びアルカリの種
類等を考慮して適宜決定されるが、通常０．１〜２モル
／リットルの範囲とすることが適当である。酸処理又は
アルカリ処理が済んだ炭素系担体は、水分を除去した
後、プラズマ処理を施す。The alkalizing treatment is a treatment in which the carbon-based carrier is immersed in an alkaline aqueous solution for a certain period of time, and then appropriately washed and dried. The alkali component contained in the aqueous alkali solution is not particularly limited, but may be an alkali metal hydroxide (eg, sodium hydroxide, potassium hydroxide, lithium hydroxide, etc.), an alkaline earth metal hydroxide (eg, calcium hydroxide) , Barium hydroxide, strontium hydroxide, etc.), ammonia, amines and the like.
The concentration of the acid component and the alkali component is appropriately determined in consideration of the type of the acid and the alkali, and is usually in the range of 0.1 to 2 mol / liter. The carbon-based support that has been subjected to the acid treatment or the alkali treatment is subjected to a plasma treatment after removing water.
【００２０】[0020]
【発明の効果】本発明の製造方法によれば、活性炭等の
炭素系担体に金属酸化物を担持した触媒等として有用な
複合体を提供することができる。According to the production method of the present invention, a composite useful as a catalyst or the like in which a metal oxide is supported on a carbon-based carrier such as activated carbon can be provided.
【００２１】[0021]
【実施例】以下本発明を実施例によりさらに説明する。 実施例1 図１に概略説明図を示す装置を用いて金属含有化合物を
吸着させた炭素系担体のプライマ処理を行った。即ち、
市販の活性炭１５ｇを秤量し、イオン交換水と共沸して
活性炭の洗浄を行った。洗浄後の活性炭を１１０℃で３
時間乾燥、脱気処理した。９．０ｇのチタンテトライソ
プロポキシド（ＴＴＩＰ）を１００ｍｌのジエチルエー
テルに溶解した。この溶液に上記脱気処理した活性炭を
添加、攪拌した後、室温で１２時間放置した。次いで、
室温で上記溶液を攪拌しながら約１５０ｍｌのイオン交
換水を徐々に加えた。さらに、この溶液を３０℃に維持
しながら、攪拌を続けた。ジエチルエーテル臭がしなく
なるまで、数回デカンテーションと洗浄とを繰り返し
た。その後、１１０℃で１８時間乾燥し、生成物から粉
末のチタン酸を活性炭から分離した。The present invention will be further described with reference to the following examples. Example 1 A carbon-based support on which a metal-containing compound was adsorbed was subjected to a primer treatment using an apparatus whose schematic diagram is shown in FIG. That is,
15 g of commercially available activated carbon was weighed and azeotroped with ion-exchanged water to wash the activated carbon. Activated carbon after washing at 110 ℃ 3
It was dried and degassed for hours. 9.0 g of titanium tetraisopropoxide (TTIP) was dissolved in 100 ml of diethyl ether. The degassed activated carbon was added to this solution, stirred, and allowed to stand at room temperature for 12 hours. Then
While stirring the above solution at room temperature, about 150 ml of ion-exchanged water was gradually added. Further, stirring was continued while maintaining the solution at 30 ° C. The decantation and washing were repeated several times until the smell of diethyl ether disappeared. Thereafter, the powder was dried at 110 ° C. for 18 hours to separate powdery titanic acid from the activated carbon from the product.
【００２２】得られた活性炭を処理室３に充填し、次い
で真空ポンプにより処理室３内を０．１ｔｏｒｒに減圧
した。所定の圧力にまで減圧した後、３００Ｗのマイク
ロ波（２．４５ＧＨｚ）を処理室に照射して処理室内を
プラズマ状態にした。１分間、２分間、３分間及び５分
間経過後、マイクロ波の照射をやめ、活性炭を処理室か
ら取り出した。得られたサンプルをＲＡＤ−Ｂで分析し
た結果、ＴｉＯ2（アナターゼまたはルチル）のピーク
が観測された。図２に２分間プラズマ処理した場合の結
果を示す。この条件ではＴｉＯ2（アナターゼ）が生成
していた。また、図３に５分間プラズマ処理した場合の
結果を示す。この条件ではＴｉＯ2（ルチル）が生成し
ていた。上記実施例では、従来、活性炭が燃えない温度
条件で生成できなかったＴｉＯ2を活性炭に担持させる
ことができた。The activated carbon thus obtained was charged into the processing chamber 3, and the pressure inside the processing chamber 3 was reduced to 0.1 torr by a vacuum pump. After the pressure was reduced to a predetermined pressure, a microwave of 300 W (2.45 GHz) was applied to the processing chamber to bring the processing chamber into a plasma state. After 1 minute, 2 minutes, 3 minutes, and 5 minutes, the microwave irradiation was stopped, and the activated carbon was removed from the processing chamber. As a result of analyzing the obtained sample by RAD-B, a peak of TiO 2 (anatase or rutile) was observed. FIG. 2 shows the result when the plasma processing is performed for 2 minutes. Under these conditions, TiO 2 (anatase) was produced. FIG. 3 shows the results of the case where the plasma treatment was performed for 5 minutes. Under these conditions, TiO 2 (rutile) was generated. In the above example, TiO 2 which could not be produced under the temperature condition in which activated carbon did not burn conventionally could be supported on activated carbon.
【００２３】実施例２ 実施例１と同様の方法により、洗浄、乾燥及び脱気した
活性炭を、硝酸ニッケル水溶液（０．１Ｍ）に添加し、
３時間攪拌した後、室温で１６時間放置した。得られた
硝酸ニッケルを吸着した活性炭を、２．５ｗｔ％のＮａ
ＯＨ水溶液でアルカリ化処理した後、８０℃で１８時間
乾燥し、生成物から沈殿物の粉末を活性炭から分離し
た。得られた活性炭を実施例１と同様にして１分間マイ
クロ波プラズマ処理した。得られたサンプルをＲＡＤ−
Ｂで分析した結果、図４に示すように酸化ニッケルのピ
ークが観測された。Example 2 In the same manner as in Example 1, washed, dried and degassed activated carbon was added to an aqueous nickel nitrate solution (0.1 M).
After stirring for 3 hours, it was left at room temperature for 16 hours. The activated carbon adsorbing the obtained nickel nitrate is replaced with 2.5 wt% of Na.
After alkalization with an aqueous OH solution, the product was dried at 80 ° C. for 18 hours, and a precipitate powder was separated from activated carbon from the product. The obtained activated carbon was subjected to microwave plasma treatment for 1 minute in the same manner as in Example 1. RAD-
As a result of analysis in B, a peak of nickel oxide was observed as shown in FIG.
【００２４】実施例３ 硝酸ニッケル水溶液（０．１Ｍ）の代わりに、硝酸コバ
ルト（０．１Ｍ）を用いた以外は実施例２と同様の浸
漬、アルカリ化、及びプラズマ処理操作を行った（マイ
クロ波プラズマ処理時間は１分間）。得られたサンプル
をＲＡＤ−Ｂで分析した結果を図５に示す。図５では酸
化コバルトのピークが観測された。Example 3 The same immersion, alkalization, and plasma treatment operations as in Example 2 were performed except that cobalt nitrate (0.1 M) was used instead of the nickel nitrate aqueous solution (0.1 M) (Micro (Wave plasma processing time is 1 minute). The result of analyzing the obtained sample by RAD-B is shown in FIG. In FIG. 5, a peak of cobalt oxide was observed.
【図１】 本発明の製造方法に使用できるプラズマ処理
装置の概略説明図。FIG. 1 is a schematic explanatory view of a plasma processing apparatus that can be used in the manufacturing method of the present invention.
【図２】 実施例１における２分間プラズマ処理したサ
ンプルのＲＡＤ−Ｂによる回折パターンを示す。FIG. 2 shows a diffraction pattern by RAD-B of a sample subjected to plasma treatment for 2 minutes in Example 1.
【図３】 実施例１における５分間プラズマ処理したサ
ンプルのＲＡＤ−Ｂによる回折パターンを示す。FIG. 3 shows a diffraction pattern by RAD-B of a sample subjected to a plasma treatment for 5 minutes in Example 1.
【図４】 実施例２で得られたサンプルのＲＡＤ−Ｂに
よる回折パターンを示す。FIG. 4 shows a diffraction pattern by RAD-B of the sample obtained in Example 2.
【図５】 実施例３で得られたサンプルのＲＡＤ−Ｂに
よる回折パターンを示す。FIG. 5 shows a diffraction pattern by RAD-B of the sample obtained in Example 3.
Claims (9)
せ、次いで前記金属含有化合物を吸着させた炭素系担体
をプラズマ処理することにより、前記金属含有化合物を
金属酸化物に変換させることを含む、炭素系担体に金属
酸化物を担持した複合体の製造方法。1. A method comprising: adsorbing a metal-containing compound on a carbon-based carrier; and subjecting the carbon-based carrier to which the metal-containing compound has been adsorbed to plasma treatment to convert the metal-containing compound into a metal oxide. A method for producing a composite in which a metal oxide is supported on a carbon-based support.
イバである請求項1に記載の製造方法。2. The method according to claim 1, wherein the carbon-based carrier is activated carbon or carbon fiber.
属を含む複合酸化物からなる群から選ばれる請求項1ま
たは2に記載の製造方法。3. The production method according to claim 1, wherein the metal oxide is selected from the group consisting of transition metal oxides and composite oxides containing transition metals.
である請求項3に記載の製造方法。4. The method according to claim 3, wherein the composite oxide is a perovskite-type composite oxide.
に浸漬し、乾燥することで炭素系担体に金属含有化合物
を吸着させる請求項１〜４のいずれか１項に記載の記載
の製造方法。5. The production method according to claim 1, wherein the carbon-based carrier is immersed in an aqueous solution containing a metal-containing compound and dried to adsorb the metal-containing compound on the carbon-based carrier. .
われる請求項１〜５のいずれか１項に記載の製造方法。6. The method according to claim 1, wherein the plasma treatment is performed under reduced pressure or normal pressure.
は酸素含有雰囲気中で行われる請求項１〜６のいずれか
１項に記載の製造方法。7. The method according to claim 1, wherein the plasma treatment is performed in an inert gas atmosphere or an oxygen-containing atmosphere.
はRFプラズマである請求項１〜７のいずれか1項に記載
の製造方法。8. The manufacturing method according to claim 1, wherein the plasma processing is microwave plasma or RF plasma.
を、プラズマ処理の前に、酸性化、アルカリ化または沈
殿処理する請求項１〜８のいずれか1項に記載の製造方
法。9. The method according to claim 1, wherein the carbon-based support having the metal-containing compound adsorbed thereon is subjected to an acidification, alkalization or precipitation treatment before the plasma treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9182086A JPH1128357A (en) | 1997-07-08 | 1997-07-08 | Manufacture of composite wherein metal oxide is supported on carbon support |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9182086A JPH1128357A (en) | 1997-07-08 | 1997-07-08 | Manufacture of composite wherein metal oxide is supported on carbon support |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1128357A true JPH1128357A (en) | 1999-02-02 |
Family
ID=16112125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9182086A Pending JPH1128357A (en) | 1997-07-08 | 1997-07-08 | Manufacture of composite wherein metal oxide is supported on carbon support |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1128357A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007145215A1 (en) | 2006-06-13 | 2007-12-21 | Hitachi Maxell, Ltd. | Carbon particle having deposited fine particles, process for producing the same, and electrode for fuel cell |
| WO2007145216A1 (en) | 2006-06-13 | 2007-12-21 | Hitachi Maxell, Ltd. | Fine particle of perovskite oxide, particle having deposited perovskite oxide, catalyst material, catalyst material for oxygen reduction, catalyst material for fuel cell, and electrode for fuel cell |
| JP2011056428A (en) * | 2009-09-11 | 2011-03-24 | Hokkaido Univ | Apparatus for manufacturing metal-supported material and method of manufacturing metal-supported material |
| JP2020023417A (en) * | 2018-08-08 | 2020-02-13 | キレスト株式会社 | Production method of composite having metal oxide fixed on carbon base material |
| CN116253365A (en) * | 2022-12-14 | 2023-06-13 | 中国科学院大连化学物理研究所 | Preparation method and application of ferric oxide catalyst |
-
1997
- 1997-07-08 JP JP9182086A patent/JPH1128357A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007145215A1 (en) | 2006-06-13 | 2007-12-21 | Hitachi Maxell, Ltd. | Carbon particle having deposited fine particles, process for producing the same, and electrode for fuel cell |
| WO2007145216A1 (en) | 2006-06-13 | 2007-12-21 | Hitachi Maxell, Ltd. | Fine particle of perovskite oxide, particle having deposited perovskite oxide, catalyst material, catalyst material for oxygen reduction, catalyst material for fuel cell, and electrode for fuel cell |
| US8007691B2 (en) | 2006-06-13 | 2011-08-30 | Hitachi Maxell Energy, Ltd. | Fine particle of perovskite oxide, particle having deposited perovskite oxide, catalyst material, catalyst material for oxygen reduction, catalyst material for fuel cell, and electrode for fuel cell |
| JP2011056428A (en) * | 2009-09-11 | 2011-03-24 | Hokkaido Univ | Apparatus for manufacturing metal-supported material and method of manufacturing metal-supported material |
| JP2020023417A (en) * | 2018-08-08 | 2020-02-13 | キレスト株式会社 | Production method of composite having metal oxide fixed on carbon base material |
| CN116253365A (en) * | 2022-12-14 | 2023-06-13 | 中国科学院大连化学物理研究所 | Preparation method and application of ferric oxide catalyst |
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