JPH03229646A - Preparation of catalyst - Google Patents
Preparation of catalystInfo
- Publication number
- JPH03229646A JPH03229646A JP2022520A JP2252090A JPH03229646A JP H03229646 A JPH03229646 A JP H03229646A JP 2022520 A JP2022520 A JP 2022520A JP 2252090 A JP2252090 A JP 2252090A JP H03229646 A JPH03229646 A JP H03229646A
- Authority
- JP
- Japan
- Prior art keywords
- carrier
- catalyst
- metal species
- supported
- dispersion
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 79
- 239000002184 metal Substances 0.000 claims abstract description 79
- 239000006185 dispersion Substances 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002612 dispersion medium Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 47
- 229910052697 platinum Inorganic materials 0.000 abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 37
- 239000000243 solution Substances 0.000 description 36
- 239000010419 fine particle Substances 0.000 description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- 239000002253 acid Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 239000002270 dispersing agent Substances 0.000 description 7
- 229910052763 palladium Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 5
- 239000011163 secondary particle Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- 238000000366 colloid method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- -1 for example Substances 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は触媒調製法にかかり、とくに燃料電池、二次電
池、電気化学センサ等に用いられる高活性触媒の調製法
に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for preparing a catalyst, and particularly to a method for preparing a highly active catalyst used in fuel cells, secondary batteries, electrochemical sensors, and the like.
［従来の技術］
従来より、高活性で微粒な金属触媒を得るために、種々
の調製法か検討されており、一般にコロイド法が行なわ
れている（特公昭６３−４６９５８号公報、特公昭６３
−４７１１５号公報）。特公昭６３−４７１１５号公報
に開示されているコロイド法は、貴金属イオン、又はそ
の錯イオン、保護コロイド及び炭素粉体を含有する水溶
液に、還元剤を作用させて、該炭素粉体上に貴金属微粒
子を担持させるものである。[Prior Art] In order to obtain highly active and fine-grained metal catalysts, various preparation methods have been studied, and the colloid method is generally used (Japanese Patent Publication No. 63-46958, Japanese Patent Publication No. 63-1983).
-47115). In the colloid method disclosed in Japanese Patent Publication No. 63-47115, a reducing agent is applied to an aqueous solution containing noble metal ions or their complex ions, protective colloids, and carbon powder, and the noble metal is deposited on the carbon powder. It supports fine particles.
しかしこのコロイド法においては、担体上に担持される
負金属微粒子の凝集を防ぎ、分散状態を良くするために
、親水性高分子化合物よりなる保護コロイドとしての分
散剤、例えばＰＶＡ （ポリビニルアルコール）等が用
いられているので、還元が十分に行えず結晶性が悪い。However, in this colloid method, in order to prevent the agglomeration of the negative metal fine particles supported on the carrier and improve the dispersion state, a dispersant is used as a protective colloid made of a hydrophilic polymer compound, such as PVA (polyvinyl alcohol), etc. is used, the reduction cannot be carried out sufficiently and the crystallinity is poor.
また、調製後もこれら分散剤が触媒表面に被膜として残
留する。Further, even after preparation, these dispersants remain as a film on the catalyst surface.
このため、担持された触媒の活性が十分に発揮できない
。For this reason, the activity of the supported catalyst cannot be fully exhibited.
また、これら分散剤を熱処理することによって除去する
ことも行なわれているが、触媒微粒子の粒成長により活
性の低下が生じることや、分散剤の分解により生じる生
成物か触媒の被毒物質となるという問題点があった。In addition, these dispersants can be removed by heat treatment, but this may result in a decrease in activity due to the growth of the catalyst fine particles, or the products generated by the decomposition of the dispersant may become substances that poison the catalyst. There was a problem.
［発明か解決しようとする課題１
本発明は、これらの問題点に鑑みてなされたものでおり
、分散剤のようなコロイド安定剤を用いずに、微粒な金
属触媒を担体に担持させ得る触媒調製法を提供すること
を目的とする。[Problem to be Solved by the Invention 1] The present invention has been made in view of these problems, and provides a catalyst capable of supporting fine metal catalyst particles on a carrier without using a colloidal stabilizer such as a dispersant. The purpose is to provide a preparation method.
［課題を解決するための手段］
本発明の触媒調製法は、還元剤及び反応剤含有の分散媒
に担体を混合して、該分散媒及び該担体に対する該担体
の割合（以下、担体濃度と称する）か３〜１２重最％（
以下、％は重量％を示す）である担体分散液を得る第１
工程と、該担体分散液を一５℃以下の温度に冷却する第
２工程と、該担体分散液を一５℃以下に維持した状態で
該担体分散液に２０〜６０％の濃度を有する金属種溶液
を添加、混合して該金属種を該担体上に担持させる第３
工程と、該金属種を加熱還元する第４工程とからなるこ
とを特徴とする。[Means for Solving the Problems] The catalyst preparation method of the present invention involves mixing a carrier into a dispersion medium containing a reducing agent and a reactant, and determining the ratio of the carrier to the dispersion medium and the carrier (hereinafter referred to as carrier concentration). ) or 3 to 12 times maximum% (
The first step to obtain a carrier dispersion liquid (hereinafter, % indicates weight %)
a second step of cooling the carrier dispersion to a temperature of -5°C or lower; and adding a metal having a concentration of 20 to 60% to the carrier dispersion while maintaining the carrier dispersion at a temperature of -5°C or lower. A third step of adding and mixing a seed solution to support the metal species on the carrier.
and a fourth step of heating and reducing the metal species.
前記還元剤としては、アルデヒド、アルコール、有機酸
等、具体的にはホルマリン、メタノール、ギ酸等を使用
することができる。As the reducing agent, aldehydes, alcohols, organic acids, etc. can be used, specifically formalin, methanol, formic acid, etc.
前記反応剤は、例えば水酸化ナトリウム、水酸化カリウ
ム、水酸化リチウムを使用することができる。As the reactant, for example, sodium hydroxide, potassium hydroxide, and lithium hydroxide can be used.
前記担体としては、カーボン、活性炭、カーボンブラッ
ク等の炭素粉体を使用することができる。As the carrier, carbon powder such as carbon, activated carbon, carbon black, etc. can be used.
また、場合によっては炭素繊維を使用することもできる
。Moreover, carbon fiber can also be used depending on the case.
前記担体濃度は、より好ましくは５〜１０％である。こ
の担体濃度が１２％を越えると、分散液中に担体を均一
に分散させることが困難となり、触媒金属種を担体に均
一に担持させることができない。また、担体濃度が３％
より低いと、担持される触媒金属種の粒径が大きくなる
。The carrier concentration is more preferably 5 to 10%. If the carrier concentration exceeds 12%, it becomes difficult to uniformly disperse the carrier in the dispersion liquid, and the catalytic metal species cannot be uniformly supported on the carrier. In addition, the carrier concentration is 3%
The lower the value, the larger the particle size of the supported catalytic metal species.
前記第２工程における冷却温度は一１０’Ｃ以下がより
好ましい。この温度が一５℃より高いと担持される触媒
金属種の粒径か大きくなる。The cooling temperature in the second step is more preferably -10'C or less. If this temperature is higher than 15° C., the particle size of the supported catalyst metal species increases.
前記金属種としては、白金、ルテニウム、ロジウム、パ
ラジウム等の白金族金属の一種又は複数種を使用するこ
とかできる。As the metal species, one or more platinum group metals such as platinum, ruthenium, rhodium, and palladium can be used.
前記金属種溶液の濃度は、より好ましくは３０〜５０％
である。この濃度が２０％より低いと担持される触媒金
属種の粒径が大きくなる。また、該濃度が６０％より高
いと担持される触媒金属種の分散状態が悪くなる。The concentration of the metal species solution is more preferably 30 to 50%.
It is. When this concentration is lower than 20%, the particle size of the supported catalyst metal species becomes large. Moreover, if the concentration is higher than 60%, the state of dispersion of the supported catalyst metal species becomes poor.
前記加熱還元は、４０’Ｃ以上の温度で、より好ましく
は６０〜８０’Ｃの温度で１〜３時間加熱することによ
り行うことかできる。The thermal reduction can be carried out by heating at a temperature of 40'C or higher, more preferably at a temperature of 60 to 80'C for 1 to 3 hours.
［作用］
本発明の触媒調製法は、所定の担体濃度を有する担体分
散液に、所定の温度以下に冷却した状態で、所定の濃度
を有する金属種溶液を添加混合することにより、触媒金
属種を担体に対して微粒な状態で均一分散させるもので
ある。[Function] In the catalyst preparation method of the present invention, a metal species solution having a predetermined concentration is added to and mixed with a carrier dispersion having a predetermined carrier concentration in a state cooled to a predetermined temperature or lower. is uniformly dispersed in fine particles in a carrier.
すなわち、担体濃度及び金属種溶液の濃度を所定の濃度
以上とし、かつ担持時の温度を一５℃以下とすることに
より、金属種の溶解度を小さくし、いわゆる過飽和状態
にする。これにより、金属種の核生成速度が高くなり核
成長か抑制される。このため、金属種の核は微粒化した
状態で担体に担持される。That is, the solubility of the metal species is reduced by setting the carrier concentration and the concentration of the metal species solution to a predetermined concentration or higher and the temperature at the time of supporting to be 15° C. or lower, thereby bringing the solubility of the metal species into a so-called supersaturated state. This increases the nucleation rate of metal species and suppresses nuclear growth. Therefore, the core of the metal species is supported on the carrier in a finely divided state.
また、担体濃度及び金属種溶液の濃度を所定の濃度以下
とすることにより、担体は均一に分散し、かつ該担体に
担持される金属種も均一に分散した状態で担持される。Further, by controlling the carrier concentration and the concentration of the metal species solution to a predetermined concentration or lower, the carrier is uniformly dispersed, and the metal species supported on the carrier is also supported in a uniformly dispersed state.
［実施例］ 以下、実施例により具体的に説明する。[Example] Hereinafter, this will be explained in detail using examples.
（実施例１）
金属種として白金（原料は塩化白金酸）、担体としてカ
ーボンブラック（以下、担体カーボンと称する）を用い
た触媒調整法について説明する。(Example 1) A catalyst preparation method using platinum (the raw material is chloroplatinic acid) as the metal species and carbon black (hereinafter referred to as carrier carbon) as the carrier will be described.
なお、本触媒調製法の全体フロー図を第５図に示す。Incidentally, an overall flowchart of the present catalyst preparation method is shown in FIG.
導電性カーボンブラック（三菱化成■製、＃３７５０）
１ｋｑに１０体積％のエタノール溶液２Ｑ、Ｉｌを添加
し、撹拌、混合を行いながら９０℃で２時間親水処理を
行った。これを洗浄、濾過して触媒調整用担体カーホン
を得た。Conductive carbon black (manufactured by Mitsubishi Kasei ■, #3750)
A 10 volume % ethanol solution 2Q, Il was added to 1 kq, and hydrophilic treatment was performed at 90° C. for 2 hours while stirring and mixing. This was washed and filtered to obtain a carrier carphone for catalyst preparation.
５ｇ反応槽に還元剤であるホルムアルデヒド溶液（ＨＣ
Ｈ０３７％含有）０．！Ｍを投入し、撹拌しなから反応
槽の外部から冷却槽及び冷却装置を用いて１０’Ｃに冷
却、保持した。液温か安定した後、反応剤である５０％
の水酸化カリウム溶液０．５１を徐々に添加した。この
ときの反応は発熱を伴うので、液温か４０℃以下になる
ように注意して添加する。添加修了後、さらに３０分間
撹拌、混合を行い分散媒を得た。このときの液温は１０
’Ｃ（±５℃）に保持する。Formaldehyde solution (HC), which is a reducing agent, is placed in a 5g reaction tank.
H037% content) 0. ! M was added, and while stirring, the reaction vessel was cooled to and maintained at 10'C using a cooling tank and a cooling device from the outside. After the liquid temperature stabilizes, 50% of the reactant
of potassium hydroxide solution was slowly added. Since the reaction at this time is accompanied by heat generation, the solution is added with care so that the liquid temperature is 40° C. or lower. After the addition was completed, stirring and mixing were further performed for 30 minutes to obtain a dispersion medium. The liquid temperature at this time is 10
'C (±5°C).
次に、親水処理を行った担体カーボンを９０ｇ精秤し、
反応槽へ徐々に添加した。この状態で担体カーホンか分
散媒の中で十分均一に分散するまで１時間撹拌、混合を
行い担体分散液を得た。なお、この担体分散液における
担体濃度は５％だった。Next, 90g of carrier carbon that had been subjected to hydrophilic treatment was accurately weighed,
Added slowly to the reaction vessel. In this state, the carrier carphone was stirred and mixed for 1 hour until it was sufficiently uniformly dispersed in the dispersion medium to obtain a carrier dispersion. Note that the carrier concentration in this carrier dispersion was 5%.
この後、反応槽の温度を一１０’Ｃ以下まで冷却した。Thereafter, the temperature of the reactor was cooled to below -10'C.
担体分散液の液温が十分安定した後、金属種溶液として
白金を１０Ｑ含む４０％塩化白金酸溶液を反応槽中へ添
加した。添加時は若干の発熱を伴うので、常時−１０’
Ｃ以下になるように冷却する（冷却装置は一１５℃（±
５℃）に制御していた）。添加修了後、３０分間撹拌、
混合を続けた。After the temperature of the carrier dispersion became sufficiently stable, a 40% chloroplatinic acid solution containing 10Q of platinum was added to the reaction tank as a metal species solution. Since some heat is generated during addition, always add -10'
Cool to below 15°C (cooling equipment should be kept at -15°C (±
The temperature was controlled at 5°C). After addition, stir for 30 minutes,
Continued mixing.
次に昇温して７５℃１２時間の加熱操作を行って金属種
を還元した。加熱還元の１麦、反応槽内へ０．５ｇのイ
オン交換水を加え、撹拌を続けて液温を室温に戻した。Next, the temperature was raised and a heating operation was performed at 75° C. for 12 hours to reduce the metal species. After heating and reducing the wheat, 0.5 g of ion-exchanged water was added to the reaction tank, and stirring was continued to return the liquid temperature to room temperature.
担持金属触媒を含む混合溶液はデカンテーションの後、
濾過、洗浄を行った。After the mixed solution containing the supported metal catalyst is decanted,
Filtered and washed.
洗浄はイオン交換水を用いて、濾液中に塩素イオンが検
出されなくなるまで十分に行った。その後、乾燥して担
持金属触媒を得た。Washing was carried out sufficiently using ion-exchanged water until no chloride ions were detected in the filtrate. Thereafter, it was dried to obtain a supported metal catalyst.
（評価）
この担持金属触媒を分析した結果、担持率は１０％、収
率はほぼ１００％であった。はぼ全量の金属種が金属に
還元されて、担体に担持されたことかわかった。なお、
担持率とは、担持された金属及び担体の総重量に対する
担持された金属の割合である。(Evaluation) As a result of analyzing this supported metal catalyst, the supporting rate was 10% and the yield was approximately 100%. It was found that almost all of the metal species were reduced to metals and supported on the carrier. In addition,
The supporting ratio is the ratio of the supported metal to the total weight of the supported metal and the carrier.
Ｘ線回折法により平均粒径を測定したところ２３六であ
った（回折面は白金（１１１）面を用いた）。また、透
過型電子顕微鏡（ＴＥＭ＞で観察した結果、白金微粒子
が担体に対してほぼ均一に分散しており、平均粒径もＸ
線回折による結果と一致していた。The average particle size was measured by X-ray diffraction and was found to be 236 (platinum (111) plane was used as the diffraction surface). Furthermore, as a result of observation using a transmission electron microscope (TEM), it was found that the platinum fine particles were almost uniformly dispersed in the carrier, and the average particle size was
This was consistent with the results obtained by line diffraction.
さらに、触媒の分散性を評価するために、触媒を酸化雰
囲気中３００℃、２時間処理し、上記と同様の方法によ
り平均粒径及び分散状態を確認した。その結果、白金の
シンタリングか生じておらず、平均粒径、分散状態に変
化かなかった。これにより、白金は担体に対して微粒な
状態で均一に分散し、強固に固着していることがわかっ
た。Further, in order to evaluate the dispersibility of the catalyst, the catalyst was treated in an oxidizing atmosphere at 300° C. for 2 hours, and the average particle size and dispersion state were confirmed by the same method as above. As a result, no sintering of platinum occurred, and there was no change in the average particle size or dispersion state. As a result, it was found that platinum was uniformly dispersed in a fine particle state and firmly fixed to the carrier.
（担体濃度と触媒平均粒径との関係）
上記実施例１において、担体分散液における担体濃度を
種々変更して、担体濃度と触媒平均粒径との関係を調べ
た。その結果を第１図に示す。(Relationship between carrier concentration and catalyst average particle diameter) In the above Example 1, the carrier concentration in the carrier dispersion was variously changed, and the relationship between the carrier concentration and the catalyst average particle diameter was investigated. The results are shown in FIG.
第１図からも明らかなように、担体濃度が１２％を越え
ると担体の均一分散が困難であり、担体濃度か５〜１０
％のとき触媒平均粒径か２５六以下となりとくに好まし
かった。As is clear from Figure 1, when the carrier concentration exceeds 12%, it is difficult to uniformly disperse the carrier;
%, the average particle diameter of the catalyst was 256 or less, which was particularly preferable.
（金属種溶液の８度と触媒平均粒径との関係〉上記実施
例１において、金属種溶液の濃度を種々変更して、金属
種溶液の濃度と触媒平均粒径との関係を調べた。その結
果を第２図に示す。(Relationship between 8 degrees of metal seed solution and catalyst average particle size) In Example 1, the concentration of the metal seed solution was variously changed and the relationship between the concentration of the metal seed solution and the catalyst average particle size was investigated. The results are shown in FIG.
第２図からも明らかなように、金属種溶液の濃度が２０
〜６０％のとき触媒平均粒径か２５六以下となりとくに
好ましかった。As is clear from Figure 2, the concentration of the metal species solution is 20
When it was 60%, the average particle diameter of the catalyst was 256 or less, which was particularly preferable.
（金属種溶液添加時の温度と触媒平均粒径との関係〉
上記実施例１において、金属種溶液添加時の温度を種々
変更して、金属種溶液添加時の温度と触媒平均粒径との
関係を調べた。その結果を第３図に示す。(Relationship between the temperature at the time of adding the metal seed solution and the catalyst average particle size) In the above Example 1, the temperature at the time of adding the metal seed solution was variously changed, and the temperature at the time of adding the metal seed solution and the catalyst average particle size were The relationship was investigated and the results are shown in Figure 3.
第３図からも明らかなように、金属種溶液添加時の温度
か一５℃以下のとき触媒平均粒径が３０六以下となり好
ましかった。As is clear from FIG. 3, when the temperature at the time of addition of the metal seed solution was 15° C. or lower, the catalyst average particle size was 30° C. or lower, which was preferable.
（担持率と触媒平均粒径との関係）
上記実施例１において、担持率を種々変更して、担持率
と触媒平均粒径との関係を調べた。その結果を後述する
比較例１の従来法における結果とともに第４図に示す。(Relationship between Support Rate and Catalyst Average Particle Size) In Example 1, the support rate was variously changed and the relationship between the support rate and catalyst average particle size was investigated. The results are shown in FIG. 4 together with the results of the conventional method of Comparative Example 1, which will be described later.
第４図からも明らかなように、本実施例にかかる触媒調
製法では、例えば４０％の高担持率においても触媒平均
粒径は３０六以下となり、触媒粒子の微粒化が可能であ
る。As is clear from FIG. 4, in the catalyst preparation method according to the present example, even at a high loading rate of 40%, for example, the average particle diameter of the catalyst is 306 or less, and it is possible to make the catalyst particles fine.
（実施例２）
前述した実施例１の触媒調整法において、金属種溶液と
して白金を４０ＣＩ含む４０％塩化白金酸溶液を用いて
、担持金属触媒を調整した。他の条件は実施例１と同じ
である。(Example 2) In the catalyst preparation method of Example 1 described above, a supported metal catalyst was prepared using a 40% chloroplatinic acid solution containing 40 CI of platinum as the metal species solution. Other conditions are the same as in Example 1.
調整した担持金属触媒を分析した結果、担持率３０％、
収率はほぼ１００％であった。この触媒の平均粒径をＸ
線回折法により測定した結果、２６六であった。また、
ＴＥＭで観察した結果、白金微粒子か担体に対してほぼ
均一に分散しており、平均粒径もＸ線回折法による結果
と一致していた。As a result of analyzing the prepared supported metal catalyst, the supporting rate was 30%,
The yield was almost 100%. The average particle size of this catalyst is
As a result of measurement by line diffraction method, it was 266. Also,
As a result of observation using a TEM, the platinum fine particles were almost uniformly dispersed in the carrier, and the average particle size was also consistent with the results obtained by the X-ray diffraction method.
（実施例３）
金属種として塩化ルテニウム（ＲｕＣｆ１３・３Ｈ２０
）を用い、担体カーホンにルテニウム（ＲＵ）を担持し
た例を示す。(Example 3) Ruthenium chloride (RuCf13.3H20
) is used to support ruthenium (RU) on the carrier carphone.
金属種溶液として、塩化ルテニウムを５％塩酸溶液に溶
かし、濃度を４０％としたものを使用する。この金属種
溶液を、還元剤としてのホルムアルデヒド溶液及び反応
剤としての水酸化カリウム溶液よりなる分散媒中に担体
カーホンを分散混合して得られた担体分散液中に徐々に
添加した。なお、このときの担体分散液は一１０℃だっ
た。また金属種溶液は担体にルテニウムが１０％担持す
るように所定量添加した。As the metal seed solution, ruthenium chloride is dissolved in a 5% hydrochloric acid solution to give a concentration of 40%. This metal species solution was gradually added to a carrier dispersion obtained by dispersing and mixing a carrier carphone in a dispersion medium consisting of a formaldehyde solution as a reducing agent and a potassium hydroxide solution as a reactant. The temperature of the carrier dispersion at this time was -10°C. Further, a predetermined amount of the metal seed solution was added so that 10% of ruthenium was supported on the carrier.
添加後、３０分間十分に撹拌混合した。さらに、５５℃
で２時間加熱還元した。還元終了後、実施例１と同様に
濾過、洗浄を行い、乾燥後担持金属触媒を得た。After the addition, the mixture was sufficiently stirred and mixed for 30 minutes. Furthermore, 55℃
The mixture was heated and reduced for 2 hours. After completion of the reduction, filtration and washing were performed in the same manner as in Example 1, and a supported metal catalyst was obtained after drying.
得られた担持金属触媒を実施例１と同様にＸ線回折及び
ＴＥＭ観察により分析した結果、ルテニウム微粒子が担
体に均一に担持されてあり、平均粒径は２２ムだった。The obtained supported metal catalyst was analyzed by X-ray diffraction and TEM observation in the same manner as in Example 1, and it was found that ruthenium fine particles were uniformly supported on the carrier, and the average particle size was 22 μm.
（実施例４〉
金属種として塩化パラジウム（ＰｄＣβ２）を用い、担
体カーボンにパラジウム（Ｐｄ）を担持した例を示す。(Example 4) An example is shown in which palladium chloride (PdCβ2) is used as the metal species and palladium (Pd) is supported on carrier carbon.
金属種溶液として、塩化パラジウムを１０％塩酸溶液に
溶かして濃度を４０％としたものを使用し、かつ加熱還
元温度を７０’Ｃとすること以外は上記実施例３と同様
の方法により担持金属触媒を得た。The supported metal was prepared in the same manner as in Example 3 above, except that palladium chloride was dissolved in a 10% hydrochloric acid solution to give a concentration of 40% as the metal seed solution, and the heating reduction temperature was 70'C. I got a catalyst.
得られた担持金属触媒をＸ線回折及びＴＥＭ観察により
分析した結果、パラジウム微粒子が担体に均一に担持さ
れており、平均粒径は２ＯＡだった。As a result of analyzing the obtained supported metal catalyst by X-ray diffraction and TEM observation, it was found that palladium fine particles were uniformly supported on the carrier, and the average particle size was 2OA.
（実施例５）
金属種として塩化ロジウム（ＲｈＣｆ１３・３Ｈ２０）
を用い、担体カーホンにロジウム（Ｒｉｌ）を担持した
例を示す。(Example 5) Rhodium chloride (RhCf13.3H20) as the metal species
An example is shown in which rhodium (Ril) is supported on the carrier carphone using the following.
金属種溶液として、塩化ロジウムを１０％塩酸溶液に溶
かして濃度を４０％としたものを使用し、かつ加熱還元
温度をｓｏ’ｃとすること以外は上記実施例３と同様の
方法により担持金属触媒を得た。The supported metal was prepared in the same manner as in Example 3 above, except that rhodium chloride was dissolved in a 10% hydrochloric acid solution to give a concentration of 40% as the metal seed solution, and the heating reduction temperature was set to SO'C. I got a catalyst.
得られた担持金属触媒を実施例１と同様にＸ線回折及び
ＴＥＭ観察により分析した結果、ロジウム微粒子が担体
に均一に担持されており、平均粒径は２０六だった。The obtained supported metal catalyst was analyzed by X-ray diffraction and TEM observation in the same manner as in Example 1, and it was found that rhodium fine particles were uniformly supported on the carrier, and the average particle size was 206.
（実施例６）
金属種として塩化白金酸（Ｈ２ＰｔＣ，ｌ！ ６・６Ｈ
２０）及び塩化ルテニウム（ＲｕＣ，ｌｌ ３ ・３Ｈ
２０）を用い、担体カーボンに白金−ルテニウム（Ｐｔ
−Ｒｕ）二元触媒を担持した例を示す。(Example 6) Chloroplatinic acid (H2PtC, l!6.6H) was used as the metal species.
20) and ruthenium chloride (RuC, ll 3 ・3H
20), platinum-ruthenium (Pt
-Ru) An example in which a binary catalyst is supported is shown.
金属種溶液として、塩化白金酸の白金と塩化ルテニウム
のルテニウムの組成比（原子モル）がＰｔ：Ｒｕ＝６：
４となるように５％塩酸溶液に溶かして、塩化白金酸と
塩化ルテニウムとを合せた濃度を４０％としたものを使
用し、加熱還元温度を６０’Ｃとし、かつ白金とルテニ
ウムとを合せて２０％担体に担持するようにすること以
外は上記実施例３と同様の方法により担持金属触媒を得
た。As a metal seed solution, the composition ratio (atomic moles) of platinum in chloroplatinic acid and ruthenium in ruthenium chloride is Pt:Ru=6:
4, dissolved in a 5% hydrochloric acid solution so that the combined concentration of chloroplatinic acid and ruthenium chloride was 40%, the thermal reduction temperature was set to 60'C, and the combined platinum and ruthenium were used. A supported metal catalyst was obtained in the same manner as in Example 3 above, except that 20% of the catalyst was supported on the carrier.
得られた担持金属触媒をＸ線回折及びＴＥＭ観察により
分析した結果、白金−ルテニウム微粒子が担体に均一に
担持されており、平均粒径は２２六だった。Analysis of the obtained supported metal catalyst by X-ray diffraction and TEM observation revealed that platinum-ruthenium fine particles were uniformly supported on the carrier, and the average particle size was 226.
（実施例７）
金属種として塩化白金酸（Ｈ２Ｐ ｔＣ，Ｑ （、・６
Ｈ２０）及び塩化パラジウム（ＰｄＣ，ｌｌ ２ ＞を
用い、担体カーホンに白金−パラジウム（Ｐｔ−Ｐｄ）
二元触媒を担持した例を示す。(Example 7) Chloroplatinic acid (H2P tC,Q (, 6
H20) and palladium chloride (PdC, ll2>) and platinum-palladium (Pt-Pd) on a carrier carphone.
An example in which a two-way catalyst is supported is shown.
金属種溶液として、塩化白金酸の白金と塩化パラジウム
のパラジウムの組成比（原子モル）がＰｔ：ｐｄ＝５：
５となるように１０％塩酸溶液に溶かして、塩化白金酸
と塩化パラジウムとを合せた濃度を４０％としたものを
使用し、加熱還元温度を７０’Ｃとし、かつ白金とパラ
ジウムとを合せて２０％担体に担持するようにすること
以外は上記実施例３と同様の方法により担持金属触媒を
得た。As a metal species solution, the composition ratio (atomic moles) of platinum in chloroplatinic acid and palladium in palladium chloride is Pt:pd=5:
5, dissolved in a 10% hydrochloric acid solution so that the combined concentration of chloroplatinic acid and palladium chloride was 40%, the heating reduction temperature was set to 70'C, and the combined platinum and palladium were used. A supported metal catalyst was obtained in the same manner as in Example 3 above, except that 20% of the catalyst was supported on the carrier.
得られた担持金属触媒を実施例１と同様にＸ線回折及び
王ＥＭ観察により分析した結果、白金パラジウム微粒子
か担体に均一に担持されており、平均粒径は２０六だっ
た。The obtained supported metal catalyst was analyzed by X-ray diffraction and EM observation in the same manner as in Example 1, and it was found that platinum-palladium fine particles were uniformly supported on the carrier, and the average particle size was 206.
（比較例１）
比較のために、ＰＶＡ （ポリヒニルアルコール）を用
いたコロイド法により白金をカーボンブラックに担持し
た触媒を調整した。(Comparative Example 1) For comparison, a catalyst in which platinum was supported on carbon black was prepared by a colloid method using PVA (polyhinyl alcohol).
イオン交換水０．５９にメタノール０．５．ｌＪを混合
した溶液にＰＶＡ （和光紬薬製、重合度５００）を２
．０ＣＩ溶解させた。これに白金を１ｇ含む５％の塩化
白金酸溶液を添加し、撹拌、混合した。この中に実施例
１で使用した親水処理を行った担体カーホン９ｇを徐々
に添加し、混合、分散した。これを還流下、撹拌、混合
を行いながら７０′Ｃ１４時間加熱還元を行った。得ら
れた担持金属触媒を含む混合液をデカンテーションの後
、イオン交換水を用いて濾過、洗浄を行った。Deionized water 0.59 to methanol 0.5. PVA (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd., polymerization degree 500) was added to the solution containing 1J.
．． Dissolved with 0CI. A 5% chloroplatinic acid solution containing 1 g of platinum was added to this, and the mixture was stirred and mixed. 9 g of the hydrophilically treated carrier carphone used in Example 1 was gradually added to the mixture, mixed and dispersed. This was heated and reduced at 70'C for 14 hours while stirring and mixing under reflux. The resulting mixed solution containing the supported metal catalyst was decanted, then filtered and washed using ion-exchanged water.
この担持金属触媒を乾燥後、分析した結果、担持率は１
０％、収率はほぼ１００％でめった。Ｘ線回折法により
平均粒径を測定した結果、３７＾であった（回折面は白
金（１１１）面を用いた〉。After drying this supported metal catalyst, analysis revealed that the supporting ratio was 1.
0%, and the yield was almost 100%. The average particle size was measured by X-ray diffraction and was 37^ (platinum (111) plane was used as the diffraction surface).
また、分散状態を確認するためにＴＥＭで観察した結、
果、白金微粒子（−次粒子）が１０数個で集団（二次粒
子群）を形成しており、前記実施例に比へて分散性が悪
かった。In addition, in order to confirm the dispersion state, the results were observed using a TEM.
As a result, more than 10 platinum fine particles (secondary particles) formed a group (secondary particle group), and the dispersibility was poorer than in the previous example.
さらに、分散性を評価するために、触媒を酸化雰囲気中
３００’Ｃ１２時間処理し、前述の分析法により平均粒
径及び分散状態を確認した。その結果、シンタリングに
よる粒成長が生じていたために平均粒径か６４六に増大
した。ＴＥＭの観察結果、二次粒子群がさらに成長し、
分散性は著しく悪化していることがわかった。Furthermore, in order to evaluate the dispersibility, the catalyst was treated in an oxidizing atmosphere at 300'C for 12 hours, and the average particle size and dispersion state were confirmed by the above-mentioned analysis method. As a result, the average grain size increased to 646 because grain growth occurred due to sintering. As a result of TEM observation, the secondary particle group further grows,
It was found that the dispersibility deteriorated significantly.
（比較例２〉
ＰＶＡの添加量を８ｇとし、かつ白金を５ｇ含む５％塩
化白金酸溶液を使用すること以外は上記比較例１と同様
の方法により触媒を調製した。(Comparative Example 2) A catalyst was prepared in the same manner as in Comparative Example 1, except that the amount of PVA added was 8 g and a 5% chloroplatinic acid solution containing 5 g of platinum was used.
調製した触媒を分析した結果、担持率は約３０％、収率
はほぼ１００％であった。Ｘ線回折法により平均粒径を
測定した結果、６０Ａであった（回折面は白金（１１１
）面を用いた）。また、分散状態を確認するために丁Ｅ
Ｍで観察した結果、白金微粒子（−次粒子）が２０〜３
０個で集団（二次粒子群）を形成しており、前記実施例
に比べて分散性が悪かった。As a result of analyzing the prepared catalyst, the supporting ratio was about 30% and the yield was almost 100%. As a result of measuring the average particle size by X-ray diffraction method, it was 60A (the diffraction surface was platinum (111
) surface). Also, to check the dispersion state,
As a result of observation with M, platinum fine particles (-order particles) were found to be 20 to 3
0 particles formed a group (secondary particle group), and the dispersibility was poorer than in the above example.
さらに、分散性を評価するために、触媒を酸化雰囲気中
３００ ’Ｃ１２時間処理し、前述の分析法により平均
粒径及び分散状態を確認した。その結果、シンタリング
による粒成長か生じていたために平均粒径が１０８２に
増大した。ＴＥＭの観察結果、二次粒子群がさらに成長
し、分散性は著しく悪化していることがわかった。Further, in order to evaluate the dispersibility, the catalyst was treated in an oxidizing atmosphere at 300'C for 12 hours, and the average particle size and dispersion state were confirmed by the above-mentioned analytical method. As a result, the average grain size increased to 1082 due to grain growth due to sintering. As a result of TEM observation, it was found that the secondary particle group further grew and the dispersibility deteriorated significantly.
［発明の効果］
以上詳）ホしたように本発明の触媒調製法は、触媒金属
種の核生成速度を高くして核成長を抑えることにより触
媒金属種を微粒化した状態で担体に担持させ、かつ該触
媒金属種を均一に分散した状態で該担体に担持させるこ
とができる。[Effects of the Invention] As described above, the catalyst preparation method of the present invention increases the nucleation rate of the catalytic metal species and suppresses the growth of nuclei, thereby allowing the catalytic metal species to be supported on the carrier in an atomized state. , and the catalyst metal species can be supported on the carrier in a uniformly dispersed state.
したがって、本発明によりｊｑられた触媒は高活性で高
分散なものとなる。Therefore, the catalyst prepared according to the present invention has high activity and high dispersion.
また、本発明の触媒調製法は、分散剤等のコロイド安定
剤を用いずに触媒の微粒化が可能であるので、調製後の
特別な雰囲気処理による分散剤等の除去工程を省くこと
ができる。In addition, the catalyst preparation method of the present invention allows the catalyst to be atomized without using a colloidal stabilizer such as a dispersant, so the step of removing the dispersant, etc. by special atmosphere treatment after preparation can be omitted. .
第１図は担体濃度と触媒平均粒径との関係を示すグラフ
、第２図は金属種溶液の濃度と触媒平均粒径との関係を
示すグラフ、第３図は金属種溶液添加時の温度と触媒平
均粒径との関係を示すグラフ、第４図は担持率と触媒平
均粒径との関係を示すグラフ、第５図は実施例にかかる
触媒調製法の全体フロー図である。Figure 1 is a graph showing the relationship between carrier concentration and catalyst average particle size, Figure 2 is a graph showing the relationship between metal seed solution concentration and catalyst average particle size, and Figure 3 is the temperature at the time of addition of metal seed solution. FIG. 4 is a graph showing the relationship between the loading ratio and the catalyst average particle size, and FIG. 5 is an overall flowchart of the catalyst preparation method according to the example.
Claims (1)
、該分散媒及び該担体に対する該担体の割合が３〜１２
重量％である担体分散液を得る第１工程と、 該担体分散液を−５℃以下の温度に冷却する第２工程と
、 該担体分散液を−５℃以下に維持した状態で該担体分散
液に２０〜６０重量％の濃度を有する金属種溶液を添加
、混合して該金属種を該担体上に担持させる第３工程と
、 該金属種を加熱還元する第４工程とからなることを特徴
とする触媒調製法。(1) A carrier is mixed with a dispersion medium containing a reducing agent and a reactant, and the ratio of the carrier to the dispersion medium and the carrier is 3 to 12.
% by weight, a second step of cooling the carrier dispersion to a temperature of -5°C or lower, and cooling the carrier dispersion while maintaining the carrier dispersion at -5°C or lower. A third step of adding and mixing a metal species solution having a concentration of 20 to 60% by weight to the liquid to support the metal species on the carrier, and a fourth step of heating and reducing the metal species. Characteristic catalyst preparation method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022520A JPH03229646A (en) | 1990-02-01 | 1990-02-01 | Preparation of catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022520A JPH03229646A (en) | 1990-02-01 | 1990-02-01 | Preparation of catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03229646A true JPH03229646A (en) | 1991-10-11 |
Family
ID=12085050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2022520A Pending JPH03229646A (en) | 1990-02-01 | 1990-02-01 | Preparation of catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03229646A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008114217A (en) * | 2006-10-12 | 2008-05-22 | Sharp Corp | Catalyst containing noble metal particle carried on carbon substrate, and its manufacturing method |
| JP2009164142A (en) * | 2006-10-12 | 2009-07-23 | Sharp Corp | Manufacturing method of catalyst for fuel cell containing noble metal particles carried on carbon substrate |
| JP2021155784A (en) * | 2020-03-26 | 2021-10-07 | トヨタ紡織株式会社 | Method for producing metal nanoparticles, method for producing membrane electrode assembly, and method for producing solid polymer electrolyte fuel cell |
-
1990
- 1990-02-01 JP JP2022520A patent/JPH03229646A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008114217A (en) * | 2006-10-12 | 2008-05-22 | Sharp Corp | Catalyst containing noble metal particle carried on carbon substrate, and its manufacturing method |
| JP2009164142A (en) * | 2006-10-12 | 2009-07-23 | Sharp Corp | Manufacturing method of catalyst for fuel cell containing noble metal particles carried on carbon substrate |
| JP2021155784A (en) * | 2020-03-26 | 2021-10-07 | トヨタ紡織株式会社 | Method for producing metal nanoparticles, method for producing membrane electrode assembly, and method for producing solid polymer electrolyte fuel cell |
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