JP2007119900A - Composite material of metal and porous substrate, and production method therefor - Google Patents
Composite material of metal and porous substrate, and production method therefor Download PDFInfo
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- JP2007119900A JP2007119900A JP2006063404A JP2006063404A JP2007119900A JP 2007119900 A JP2007119900 A JP 2007119900A JP 2006063404 A JP2006063404 A JP 2006063404A JP 2006063404 A JP2006063404 A JP 2006063404A JP 2007119900 A JP2007119900 A JP 2007119900A
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- Prior art keywords
- metal
- porous substrate
- composite material
- porous
- palladium
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- 239000000758 substrate Substances 0.000 title claims abstract description 146
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 116
- 239000002184 metal Substances 0.000 title claims abstract description 116
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 19
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000000084 colloidal system Substances 0.000 claims abstract description 12
- 150000002500 ions Chemical class 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 159
- 229910052763 palladium Inorganic materials 0.000 claims description 74
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 60
- 239000011148 porous material Substances 0.000 claims description 49
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 34
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 31
- 239000003054 catalyst Substances 0.000 claims description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 26
- 238000007772 electroless plating Methods 0.000 claims description 24
- 238000005868 electrolysis reaction Methods 0.000 claims description 24
- 239000010948 rhodium Substances 0.000 claims description 15
- 239000010931 gold Substances 0.000 claims description 14
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- 238000004174 sulfur cycle Methods 0.000 claims description 11
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 8
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- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
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- 239000004332 silver Substances 0.000 claims description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 7
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- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 7
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- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 12
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- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 11
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 11
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- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 7
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
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- 229910002857 Sr0.8La0.2TiO3 Inorganic materials 0.000 description 4
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- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 229910052691 Erbium Inorganic materials 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 229910052689 Holmium Inorganic materials 0.000 description 3
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 3
- 229910052765 Lutetium Inorganic materials 0.000 description 3
- 229910052772 Samarium Inorganic materials 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 3
- 229910052771 Terbium Inorganic materials 0.000 description 3
- 229910052775 Thulium Inorganic materials 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
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- 238000004458 analytical method Methods 0.000 description 3
- 239000013590 bulk material Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
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Abstract
Description
本発明は、金属−多孔質基材複合材料及びその製造方法に関する。さらに詳述すると、本発明は、多孔質基材のミクロ構造と表面積を損なうことなく、その表面に微小な粒状もしくは針状金属を均一に被覆することにより、被覆金属の表面積を増大させた金属−多孔質基材複合材料及び当該材料を無電解めっき法を用いて製造する方法に関する。 The present invention relates to a metal-porous substrate composite material and a method for producing the same. More specifically, the present invention relates to a metal in which the surface area of the coated metal is increased by uniformly coating the surface with fine granular or acicular metal without impairing the microstructure and surface area of the porous substrate. -It relates to a porous substrate composite material and a method for producing the material using an electroless plating method.
触媒金属を担体に担持させる技術が特許文献１及び特許文献２に開示されている。特許文献１では、パラジウム化合物を濃強酸に溶かしてｐＨを２以下とし、当該溶液をアルミナ担体に担持させ、焼成することで、酸素過剰で未燃炭化水素とＳＯｘを含む排ガス中の未燃炭化水素酸化用のパラジウム担持アルミナ触媒を製造している。 Patent Documents 1 and 2 disclose techniques for supporting a catalyst metal on a carrier. In Patent Document 1, a palladium compound is dissolved in a concentrated strong acid so as to have a pH of 2 or less, and the solution is supported on an alumina carrier and calcined, so that unburned in exhaust gas containing unburned hydrocarbon and SO x with excess oxygen. Manufactures palladium-supported alumina catalysts for hydrocarbon oxidation.
また、特許文献２では、無電解めっき法により、アルミナ担体に触媒金属を微粒子状に担持させて触媒活性、触媒能力の低下を防ぐようにしている。
しかしながら、特許文献１に係る技術によれば、熱処理の過程において、基材表面に微細な粒子状に分散したパラジウムが焼結し、複数個まとまって大きな粒子として成長してしまい、微細な粒子状態化によって向上した触媒活性が再び低下してしまうという問題があった。 However, according to the technique according to Patent Document 1, palladium dispersed in the form of fine particles is sintered on the surface of the base material in the process of heat treatment, and a plurality of particles grow together to form large particles. There was a problem that the catalytic activity improved by the conversion was lowered again.
また、特許文献２に係る技術によれば、触媒金属は多孔質基材であるアルミナの細孔底部から開口部にかけては担持されず、最表面に担持されるのみである。従って、基材表面のミクロ構造と表面積を損なうことなく金属を担持させることは不可能であった。 Further, according to the technique according to Patent Document 2, the catalyst metal is not supported from the pore bottom portion to the opening portion of alumina, which is a porous base material, but only supported on the outermost surface. Therefore, it has been impossible to support a metal without impairing the microstructure and surface area of the substrate surface.
さらに、多孔質基材に金属をめっきする場合、めっき浴を撹拌等しても多孔質基材の微細孔内への金属イオンの輸送が遅いため、微細孔内への金属の被覆が不均一になったり、または被覆できないという問題があった。 In addition, when metal is plated on a porous substrate, the metal coating in the micropores is uneven because the transport of metal ions into the micropores of the porous substrate is slow even if the plating bath is stirred. There was a problem that it was not possible to be coated.
そこで、本発明は、多孔質基材上にそのミクロ構造と表面積を損なうことなく金属を均一に担持させ、当該金属を粒状もしくは針状にして表面積をさらに大きくした金属−多孔質基材複合材料およびその製造方法を提供することを目的とする。 Therefore, the present invention provides a metal-porous substrate composite material in which a metal is uniformly supported on a porous substrate without impairing its microstructure and surface area, and the metal is made granular or acicular to further increase the surface area. And it aims at providing the manufacturing method.
かかる課題を解決するための本発明の金属−多孔質基材複合材料の製造方法は、金属Ｍ２よりも酸化還元電位の低い金属Ｍ３のイオンを含む溶液に超音波をかけながら多孔質基材を浸漬して多孔質基材に金属イオンＭ３を担持させる工程と、金属イオンＭ３を担持した多孔質基材を純水あるいは希薄酸溶液に浸漬する工程と、金属Ｍ２のイオンを含む溶液に超音波をかけながら金属イオンＭ３を担持した多孔質基材を浸漬して多孔質基材に金属Ｍ２のコロイドを担持させる工程と、金属イオンＭ２のコロイドを担持した多孔質基材を純水あるいは希薄酸溶液に浸漬する工程と、金属Ｍ１のイオン及び還元剤を含み平滑化剤の濃度を５０ｐｐｍ以下とした溶液に金属Ｍ２のコロイドを担持した多孔質基材を浸漬する無電解めっき工程とを含むようにしている。 Metal of the present invention to solve such a problem - the production method of the porous substrate composites, porous substrate while applying ultrasonic waves to a solution containing ions of low metal M 3 redox potential than the metal M 2 a step of supporting the metal ion M 3 by immersing the wood to the porous substrate, a step of immersing the metal ion M 3 and carrying porous substrate in pure water or dilute acid solutions, the metal M 2 ions a step of the metal ion M 3 by immersing the supported porous substrate into the porous substrate carrying the colloidal metal M 2 while applying ultrasonic waves to a solution containing, porous carrying a colloidal metal ion M 2 immersing the substrate in pure water or dilute acid solution, the ions and the reducing agent comprises a porous substrate concentrations in solution with 50ppm or less carrying the colloidal metal M 2 of smoothing agent of metal M 1 Immerse the electroless plating process Is included.
ここで、純水とは、蒸留水やイオン交換処理した水のことを言う。不純物の多い水道水は無電解めっき反応に影響を与える虞があるため使用しない方がよい。 Here, pure water means distilled water or water subjected to ion exchange treatment. Do not use tap water with a lot of impurities because it may affect the electroless plating reaction.
したがって、多孔質基材の細孔底部から開口部を含む表面全体に開口部を閉塞することなく金属を均一に被覆することが可能となる。また、金属を粒状もしくは針状にして、その大きさも２μｍ以下とすることが可能となり、本発明の金属−多孔質基材複合材料が得られる。 Therefore, the metal can be uniformly coated without blocking the opening from the bottom of the porous substrate to the entire surface including the opening. Further, the metal can be made granular or needle-like and the size thereof can be 2 μm or less, and the metal-porous substrate composite material of the present invention can be obtained.
また、本発明の金属−多孔質基材複合材料によれば、多孔質基材上に担持された金属により、多孔質基材のミクロ構造と表面積が損なわれるということがない。しかも、担持された金属は微小な粒状もしくは針状であることから、その表面積がさらに増加した金属−多孔質基材複合材料が提供される。 Moreover, according to the metal-porous substrate composite material of the present invention, the metal supported on the porous substrate does not impair the microstructure and surface area of the porous substrate. Moreover, since the supported metal is in the form of fine particles or needles, a metal-porous substrate composite material having a further increased surface area is provided.
ここで、ミクロ構造とは、μｍレベルのみならず、ｎｍレベルの細孔も有するような構造を意味している。 Here, the microstructure means a structure having not only μm level but also nm level pores.
また、多孔質基材上に担持される金属Ｍ１はパラジウム（Ｐｄ）、白金（Ｐｔ)、ルテニウム（Ｒｕ）、イリジウム（Ｉｒ)、ロジウム（Ｒｈ)、金（Ａｕ）、銀（Ａｇ)およびニッケル（Ｎｉ）の群より選ばれた１種もしくは２種以上の金属、或いは２種以上を含む合金であることが好ましい。 The metal M 1 supported on the porous substrate is palladium (Pd), platinum (Pt), ruthenium (Ru), iridium (Ir), rhodium (Rh), gold (Au), silver (Ag) and One or two or more metals selected from the group of nickel (Ni) or an alloy containing two or more are preferable.
上記金属は触媒活性の高い金属である。したがって、上記金属を本発明の金属−多孔質基材複合材料に適用することで、表面積の増加の効果と相俟って高触媒活性な材料となる。また、本発明の金属−多孔質基材複合材料を用いて、触媒や電極を提供することができ、本発明の金属−多孔質基材複合材料を用いた電極により構成された電気化学セルを提供することも可能である。 The metal is a metal having high catalytic activity. Therefore, by applying the above metal to the metal-porous substrate composite material of the present invention, it becomes a highly catalytically active material combined with the effect of increasing the surface area. Further, a catalyst or an electrode can be provided by using the metal-porous substrate composite material of the present invention, and an electrochemical cell constituted by an electrode using the metal-porous substrate composite material of the present invention is provided. It is also possible to provide.
さらに、金属−多孔質基材複合材料を用いた電極により構成された硫酸電解法による水素製造用電気化学セルや硫黄サイクルハイブリッド水素製造用電気化学セル提供することも可能である。 Furthermore, it is also possible to provide an electrochemical cell for hydrogen production or an electrochemical cell for sulfur cycle hybrid hydrogen production by a sulfuric acid electrolysis method constituted by an electrode using a metal-porous substrate composite material.
以上、請求項１に記載の発明によれば、多孔質基材の細孔底部から開口部を含む表面全体に開口部を閉塞することなく金属がむらなく均一に被覆されているので、多孔質基材上に担持された金属により多孔質基材のミクロ構造と表面積が損なわれるということがない。しかも、担持された金属は２μｍ以下の微小な粒状もしくは針状であることから、その表面積がさらに増加した金属−多孔質基材複合材料を提供することが可能となる。 As described above, according to the first aspect of the present invention, the entire surface including the opening from the pore bottom of the porous base material is uniformly coated with the metal without blocking the opening. The metal supported on the substrate does not impair the microstructure and surface area of the porous substrate. Moreover, since the supported metal is in the form of fine particles or needles of 2 μm or less, it becomes possible to provide a metal-porous substrate composite material whose surface area is further increased.
請求項２に記載の発明によれば、パラジウム（Ｐｄ）、白金（Ｐｔ)、ルテニウム（Ｒｕ）、イリジウム（Ｉｒ)、ロジウム（Ｒｈ)、金（Ａｕ）、銀（Ａｇ)およびニッケル（Ｎｉ）の群より選ばれた１種もしくは２種以上の金属、或いは２種以上を含む合金は触媒活性が高い。したがって、本発明の金属−多孔質基材複合材料に適用することで、表面積の増加の効果と相俟って高触媒活性な材料となる。 According to the invention described in claim 2, palladium (Pd), platinum (Pt), ruthenium (Ru), iridium (Ir), rhodium (Rh), gold (Au), silver (Ag) and nickel (Ni) One or two or more metals selected from the group or alloys containing two or more have high catalytic activity. Therefore, when applied to the metal-porous substrate composite material of the present invention, the material has a high catalytic activity in combination with the effect of increasing the surface area.
請求項３に記載の発明によれば、本発明の金属−多孔質基材複合材料を触媒として用いることが可能である。 According to the invention described in claim 3, the metal-porous substrate composite material of the present invention can be used as a catalyst.
請求項４に記載の発明によれば、本発明の金属−多孔質基材複合材料は電極として用いることが可能である。 According to the invention described in claim 4, the metal-porous substrate composite material of the present invention can be used as an electrode.
請求項５に記載の発明によれば、本発明の金属−多孔質基材複合材料を用いた電極により構成された電気化学セルを提供することができる。 According to invention of Claim 5, the electrochemical cell comprised by the electrode using the metal-porous base material composite material of this invention can be provided.
請求項６に記載の発明によれば、本発明の金属−多孔質基材複合材料を用いた電極により構成された硫酸電解法による水素製造用電気化学セルを提供することができる。この硫酸電解法による水素製造用電気化学セルは、電極として硫酸中でも化学的安定性が高い本発明の金属−多孔質基材複合材料を用いていることから、長時間の使用にも十分に耐えうる。しかも、陰極として用いれば水素を高効率に製造でき、陽極として用いれば酸素を高効率に製造することが可能である。また、高コストな金属であっても少量を電子導電性セラミックスに担持して用いればよいので、低コスト化も可能となる。 According to invention of Claim 6, the electrochemical cell for hydrogen manufacture by the sulfuric acid electrolysis method comprised by the electrode using the metal-porous base material composite material of this invention can be provided. This electrochemical cell for hydrogen production by sulfuric acid electrolysis uses the metal-porous substrate composite material of the present invention, which has high chemical stability even in sulfuric acid, as an electrode, so it can sufficiently withstand long-term use. sell. Moreover, hydrogen can be produced with high efficiency when used as a cathode, and oxygen can be produced with high efficiency when used as an anode. In addition, even a high-cost metal may be used by supporting a small amount on an electronic conductive ceramic, so that the cost can be reduced.
請求項７に記載の発明によれば、本発明の金属−多孔質基材複合材料を用いた電極により構成された硫黄サイクルハイブリッド水素製造用電気化学セルを提供することができる。この硫黄サイクルハイブリッド水素製造用電気化学セルは、電極として本発明の金属−多孔質基材複合材料を用いていることから、硫黄サイクルハイブリッド法において反応ガスとして使用するＳＯ２及び電解液中に含まれるＨ２Ｏとの電極（陽極）の金属との接触面積の向上により反応場が増大し、電極（過電圧の減少）及び触媒特性が向上する。さらには、高コストな金属であっても少量を基材に担持して用いればよいので、低コスト化も可能となる。また、本発明の金属−多孔質基材複合材料は化学的安定性が高いので、硫黄サイクルハイブリッド法のような過酷な使用条件（硫酸中で使用する）においても長時間の使用に十分に耐えうる。しかも、陰極として用いれば、水素還元反応に対して触媒能を持つため、水素を高効率に製造でき、陽極として用いれば分極（陽極酸化）が起こりにくくなり、電極の長時間安定性を保つことができる。 According to invention of Claim 7, the electrochemical cell for sulfur cycle hybrid hydrogen manufacture comprised by the electrode using the metal-porous base material composite material of this invention can be provided. Since this electrochemical cell for sulfur cycle hybrid hydrogen production uses the metal-porous substrate composite material of the present invention as an electrode, it is contained in SO 2 and an electrolyte used as a reaction gas in the sulfur cycle hybrid method. By increasing the contact area of the electrode (anode) with H 2 O, the reaction field is increased, and the electrode (reduction in overvoltage) and catalytic properties are improved. Furthermore, even if it is a high-cost metal, a small amount may be carried on the base material, so that the cost can be reduced. In addition, since the metal-porous substrate composite material of the present invention has high chemical stability, it is sufficiently resistant to long-term use even under severe use conditions (used in sulfuric acid) such as the sulfur cycle hybrid method. sell. Moreover, when used as a cathode, it has a catalytic ability for hydrogen reduction reaction, so that hydrogen can be produced with high efficiency, and when used as an anode, polarization (anodization) hardly occurs, and the stability of the electrode for a long time is maintained. Can do.
また、多孔質基材に金属をめっきする場合、めっき浴を撹拌等しても微細孔内への金属イオンの輸送が遅いために通常微細孔内への金属の被覆が不均一になったり、または被覆できなかったりするが、請求項８に記載の発明によれば、多孔質基材の細孔底部から開口部を含む表面全体に開口部を閉塞することなく金属を均一に被覆することが可能となるとともに、金属を粒状もしくは針状にして、その大きさも２μｍ以下に自由に制御することが可能となり、本発明の金属−多孔質基材複合材料が得られうる。しかも、ＰＶＤ法（物理的蒸着法）等を用いた基材への金属コーティング技術と比較して、簡易な設備で行える上に低コストであり、大型の基材にも簡易に金属をコーティングすることが可能である。 In addition, when plating a metal on a porous substrate, even if the plating bath is stirred or the like, the metal ions are normally not uniformly coated in the micropores because the transport of metal ions into the micropores is slow, Or although it cannot coat | cover, according to invention of Claim 8, it can coat | cover metal uniformly, without obstruct | occluding an opening part from the pore bottom part of a porous base material to the whole surface including an opening part. In addition, the metal can be made granular or needle-like and the size thereof can be freely controlled to 2 μm or less, and the metal-porous substrate composite material of the present invention can be obtained. In addition, compared to metal coating technology on substrates using PVD (physical vapor deposition), etc., it can be done with simple equipment and is low cost, and even large substrates can be coated with metal easily. It is possible.
以下、本発明の構成を図面に示す実施形態に基づいて詳細に説明する。 Hereinafter, the configuration of the present invention will be described in detail based on embodiments shown in the drawings.
本発明の金属−多孔質基材複合材料は、多孔質基材と、多孔質基材に担持された金属とを備え、多孔質基材の細孔底部から開口部を含む表面全体に開口部を閉塞することなく金属を均一に被覆し、且つ金属が粒状もしくは針状であり、その大きさが２μm以下というものである。 The metal-porous substrate composite material of the present invention comprises a porous substrate and a metal supported on the porous substrate, and the entire surface including the opening from the pore bottom of the porous substrate has an opening. The metal is uniformly coated without clogging the metal, and the metal is granular or acicular, and its size is 2 μm or less.
尚、粒状もしくは針状金属の大きさの下限値に関しては、原子オーダー（オングストロームレベル）である。しかしながら、ＦＥ−ＳＥＭの限界分解能は２ｎｍであり、２ｎｍ程度の粒状もしくは針状金属が観察されたものの、それ以下のサイズの粒状もしくは針状金属の観察は困難であった。 The lower limit of the size of the granular or acicular metal is on the atomic order (angstrom level). However, the limit resolution of FE-SEM is 2 nm, and although granular or acicular metal of about 2 nm was observed, it was difficult to observe granular or acicular metal having a size smaller than that.
ここで、金属材料としては、無電解めっき法によりめっきすることが可能な金属であればよいが、触媒活性の高い金属であるパラジウム（Ｐｄ）、白金（Ｐｔ)、ルテニウム（Ｒｕ）、イリジウム（Ｉｒ)、ロジウム（Ｒｈ)、金（Ａｕ）、銀（Ａｇ)およびニッケル（Ｎｉ）の群より選ばれた１種もしくは２種以上の金属、或いは２種以上を含む合金が特に好ましい。 Here, the metal material may be any metal that can be plated by an electroless plating method, but palladium (Pd), platinum (Pt), ruthenium (Ru), iridium (metals having high catalytic activity). Particularly preferred are one or more metals selected from the group of Ir), rhodium (Rh), gold (Au), silver (Ag) and nickel (Ni), or alloys containing two or more.
次に、多孔質基材としては、例えば、カーボン材料、シリカ、ガラス、有機基板、表面が酸化しやすい金属（アルミニウム、チタン、ジルコニウム、タンタル等）、各種セラミックス等を採用できるが、これらに限られるものではない。また、人為的に微細な表面凹凸形状を形成したような基材に対しても本発明を適用可能である。 Next, as the porous substrate, for example, carbon materials, silica, glass, organic substrates, metals whose surfaces are easily oxidized (aluminum, titanium, zirconium, tantalum, etc.), various ceramics, and the like can be used. It is not something that can be done. In addition, the present invention can be applied to a base material on which fine surface irregularities are artificially formed.
ここで、多孔質基材としては、電気化学セルの電極として求められる充分な耐食性と電子導電性を併せ持つ基材であることが好ましい。電気化学セルでは、陽極、陰極および電解質で構成されるが、陽極として使用する一例を挙げれば、本願出願人が既に出願した特開２００５−３３０１３３の発明に係る電子導電性セラミックス材料を使用することで、非常に優れた電極を提供でき、特に、過酷な電解条件（５０重量％硫酸、８０℃）で行う硫黄サイクルハイブリッド水素製造用の電気化学セルの陽極電極として求められる耐食性と導電性を兼ね備えた好適な電極を提供できる。 Here, the porous substrate is preferably a substrate having both sufficient corrosion resistance and electronic conductivity required for an electrode of an electrochemical cell. An electrochemical cell is composed of an anode, a cathode and an electrolyte. To give an example of use as an anode, use an electroconductive ceramic material according to the invention of Japanese Patent Application Laid-Open No. 2005-330133 filed by the present applicant. In particular, it provides both excellent corrosion resistance and electrical conductivity required as an anode electrode for electrochemical cells for sulfur cycle hybrid hydrogen production under severe electrolysis conditions (50 wt% sulfuric acid, 80 ° C). A suitable electrode can be provided.
特開２００５−３３０１３３の発明に係る電子導電性セラミックス材料は、Ａサイトに希土類元素ＲＥを有する立方晶系チタン酸化物パイロクロアのうち、当該Ａサイトの元素ＲＥがＬｕ、Ｙｂ、Ｔｍ、Ｅｒ、Ｈｏ、Ｙ、Ｓｃ、Ｄｙ、Ｔｂ、Ｇｄ、Ｅｕ、Ｓｍ、Ｃｅの各元素のうちの一つまたは二つ以上から成る複合酸化物 ＲＥ２−ｘＴｉ２Ｏ７−δ であって、Ａサイト元素ＲＥの不定比量ｘが当該Ａサイト元素ＲＥに応じて、０＜ｘ＜０．５の範囲内とされる電子導電性セラミックス粉体が焼結され、その後還元処理されることによって形成される立方晶系チタン酸化物パイロクロア焼結体である。または、Ａサイトに希土類元素ＲＥを有する立方晶系チタン酸化物パイロクロアのうち、当該Ａサイトの元素ＲＥがＬｕ、Ｙｂ、Ｔｍ、Ｅｒ、Ｈｏ、Ｙ、Ｓｃ、Ｄｙ、Ｔｂ、Ｇｄ、Ｅｕ、Ｓｍ、Ｃｅの各元素のうちの一つまたは二つ以上から成る複合酸化物であって、前記Ａサイト元素ＲＥの不定比量ｘが当該Ａサイト元素ＲＥに応じて、０＜ｘ＜０．５の範囲内とされ、尚かつＢサイトの一部が遷移金属元素Ｍで置換された複合酸化物 ＲＥ２−ｘＴｉ２−ｙＭｙＯ７−δ （ただし ＭはＣｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｒｕ、Ｒｈ、Ｐｄ、Ｏｓ、Ｉｒ、Ｐｔのうちの一つまたは二つ以上）であって、当該Ｂサイトにおける前記遷移金属元素Ｍの置換量ｙが、０＜ｙ≦０．２の範囲内とされる電子導電性セラミックス粉体が焼結され、その後還元処理されることによって形成される立方晶系チタン酸化物パイロクロア焼結体である。これらの電子導電性セラミックス材料は、Ａサイトを不定比化した上で還元処理し、酸素を欠損（欠損量δ）させているものであるため、ｄ軌道電子を有するチタンの価数が＋４価から＋３価に変わり、室温近傍においても電子導電性を発現させることができる。また、チタン酸化物は、電気分解環境である濃硫酸中でも長時間に亘り高耐食性を示す。 The electron conductive ceramic material according to the invention of JP-A-2005-330133 is a cubic titanium oxide pyrochlore having a rare earth element RE at the A site, and the element RE at the A site is Lu, Yb, Tm, Er, Ho. , Y, Sc, Dy, Tb, Gd, Eu, Sm, Ce, or a complex oxide RE 2-x Ti 2 O 7- δ composed of one or more of each element, and an A-site element It is formed by sintering an electronically conductive ceramic powder in which the non-stoichiometric amount x of RE is in the range of 0 <x <0.5 in accordance with the A-site element RE and then subjected to reduction treatment. It is a cubic titanium oxide pyrochlore sintered body. Alternatively, among cubic titanium oxide pyrochlores having a rare earth element RE at the A site, the element RE at the A site is Lu, Yb, Tm, Er, Ho, Y, Sc, Dy, Tb, Gd, Eu, Sm. , Ce, or a complex oxide composed of one or more of the elements, wherein the non-stoichiometric amount x of the A-site element RE is 0 <x <0.5 depending on the A-site element RE. And a portion of the B site substituted with a transition metal element M. RE 2-x Ti 2- y My O 7- δ (where M is Cr, Mn, Fe, Co) , Ni, Ru, Rh, Pd, Os, Ir, Pt), and the substitution amount y of the transition metal element M at the B site is 0 <y ≦ 0.2. The electronically conductive ceramic powder that is within the range of 3 is a cubic titanium oxide pyrochlore sintered body formed by post-reduction treatment. Since these electron conductive ceramic materials are obtained by reducing the A site after making the A-site non-stoichiometric, oxygen is deficient (deficit amount δ), the valence of titanium having d-orbital electrons is +4. From + to +3 valence, electronic conductivity can be exhibited even near room temperature. Titanium oxide exhibits high corrosion resistance for a long time even in concentrated sulfuric acid, which is an electrolysis environment.
他の電子導電性セラミックス材料としては、主成分の組成式がＳｒ１−ｘＴｉ１−ｙＭｙＯ３＋δで表され、ＭはＮｂ、Ｔａのうち一つもしくは両方を含むＢサイトを部分置換可能な元素であり、０＜ｘ＜０．１５、０＜ｙ＜０．３、０≦δ≦０．４５であるＡサイト欠損形ストロンチウムチタネートが還元処理されてなるセラミックス粉体、あるいは主成分の組成式が（Ｓｒ１−ｚＲＥｚ）１−ｘＴｉ１−ｙＭｙＯ３＋δで表され、ＲＥはＳｃ、Ｙおよびランタノイド系列元素（Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ）のうち一つもしくは２つ以上を含むＡサイトを部分置換可能な元素であり、ＭはＮｂ、Ｔａのうち一つもしくは両方を含むＢサイトを部分置換可能な元素であり、０＜ｘ＜０．１５、０＜ｙ＜０．３、０＜ｚ＜０．３、０≦δ≦０．４５であるＡサイト欠損形ストロンチウムチタネートが還元処理されてなるセラミックス粉体を焼結してなるセラミックス焼結体が挙げられる。このセラミックス焼結体は、Ａサイトを欠損させて不定比化し、電荷補償のためにＢサイトを部分置換した上で還元処理しているので、チタンの価数が＋４価から＋３価に変化してｄ軌道に電子を1個有するようになり、電子導電性を有し、電気分解環境である濃硫酸中でも長時間に亘り高耐食性を示す。 As another electronic conductive ceramic material, the composition formula of the main component is represented by Sr 1-x Ti 1-y M y O 3 + δ , where M is a partial substitution of the B site containing one or both of Nb and Ta Ceramic powder obtained by reducing A-site deficient strontium titanate that is a possible element and 0 <x <0.15, 0 <y <0.3, and 0 ≦ δ ≦ 0.45, or a main component represented by the composition formula (Sr 1-z RE z) 1-x Ti 1-y M y O 3 + δ, RE is Sc, Y and lanthanoid series elements (La, Ce, Pr, Nd , Pm, Sm, Eu , Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) is an element capable of partially substituting the A site containing one or more, and M is one or both of Nb and Ta. Partial replacement of B site is possible A ceramic obtained by reduction treatment of an A-site deficient strontium titanate that is elemental and has 0 <x <0.15, 0 <y <0.3, 0 <z <0.3, and 0 ≦ δ ≦ 0.45 A ceramic sintered body obtained by sintering powder is exemplified. In this ceramic sintered body, the A site is deficient and non-stoichiometric, and the B site is partially substituted for charge compensation and reduction treatment is performed, so the valence of titanium changes from +4 to +3. It has one electron in the d orbital, has electronic conductivity, and exhibits high corrosion resistance for a long time even in concentrated sulfuric acid which is an electrolysis environment.
ここで、硫黄サイクルハイブリッド法の温度と各反応工程を図１６に示す。硫黄サイクルハイブリッド法は、熱分解工程（熱化学法）と電気分解工程（電気分解法）で構成されている。熱分解工程では、電気分解により得られた硫酸（Ｈ２ＳＯ４）が８０℃を越える温度で蒸発し始める。
Ｈ２ＳＯ４ (液相) → Ｈ２ＳＯ４ (気相) （熱分解工程１）
Here, the temperature and each reaction process of the sulfur cycle hybrid method are shown in FIG. The sulfur cycle hybrid method is composed of a thermal decomposition step (thermochemical method) and an electrolysis step (electrolysis method). In the pyrolysis step, sulfuric acid (H 2 SO 4 ) obtained by electrolysis starts to evaporate at a temperature exceeding 80 ° C.
H 2 SO 4 (liquid phase) → H 2 SO 4 (gas phase) (thermal decomposition step 1)
次に、５００℃付近で、硫酸は三酸化硫黄（ＳＯ３）と水（Ｈ２Ｏ）に分解する。
Ｈ２ＳＯ４(気相) → ＳＯ３(気相)＋Ｈ２Ｏ(気相) （熱分解工程２）
Next, at around 500 ° C., sulfuric acid decomposes into sulfur trioxide (SO 3 ) and water (H 2 O).
H 2 SO 4 (gas phase) → SO 3 (gas phase) + H 2 O (gas phase) (thermal decomposition step 2)
さらに、三酸化硫黄は８５０℃付近で、二酸化硫黄（ＳＯ２）と酸素（Ｏ２）に分解する。
ＳＯ３(気相) → ＳＯ２(気相) ＋ １／２ Ｏ２(気相) （熱分解工程３）
Furthermore, sulfur trioxide decomposes into sulfur dioxide (SO 2 ) and oxygen (O 2 ) at around 850 ° C.
SO 3 (gas phase) → SO 2 (gas phase) + 1/2 O 2 (gas phase) (thermal decomposition step 3)
次に、このＳＯ２とＯ２の混合ガスからＳＯ２を分離し、もう一度電気分解槽に送り込むと水との平衡反応により亜硫酸（Ｈ２ＳＯ３）が生成する。
ＳＯ２(気相) ＋ Ｈ２Ｏ(液相) → Ｈ２ＳＯ３(液相) （亜硫酸再生工程）
Next, when SO 2 is separated from the mixed gas of SO 2 and O 2 and sent again to the electrolysis tank, sulfurous acid (H 2 SO 3 ) is generated by an equilibrium reaction with water.
SO 2 (gas phase) + H 2 O (liquid phase) → H 2 SO 3 (liquid phase) (sulfurous acid regeneration step)
電気分解では、カソード（陰極）側で水素イオンが還元され、水素ガスを生成する。
アノード（陽極）側で亜硫酸（ＳＯ２ガス）が酸化され、副生成物として硫酸ができる。
電気分解工程：カソード（陰極）反応：２Ｈ＋ ＋２ｅ → Ｈ２(気相)
アノード（陽極）反応：ＳＯ２ ＋ ２Ｈ２Ｏ → ２Ｈ＋＋ Ｈ２ＳＯ４＋２ｅ
Total反応： ＳＯ２ ＋ ２Ｈ２Ｏ → Ｈ２ ＋ Ｈ２ＳＯ４
In electrolysis, hydrogen ions are reduced on the cathode (cathode) side to generate hydrogen gas.
Sulfurous acid (SO 2 gas) is oxidized on the anode (anode) side, and sulfuric acid is produced as a by-product.
Electrolysis process: cathode (cathode) reaction: 2H + + 2e → H 2 (gas phase)
Anode (anode) reaction: SO 2 + 2H 2 O → 2H + + H 2 SO 4 + 2e
Total reaction: SO 2 + 2H 2 O → H 2 + H 2 SO 4
硫酸は熱分解工程により再び分解され、上記サイクルの中で繰り返し使用される。電極は、電気分解で副生成物として得られた硫酸に曝されることになるため、高い耐硫酸特性が不可欠となる。また、電流の増加とともに得られる水素量も増加するので、ジュール熱による効率低下を防ぐため、高い電子導電性を有することが重要である。 Sulfuric acid is decomposed again by the thermal decomposition process and used repeatedly in the above cycle. Since the electrode is exposed to sulfuric acid obtained as a by-product by electrolysis, high sulfuric acid resistance is indispensable. In addition, since the amount of hydrogen obtained increases with an increase in current, it is important to have high electronic conductivity in order to prevent a decrease in efficiency due to Joule heat.
本発明の金属−多孔質基材複合材料は、多孔質基材と、多孔質基材に担持された金属とを備え、多孔質基材の細孔底部から開口部を含む表面全体に開口部を閉塞することなく金属が均一に被覆されており、且つ金属が粒状もしくは針状であり、その大きさが２μｍ以下であるから、反応ガスと金属の接触面積の向上、金属と電子導電性セラミックスの接触面積の向上により、反応場が増大し、電極及び触媒特性が向上する。さらには、高コストな金属であっても少量を電子導電性セラミックスに担持して用いればよいので、低コスト化も可能となる。この点からも、非常に優れた電極を提供でき、特に、硫黄サイクルハイブリッド水素製造用の電気化学セルの陽極電極として非常に好適な電極を提供できる。また、多孔質基材に担持された前記した金属は水素に対しても高い触媒能を持ち、且つ高い表面積であるため、水素析出に対する陰極過電位も低くなり、水素製造用の電気化学セルの陰極電極としても非常に好適な電極を提供できる。 The metal-porous substrate composite material of the present invention comprises a porous substrate and a metal supported on the porous substrate, and the entire surface including the opening from the pore bottom of the porous substrate has an opening. The metal is uniformly coated without clogging, and the metal is granular or needle-shaped, and the size thereof is 2 μm or less, so that the contact area between the reaction gas and the metal is improved, and the metal and the electronic conductive ceramics. By improving the contact area, the reaction field is increased and the electrode and catalyst characteristics are improved. Furthermore, even a high-cost metal may be used by supporting a small amount on an electronic conductive ceramic, so that the cost can be reduced. Also from this point, it is possible to provide a very excellent electrode, and in particular, it is possible to provide a very suitable electrode as an anode electrode of an electrochemical cell for producing sulfur cycle hybrid hydrogen. In addition, since the metal supported on the porous base material has a high catalytic ability for hydrogen and has a high surface area, the cathode overpotential for hydrogen deposition is also low, and the electrochemical cell for hydrogen production is low. A very suitable electrode can be provided as a cathode electrode.
上記金属−多孔質基材複合材料は無電解めっき法を用いて製造される。以下、図８に示す本発明の無電解めっき法を用いた金属−多孔質基材複合材料の製造方法について詳細に説明する。 The metal-porous substrate composite material is manufactured using an electroless plating method. Hereinafter, the manufacturing method of the metal-porous substrate composite material using the electroless plating method of the present invention shown in FIG. 8 will be described in detail.
無電解めっき法は、４つの前処理工程、即ち、脱脂処理工程、酸性化処理工程、感受性化処理工程および活性化処理工程と、目的の金属をコーティングする無電解めっき処理工程よりなる。これらの工程の概略を詳細に説明すると以下のようになる。脱脂処理及び酸性化処理（１）により多孔質基材１を脱脂及び酸性化する。感受性化処理（２）により多孔質基材１を感受性化して金属イオンＭ３２を多孔質基材１の表面に吸着させる。純水浸漬処理（３）により細孔底部に近づくに従って、金属イオンＭ３２の吸着量が多い状態を形成する。活性化処理（４）により金属Ｍ２のコロイド３を生成させる。最後に、無電解めっき（５）により、金属Ｍ３４を形成して、多孔質基材１の表面を被覆する。 The electroless plating method includes four pretreatment steps, that is, a degreasing treatment step, an acidification treatment step, a sensitization treatment step and an activation treatment step, and an electroless plating treatment step for coating a target metal. The outline of these steps will be described in detail as follows. The porous substrate 1 is degreased and acidified by degreasing treatment and acidification treatment (1). The porous substrate 1 is sensitized by the sensitization treatment (2), and the metal ions M 3 2 are adsorbed on the surface of the porous substrate 1. As the bottom of the pore is approached by the pure water immersion treatment (3), a state in which the adsorption amount of the metal ion M 3 2 is increased is formed. The colloid 3 of the metal M 2 is generated by the activation process (4). Finally, metal M 3 4 is formed by electroless plating (5) to cover the surface of the porous substrate 1.
脱脂処理工程では、金属膜を成膜する際の障害となる虞がある無機物あるいは有機物（特に、人体から出る油脂等）を多孔質基材から洗浄・除去する。具体的には、無機物あるいは有機物を除去できるような洗浄剤、例えばアセトンや水酸化ナトリウム溶液を用いて多孔質基材を超音波洗浄し、無機物および有機物を洗浄・除去する。ここで、超音波洗浄を長時間行うと、多孔質基材のミクロ構造が破壊される虞がある。したがって、この工程においては、超音波洗浄時間は１０分以内とすることが必要である。また、水酸化ナトリウム溶液等のアルカリ溶液を用いた場合には、アルカリ溶液を多孔質基材から可能な限り除去しておくために水洗を行う必要があり、特に超音波をかけながら水洗することが好ましい。これにより、次工程の酸性化処理をより確実に行うことが可能となる。ここで、超音波の周波数は、中強度（４０〜４５ｋＨｚ）程度以下の強度領域で行う必要があるが、基材の強度が充分でない場合には、あるいは表面粗さが大きい、つまりミクロ構造が緻密な場合には、小強度（１００ｋＨｚ以上）程度より大きい低パワーで行った方が良い。また、以降の工程においては、超音波の周波数を１００ｋＨｚ程度とするのが好適であるが、基材の表面粗さ、つまり細孔径や細孔深さ、強度により最適な周波数を適宜選択しても良い。尚、多孔質基材が無機物および有機物により汚染されていない場合には、脱脂処理工程を省略することができる。 In the degreasing treatment step, inorganic or organic substances (especially oils and fats etc. coming from the human body) that may become an obstacle when forming the metal film are washed and removed from the porous substrate. Specifically, the porous substrate is ultrasonically cleaned using a cleaning agent capable of removing inorganic or organic substances such as acetone or sodium hydroxide solution, and the inorganic and organic substances are cleaned and removed. Here, if ultrasonic cleaning is performed for a long time, the microstructure of the porous substrate may be destroyed. Therefore, in this step, the ultrasonic cleaning time needs to be within 10 minutes. In addition, when an alkaline solution such as a sodium hydroxide solution is used, it is necessary to wash with water in order to remove the alkaline solution from the porous substrate as much as possible. Is preferred. Thereby, it becomes possible to perform the acidification process of the following process more reliably. Here, the frequency of the ultrasonic wave needs to be performed in an intensity region of medium intensity (40 to 45 kHz) or less, but when the strength of the substrate is not sufficient, or the surface roughness is large, that is, the microstructure is In a dense case, it is better to perform at a low power greater than a small strength (100 kHz or more). In the subsequent steps, it is preferable to set the ultrasonic frequency to about 100 kHz. However, the optimum frequency is appropriately selected according to the surface roughness of the substrate, that is, the pore diameter, pore depth, and strength. Also good. In addition, when the porous base material is not contaminated with an inorganic substance and an organic substance, the degreasing treatment step can be omitted.
酸性化処理工程では、次工程の感受性化処理工程の前処理として多孔質基材表面を酸性化する。具体的には、例えば濃度を５〜２０重量％とした塩酸水溶液を用いて、８分間以上浸漬する。浸漬処理の際には、浸漬後に２分程度超音波処理を行った後に８分間放置するのがより好ましい。超音波をかけながら浸漬処理することで、多孔質基材の細孔内に残存したアルカリ溶液等が除去されやすくなり、表面が効率的に酸性化される。尚、塩酸水溶液の濃度を５重量％未満として、処理時間を８分より短くした場合、以下のような問題が生じる虞があるので好ましくない。 In the acidification treatment step, the surface of the porous substrate is acidified as a pretreatment for the next sensitization treatment step. Specifically, for example, it is immersed for 8 minutes or more using a hydrochloric acid aqueous solution having a concentration of 5 to 20% by weight. In the immersion treatment, it is more preferable to leave it for 8 minutes after performing ultrasonic treatment for about 2 minutes after immersion. By soaking while applying ultrasonic waves, the alkaline solution remaining in the pores of the porous substrate is easily removed, and the surface is acidified efficiently. If the concentration of the aqueous hydrochloric acid solution is less than 5% by weight and the treatment time is shorter than 8 minutes, the following problems may occur, which is not preferable.
まず、脱脂処理で用いた水酸化ナトリウム溶液等のアルカリ溶液が多孔質基材内に残存している場合、アルカリ溶液が十分に中和されないため、感受性化処理工程時に酸性である主塩と中和反応を起こしたり、沈殿を起こしたりしてしまう。ここでは、主塩として塩化スズを用いた場合について説明するが、これ以外の主塩を用いた場合にも同様の問題が生じる虞がある。
[脱脂処理]
[化学式１]
Ｈ３Ｃ（ＣＨ２）ｎ＋２ＣＯＯＨ ＋ ＮａＯＨ ＝Ｈ３Ｃ（ＣＨ２）ｎ＋２ＣＯＯＮａ ＋ Ｈ２Ｏ
[酸性化処理]
[化学式２]
ＯＨ− ＋ Ｈ＋ ＝ Ｈ２Ｏ
[感受性化処理]
[化学式３]
Ｓｎ２＋ ＋ ２ＯＨ− ＝Ｓｎ（ＯＨ）２↓
したがって、多孔質基材の感受性化処理に必要なＳｎ２＋が得られないため、感受性化処理液が無効になり、次工程の活性化処理ができなくなるという虞がある。
First, when an alkaline solution such as a sodium hydroxide solution used in the degreasing treatment remains in the porous substrate, the alkaline solution is not sufficiently neutralized. It causes a sum reaction or precipitation. Here, the case where tin chloride is used as the main salt will be described, but the same problem may occur when other main salts are used.
[Degreasing]
[Chemical formula 1]
H 3 C (CH 2) n + 2 COOH + NaOH = H 3 C (CH 2) n + 2 COONa + H 2 O
[Acid treatment]
[Chemical formula 2]
OH − + H + = H 2 O
[Sensitivity treatment]
[Chemical formula 3]
Sn 2+ + 2OH − = Sn (OH) 2 ↓
Therefore, Sn 2+ necessary for the sensitization treatment of the porous substrate cannot be obtained, so that the sensitization treatment solution becomes ineffective, and the activation process of the next step may not be performed.
また、多孔質基材表面の酸性度が十分に高まらないため、感受性化処理の際、Ｓｎ２＋が水と反応し、水酸化スズ沈殿物が生成される。
[化学式４]
Ｓｎ２＋＋２Ｈ２Ｏ = Ｓｎ（ＯＨ）２↓＋２Ｈ＋
この結果、塩化スズ溶液が白濁し、感受性化処理能力を失ってしまう虞がある。
In addition, since the acidity of the surface of the porous substrate is not sufficiently increased, Sn 2+ reacts with water during the sensitization treatment, and a tin hydroxide precipitate is generated.
[Chemical formula 4]
Sn 2+ + 2H 2 O = Sn (OH) 2 ↓ + 2H +
As a result, the tin chloride solution may become cloudy and lose the sensitizing ability.
次に、塩酸水溶液の濃度が２０％を超える場合には、前処理の器具の耐食性の要求が高まるだけでなく、塩酸ガスなどで作業環境が悪化する虞があり好ましくない。以上より、塩酸水溶液の濃度は５〜２０％とするのが好適である。 Next, when the concentration of the hydrochloric acid aqueous solution exceeds 20%, not only the corrosion resistance requirement of the pretreatment apparatus is increased, but the working environment may be deteriorated by hydrochloric acid gas or the like, which is not preferable. From the above, the concentration of the hydrochloric acid aqueous solution is preferably 5 to 20%.
尚、塩酸によりエッチングされるような多孔質基材の場合には、酸性化処理と同時に表面を粗くする処理、即ち、感受性化処理も同時に行われる。 In the case of a porous substrate that is etched with hydrochloric acid, a treatment for roughening the surface, that is, a sensitization treatment is performed at the same time as the acidification treatment.
また、酸性化処理工程に用いる溶液は塩酸水溶液に限られず、例えば、硫酸や硝酸、クロム酸又はクロム酸を含む混酸液を、多孔質基材表面の酸性度が十分に高まる程度、脱脂処理工程時にアルカリ溶液を用いた場合にはそのアルカリ溶液が十分に中和される程度の濃度にして使用することで、塩酸水溶液を用いた場合と同様の効果を発揮する。 In addition, the solution used in the acidification treatment step is not limited to a hydrochloric acid aqueous solution. For example, a mixed acid solution containing sulfuric acid, nitric acid, chromic acid, or chromic acid is used in a degreasing treatment step to the extent that the acidity of the porous substrate surface is sufficiently increased. When an alkaline solution is sometimes used, the same effect as when a hydrochloric acid aqueous solution is used can be obtained by using the alkaline solution at a concentration that is sufficiently neutralized.
感受性化処理工程は、感受性化工程は次工程の活性化処理に対する感受性を付与する工程であり、ここでは多孔質基材に直接成膜することが極めて困難なパラジウム等の貴な金属を成膜可能なものとするための工程である。ここでは、主塩として塩化スズを用いた場合について説明する。反応浴、即ち、感受性化処理液には、パラジウム等の貴金属よりも酸化還元電位の小さいスズを含む塩化スズと塩酸を混合して用い、その溶液のｐＨが１以下になるようにする。溶液のｐＨが１を超える場合には、溶液中の＋２価のスズイオンを安定化させることができないので好ましくない。また、塩化スズと塩酸の混合比については、例えば、塩化スズ溶液濃度を１０〜６０ｇ／Ｌ、塩酸（３６重量％）と純水により塩酸溶液濃度を１０〜１００ｍＬ／Ｌとして、塩化スズ１ｇに対して塩酸（３６重量％）を１〜４ｍｌの割合とすればよいが、これに限られるものではなく、溶液のｐＨを１以下にして、＋２価のスズイオンを安定化させることが重要である。尚、感受性化処理温度は、１０℃〜４０℃とすればよいが、２０℃〜３０℃とすることが好ましい。１０℃未満では基材表面との濡れ性が低く、スズイオンの均一吸着が難しくなってしまい、また、４０℃を超えると感受性化処理液と酸素との反応速度が極めて速くなってしまい、液の使用寿命が短くなるので好ましくない。 In the sensitization process, the sensitization process is a process for imparting sensitivity to the activation process of the next process. Here, a noble metal such as palladium, which is extremely difficult to form directly on the porous substrate, is formed. It is a process for making it possible. Here, the case where tin chloride is used as the main salt will be described. In the reaction bath, that is, the sensitizing treatment liquid, tin chloride containing tin having a redox potential lower than that of a noble metal such as palladium and hydrochloric acid are mixed and used so that the pH of the solution becomes 1 or less. When the pH of the solution exceeds 1, it is not preferable because +2 tin ions in the solution cannot be stabilized. Regarding the mixing ratio of tin chloride and hydrochloric acid, for example, the tin chloride solution concentration is 10 to 60 g / L, and the hydrochloric acid solution concentration is 10 to 100 mL / L with hydrochloric acid (36 wt%) and pure water. In contrast, hydrochloric acid (36% by weight) may be in a ratio of 1 to 4 ml, but is not limited thereto, and it is important to stabilize the divalent tin ion by setting the pH of the solution to 1 or less. . The sensitizing treatment temperature may be 10 ° C to 40 ° C, but is preferably 20 ° C to 30 ° C. If it is less than 10 ° C., the wettability with the substrate surface is low and uniform adsorption of tin ions becomes difficult, and if it exceeds 40 ° C., the reaction rate between the sensitizing solution and oxygen becomes extremely fast, This is not preferable because the service life is shortened.
上記の感受性化処理液に超音波をかけながら、酸性化処理を施した多孔質基材を浸漬して感受性化処理を行う。これにより、多孔質基材の最表面（凸部）だけでなく、開口部から細孔底部までの領域にも、開口部が閉塞することなく、Ｓｎ２＋が均一に吸着される。尚、浸漬処理の際には、超音波をかけ続ける必要はなく、少なくとも細孔内部まで感受性化処理液が行き渡れば、その後は超音波をかける必要はない。超音波をかける時間が長すぎる場合には、Ｓｎ２＋の吸着に悪影響を及ぼし、Ｓｎ２＋が均一に吸着されなくなるので好ましくない。つまり、超音波をかける時間は、Ｓｎ２＋の吸着に悪影響を及ぼさない範囲で、少なくとも細孔内部まで感受性化処理液が行き渡る程度に行えばよい。例えば、浸漬後に１分程度超音波処理を行った後に3-5分間放置することで、十分に感受性化する。また、超音波は浸漬初期のみかけ続けるようにしてもよいし、間欠的に超音波をかけて細孔内部まで感受性化処理液を行き渡るようにしてもよい。また、Ｓｎ２＋の吸着に悪影響を及ぼさなければ、浸漬中に超音波をかけ続けても良い。 The sensitizing treatment is performed by immersing the acidified porous substrate while applying ultrasonic waves to the sensitizing treatment liquid. Thereby, Sn <2+> is adsorb | sucked uniformly not only to the outermost surface (convex part) of a porous base material but to an area | region from an opening part to a pore bottom part, without an opening part obstruct | occluding. In the immersion treatment, it is not necessary to continue to apply ultrasonic waves, and it is not necessary to apply ultrasonic waves thereafter if the sensitizing treatment solution reaches at least the inside of the pores. If time applying ultrasonic is too long, adversely affect the adsorption of Sn 2+, since Sn 2+ can not be uniformly adsorbed undesirable. That is, the time for applying the ultrasonic wave may be such that the sensitizing treatment solution reaches at least the inside of the pores within a range that does not adversely affect the adsorption of Sn 2+ . For example, after immersing for about 1 minute after immersion, it is sufficiently sensitized by leaving it for 3-5 minutes. Moreover, the ultrasonic wave may be applied only at the initial stage of immersion, or the ultrasonic wave may be intermittently applied to spread the sensitizing treatment liquid to the inside of the pores. In addition, ultrasonic waves may be continuously applied during immersion as long as Sn 2+ adsorption is not adversely affected.
次に、Ｓｎ２＋が吸着された多孔質基材を純水中に数秒〜３０秒浸漬する（以後、これを純水浸漬処理と呼ぶ）。この処理により、多孔質基材に吸着されたＳｎ２＋の吸着量に勾配を与える。より詳細に説明すると以下のようになる。多孔質基材を純水中に浸漬した場合、Ｓｎ２＋の吸着量は最表面（凸部）、開口部、細孔底部の順、即ち、最表面（凸部）に近づくに従って減少し易くなる。したがって、多孔質基材を純水中に浸漬することにより、細孔底部、開口部、最表面（凸部）の順、即ち、細孔底部に近づくに従って感受性が高い状態となる。次工程の活性化処理においては、パラジウムイオンは感受性の高い領域で反応し易いので、イオン輸送しやすい最表面（凸部）よりも多くの触媒核を細孔底部に形成できるようになる。つまり、純水浸漬処理をおこなうことで、次工程の活性化処理において、細孔底部、開口部、最表面（凸部）の順、即ち、細孔底部に近づくに従って、触媒活性が高い状態となる。最終的に多孔質基材にパラジウムなどの金属がコーティングされる際、パラジウムめっき反応は触媒活性の高い領域で反応し易くなり、細孔底部に近づくに従ってイオン輸送が遅くなるにも関わらず、多孔質基材の全面に均一にコーティングされることになる。 Next, the porous substrate on which Sn 2+ has been adsorbed is immersed in pure water for several seconds to 30 seconds (hereinafter referred to as pure water immersion treatment). By this treatment, a gradient is given to the adsorption amount of Sn 2+ adsorbed on the porous substrate. More detailed description is as follows. When the porous substrate is immersed in pure water, the amount of Sn 2+ adsorbed tends to decrease in the order of the outermost surface (convex portion), opening, and bottom of the pore, that is, the outermost surface (convex portion). . Therefore, by immersing the porous substrate in pure water, the sensitivity becomes higher as the pore bottom, the opening, and the outermost surface (convex portion) are arranged in this order, that is, as the pore bottom is approached. In the activation process of the next step, palladium ions easily react in a sensitive region, so that more catalyst nuclei can be formed at the bottom of the pores than the outermost surface (convex portion) that is easy to transport ions. That is, by performing the pure water immersion treatment, in the activation process of the next step, the catalyst activity becomes higher in the order of the pore bottom, the opening, and the outermost surface (convex portion), that is, the closer to the pore bottom. Become. When the porous substrate is finally coated with a metal such as palladium, the palladium plating reaction is likely to react in a region where the catalytic activity is high, and although the ion transport becomes slower as it approaches the bottom of the pore, it is porous. The entire surface of the quality base material is uniformly coated.
尚、純水中への浸漬時間については数秒〜３０秒としているが、この範囲に限られるものではなく、最適な浸漬時間は多孔質基材の表面粗さ、つまり細孔径や細孔の深さにより適宜変動する。即ち、多孔質基材の表面粗さが小さい、つまり細孔径が大きく、細孔深さが浅い場合には、細孔底部に存在するＳｎ２＋の吸着量が減少しやすいので浸漬時間を短くする必要があるし、表面粗さが大きい、つまり細孔径が小さく、細孔深さが深い場合には、細孔底部に存在するＳｎ２＋の吸着量が減少しにくいので浸漬時間をある程度長くしても問題はない。尚、細孔がナノオーダーの大きさの場合、純水により処理することで細孔中でｐＨが大きく変化し、吸着されたスズイオンが沈殿してしまう虞がある。このような場合には１％程度の希薄酸溶液、例えば１重量％希塩酸溶液により処理することが好ましい。 The immersion time in pure water is several seconds to 30 seconds, but is not limited to this range, and the optimal immersion time is the surface roughness of the porous substrate, that is, the pore diameter and the pore depth. Varies as appropriate. That is, when the surface roughness of the porous substrate is small, that is, the pore diameter is large and the pore depth is shallow, the amount of Sn 2+ adsorbed at the bottom of the pore is likely to decrease, so the immersion time is shortened. If the surface roughness is large, that is, the pore diameter is small and the pore depth is deep, the amount of Sn 2+ adsorbed at the bottom of the pore is difficult to decrease. There is no problem. In addition, when a pore is a nano-order magnitude | size, there exists a possibility that pH may change a lot in a pore by processing with a pure water, and the adsorbed tin ion may precipitate. In such a case, it is preferable to treat with about 1% dilute acid solution, for example, 1% by weight dilute hydrochloric acid solution.
また、上記の感受性化処理工程では、主塩として塩化スズを用いた場合について説明したが、スズ以外にもめっきに対する活性化核としての金属より酸化還元電位が小さく、多孔質基材に担持され得る金属を含むものであれば適用可能であり、例えば亜鉛（Ｚｎ）等を採用できるが、これらに限られるものではない。さらに、塩化物ではなく、硫酸化物や硝酸化物等であっても適用可能である。 In the above sensitization process, the case where tin chloride is used as the main salt has been described. However, in addition to tin, the oxidation-reduction potential is smaller than that of a metal as an activation nucleus for plating and is supported on a porous substrate. For example, zinc (Zn) can be used as long as it contains a metal to be obtained. However, the present invention is not limited thereto. Furthermore, it is applicable not only to chloride but also to sulfate or nitrate.
活性化処理工程では、めっきしようとする金属に対するめっき反応を引き起こす触媒性を有する金属核を形成する。ここでは、パラジウムを触媒核として形成する場合の活性化処理工程について説明する。反応浴、即ち、活性化処理液として、０．５〜２．０ｇ／Ｌの濃度の塩化パラジウム水溶液と濃塩酸（３６％重量）を１０〜５０ｍＬ／Ｌとした塩酸溶液を混合して用いる。ここで、塩化パラジウムと濃塩酸の混合比は１ｇ：２〜１００ｍＬとする。塩化パラジウム溶液の濃度が０．５ｇ／Ｌより小さい場合、形成されるパラジウム触媒核が少ないため、次工程において、無電解めっき反応が起きない又は不均一になる。また、塩酸溶液の濃度に関しては、１０ｍＬ／Ｌより小さい場合は塩化パラジウムが溶けにくく、５０ｍＬ／Ｌより大きくなると設備の耐食性などに問題があるため好ましくない。また、塩化パラジウム溶液の濃度が２．０ｇ／Ｌより大きい場合、パラジウム触媒核が過剰に形成されてしまい、連続めっき膜になってしまうかもしくはめっき液を安定化させることができないので好ましくない。上記活性化処理液に前工程の感受性化処理により細孔底部に近づくに従って感受性が高い状態とした多孔質基材を超音波をかけながら浸漬する。温度に関しては、１０℃〜４０℃とすればよいが、２０℃〜３０℃とすることが好ましい。１０℃未満では反応速度が非常に遅くなってしまい、また、４０℃を超えると反応速度が速くなってしまい、特に最表面（凸部）や開口部付近の反応速度（イオン輸送速度）が極めて速くなってしまい、感受性化処理により形成した感受性勾配の効果が減少してしまう虞があるので好ましくない。また、この場合にも、浸漬処理の際には、超音波をかけ続ける必要はなく、少なくとも細孔内部まで活性化処理液が行き渡れば、その後は超音波をかける必要はない。超音波をかける時間が長すぎる場合には、パラジウム触媒核の吸着に悪影響を及ぼし、パラジウム触媒核が均一に吸着されなくなるので好ましくない。つまり、超音波をかける時間は、パラジウム触媒核の吸着に悪影響を及ぼさない範囲で、少なくとも細孔内部まで活性化処理液が行き渡る程度に行えばよい。例えば、浸漬後に１分程度超音波処理を行った後に残りの時間放置することで、十分に感受性化する。また、超音波は浸漬初期のみかけ続けるようにしてもよいし、間欠的に超音波をかけて細孔内部まで活性化処理液を行き渡るようにしてもよい。また、パラジウム触媒核の吸着に悪影響を及ぼさなければ、浸漬中に超音波をかけ続けても良い。この活性化処理により、吸着している＋２価のスズイオンを＋４価に酸化させ、このとき、パラジウムイオンが金属コロイドに変化し、多孔質基材表面の＋４価のスズイオンが、コロイド状のパラジウム金属の回りを囲むように移動する。ここで、金属核を露出するために、純水で３０秒〜５分間洗浄して、コロイド状のパラジウム金属の回りの塩化スズを洗い流すようにする。ここで、細孔がナノオーダーの大きさで、金属核を露出を十分に行えない場合には１重量％程度の希薄酸、例えば１重量％希塩酸溶液により処理することが好ましい。希薄酸溶液で処理してコロイド状のパラジウム金属の回りの塩化スズを洗い流すことにより、次工程の無電解めっき時に用いるめっき浴の劣化がより確実に防止される。尚、スズ吸着量の濃度勾配は、Ｐｄコロイドの濃度勾配に反映される。即ち、多孔質基材の細孔底部に近づくに従って触媒活性が高い状態となる。さらに、当該純水浸漬処理あるいは希薄酸浸漬処理により、最表面（凸部）や開口部付近のＰｄコロイドが減少して、多孔質基材の細孔底部に近づくに従って触媒活性が高い状態がより顕著となる。 In the activation process, a metal nucleus having catalytic properties that causes a plating reaction on the metal to be plated is formed. Here, an activation treatment process in the case of forming palladium as a catalyst nucleus will be described. As a reaction bath, that is, an activation treatment liquid, a palladium chloride aqueous solution having a concentration of 0.5 to 2.0 g / L and a hydrochloric acid solution in which concentrated hydrochloric acid (36% by weight) is 10 to 50 mL / L are mixed and used. Here, the mixing ratio of palladium chloride and concentrated hydrochloric acid is 1 g: 2 to 100 mL. When the concentration of the palladium chloride solution is smaller than 0.5 g / L, since the number of palladium catalyst nuclei formed is small, the electroless plating reaction does not occur or becomes uneven in the next step. Further, regarding the concentration of the hydrochloric acid solution, if it is less than 10 mL / L, palladium chloride is difficult to dissolve, and if it exceeds 50 mL / L, there is a problem in the corrosion resistance of the equipment, etc., which is not preferable. On the other hand, if the concentration of the palladium chloride solution is larger than 2.0 g / L, an excessive amount of palladium catalyst nuclei is formed, which is not preferable because a continuous plating film is formed or the plating solution cannot be stabilized. A porous base material having a higher sensitivity as it approaches the pore bottom by the sensitization treatment in the previous step is immersed in the activation treatment liquid while applying ultrasonic waves. The temperature may be 10 ° C to 40 ° C, but is preferably 20 ° C to 30 ° C. If it is less than 10 ° C., the reaction rate becomes very slow, and if it exceeds 40 ° C., the reaction rate becomes fast. Especially, the reaction rate (ion transport rate) near the outermost surface (convex part) and the opening is extremely high. This is not preferable because the speed is increased and the effect of the sensitivity gradient formed by the sensitization process may be reduced. Also in this case, it is not necessary to continue to apply ultrasonic waves during the immersion treatment, and it is not necessary to apply ultrasonic waves after the activation treatment liquid reaches at least the inside of the pores. If the time for applying ultrasonic waves is too long, it adversely affects the adsorption of the palladium catalyst nuclei, and the palladium catalyst nuclei are not uniformly adsorbed, which is not preferable. That is, the time for applying the ultrasonic wave may be such that the activation treatment liquid reaches at least the inside of the pores within a range that does not adversely affect the adsorption of the palladium catalyst nucleus. For example, after performing immersion for about 1 minute after immersion, the mixture is allowed to stand for the rest of the time, thereby sufficiently sensitizing. In addition, ultrasonic waves may be applied only at the initial stage of immersion, or the ultrasonic waves may be intermittently applied to spread the activation treatment liquid to the inside of the pores. In addition, ultrasonic waves may be continuously applied during the immersion as long as they do not adversely affect the adsorption of the palladium catalyst nuclei. By this activation treatment, the adsorbed +2 valent tin ion is oxidized to +4 valence. At this time, the palladium ion is changed to a metal colloid, and the +4 valent tin ion on the surface of the porous substrate is converted into colloidal palladium metal. Move so that it surrounds. Here, in order to expose the metal nucleus, it is washed with pure water for 30 seconds to 5 minutes to wash away the tin chloride around the colloidal palladium metal. Here, when the pores are on the order of nanometers and the metal nuclei cannot be exposed sufficiently, it is preferable to treat with about 1% by weight dilute acid, for example, 1% by weight dilute hydrochloric acid solution. By treating with a dilute acid solution to wash away the tin chloride around the colloidal palladium metal, deterioration of the plating bath used in the electroless plating in the next step can be prevented more reliably. Note that the concentration gradient of tin adsorption is reflected in the concentration gradient of Pd colloid. That is, the catalytic activity becomes higher as the pore bottom of the porous substrate is approached. Furthermore, the pure water immersion treatment or dilute acid immersion treatment reduces the Pd colloid near the outermost surface (convex portion) and the opening, and the catalytic activity increases as it approaches the pore bottom of the porous substrate. Become prominent.
ここで、感受性化処理、純水浸漬処理および活性化処理工程は、通常１サイクル行えば、細孔底部から開口部までの領域にＰｄコロイドの触媒核が形成され、且つ細孔底部に近づくに従って触媒活性が高い状態となる。しかし、細孔径が小さく、細孔深さが深い場合には、細孔底部から開口部までの領域にＰｄコロイドの触媒核が形成されない虞があるので、このような場合、あるいは細孔底部側の触媒活性をより高めたい場合には、２サイクル以上行うことでより確実に細孔底部から開口部までの領域にＰｄコロイドの触媒核が形成され、且つ細孔底部に近づくに従って触媒活性が高い状態とすることが可能である。 Here, if the sensitization treatment, the pure water immersion treatment and the activation treatment step are usually performed for one cycle, the catalyst nucleus of the Pd colloid is formed in the region from the bottom of the pore to the opening, and as it approaches the bottom of the pore. The catalyst activity becomes high. However, when the pore diameter is small and the pore depth is deep, there is a possibility that the catalyst nucleus of the Pd colloid is not formed in the region from the pore bottom to the opening. When it is desired to further increase the catalytic activity of Pd, a Pd colloidal catalyst nucleus is more reliably formed in the region from the bottom of the pore to the opening by performing two or more cycles, and the catalytic activity increases as it approaches the bottom of the pore. It is possible to be in a state.
尚、活性化処理工程で用いられる金属は、パラジウムには限られず、感受性化処理時に用いた金属よりも酸化還元電位が高い金属であれば適用可能であり、例えば銀、銅、ニッケルなども採用することができるが、これらに限られるものではない。また、塩化物以外にも、硫酸化物や硝酸化物等を適用することが可能である。 The metal used in the activation process is not limited to palladium, and any metal having a higher oxidation-reduction potential than the metal used in the sensitization process can be used. For example, silver, copper, nickel, etc. are also used. You can, but you are not limited to these. In addition to chlorides, sulfates and nitrates can be applied.
無電解めっき処理工程では、前処理工程により触媒性表面を有するようになった多孔質基材に無電解めっき反応により目的の金属をコーティングする。ここではパラジウムをコーティングする場合について説明する。めっき浴として安定な金属塩素錯化イオンを得るために、主塩として塩化パラジウム溶液を用い、その濃度を３〜１５ｇ／Ｌとすればよく、１０ｇ／Ｌとすることがより好ましい。主還元剤としては、環境に優しく且つ安価な次亜リン酸ナトリウム溶液を３〜２０ｇ／Ｌの濃度で用いればよく、１０ｇ／Ｌとすることがより好ましい。塩化パラジウム溶液と次亜リン酸ナトリウム溶液の濃度がそれぞれ上記範囲より大きくなると、反応速度が速くなる、即ち、パラジウムの析出速度が速くなりすぎて多孔質基材の最表面のみにパラジウムイオンがコーティングされ、ミクロ構造全体にパラジウムがコーティングされなくなる虞がある。また、濃度がそれぞれ上記範囲より小さくなると反応速度が遅くなり、パラジウムの析出速度が遅くなりすぎて、コーティングに時間がかかりすぎてしまう。次に、次亜リン酸ナトリウムと塩化パラジウムと濃度比については、１．２〜１．８のモル比が好適で、それより小さい場合には、還元力が不十分で、パラジウムを全部析出できない虞がある。一方、それより大きい場合、めっき液が不安定になり、自発反応が起きやすく、基材にめっきすることができなくなる虞がある。 In the electroless plating treatment step, the target metal is coated by an electroless plating reaction on the porous substrate having a catalytic surface in the pretreatment step. Here, a case where palladium is coated will be described. In order to obtain a stable metal chloride complex ion as a plating bath, a palladium chloride solution is used as the main salt, and the concentration may be 3 to 15 g / L, and more preferably 10 g / L. As the main reducing agent, an environmentally friendly and inexpensive sodium hypophosphite solution may be used at a concentration of 3 to 20 g / L, and more preferably 10 g / L. When the concentrations of the palladium chloride solution and sodium hypophosphite solution are larger than the above ranges, the reaction rate increases, that is, the palladium deposition rate becomes too high, and only the outermost surface of the porous substrate is coated with palladium ions. As a result, palladium may not be coated on the entire microstructure. On the other hand, when the concentration is smaller than the above range, the reaction rate becomes slow, the deposition rate of palladium becomes too slow, and the coating takes too much time. Next, as for the concentration ratio of sodium hypophosphite and palladium chloride, a molar ratio of 1.2 to 1.8 is preferable, and if it is smaller than that, the reducing power is insufficient and it is not possible to deposit all the palladium. There is a fear. On the other hand, if it is larger than that, the plating solution becomes unstable, and a spontaneous reaction is likely to occur, which may make it impossible to plate the substrate.
上記めっき浴を適当に攪拌しながら前処理工程により触媒性表面を有するようになった多孔質基材を浸漬する。液温は２５〜６０℃で行えばよく、４０℃程度とすることがより好ましい。２５℃未満では反応速度が非常に遅くなってしまい、また、６０℃を超えるとめっき溶液の自発反応が生じ、基材へのめっきができなくなる虞がある。 The porous base material having a catalytic surface in the pretreatment step is immersed while the plating bath is appropriately stirred. The liquid temperature may be 25 to 60 ° C, more preferably about 40 ° C. If it is less than 25 ° C., the reaction rate becomes very slow, and if it exceeds 60 ° C., spontaneous reaction of the plating solution occurs, which may make it impossible to plate the substrate.
ここで、めっきされた金属の粒径は、前処理工程、めっき液濃度、温度、基材種類などの影響も大きいが、反応時間により簡易に制御することができる。即ち、反応時間を長くすれば金属粒径は大きくなり、反応時間を短くすれば金属の粒径は小さくなる。例えば、上記パラジウムめっき条件であれば２分間で８０ｎｍ程度、１５分間で２μｍ程度になる。勿論、反応時間以外の条件を変えることにより粒径の大きさを制御することも可能である。 Here, the particle diameter of the plated metal is greatly influenced by the pretreatment process, the concentration of the plating solution, the temperature, the type of the substrate, and the like, but can be easily controlled by the reaction time. That is, if the reaction time is increased, the metal particle size is increased, and if the reaction time is decreased, the metal particle size is decreased. For example, under the above palladium plating conditions, the thickness is about 80 nm in 2 minutes and about 2 μm in 15 minutes. Of course, it is also possible to control the particle size by changing conditions other than the reaction time.
また、めっき浴のｐＨは６〜１１とすればよいが、９程度とすることがより好ましい。その範囲を超えると、錯化イオンの安定性とめっき酸化還元反応バランスを崩れる恐れがあるため好ましくない。 Moreover, although pH of a plating bath should just be 6-11, it is more preferable to set it as about 9. Exceeding this range is not preferable because the complex ion stability and the plating oxidation-reduction reaction balance may be lost.
尚、ここでは主塩として塩化パラジウムを用いた場合について説明したが、無電解めっきできる金属であればパラジウム以外にも適用することが可能である。また、塩化物ではなく、硫酸化物や硝酸化物等であっても適用可能である。 Although the case where palladium chloride is used as the main salt has been described here, any metal other than palladium can be applied as long as it can be electrolessly plated. Moreover, it is applicable even if it is not a chloride but a sulfate or a nitrate.
また、還元剤には、次亜リン酸ナトリウム溶液を用いたが、例えば、これ以外にも水酸化ホウ素ナトリウム、ヒドラジン等を主還元剤として、もしくは副還元剤として採用することができるが、これらに限られるものではない。尚、ヒドラジンを用いる場合には２０ｍＬ／Ｌ以下、特に、１５ｍＬ／Ｌ程度とすることが好適である。 In addition, a sodium hypophosphite solution was used as the reducing agent. For example, sodium borohydride, hydrazine, etc. can be used as the main reducing agent or as a secondary reducing agent. It is not limited to. When hydrazine is used, it is preferably 20 mL / L or less, particularly about 15 mL / L.
さらに、めっきする金属イオンを安定にして、析出を穏やかに進行させ、均一なめっき層を得るために、錯化剤を添加してもよい。錯化剤としては、例えばエチレンジアミン、有機酸（酢酸、グリコール酸、クエン酸、酒石酸等）のアルカリ塩、チオグリコール酸、アンモニア、ヒドラジン、トリエタノールアミン、グリシン、ｏ−アミノフェノール、ピリジン等を採用できるが、これに限られるものではない。尚、エチレンジアミンを用いる場合には錯化剤としての効果を効率よく得るために５〜２０ｍＬ／Ｌ程度とすればよいが、１０ｍＬ／Ｌ程度とすることがより好ましい。 Furthermore, a complexing agent may be added in order to stabilize the metal ions to be plated, to cause the precipitation to proceed gently, and to obtain a uniform plating layer. Examples of complexing agents include ethylenediamine, alkali salts of organic acids (such as acetic acid, glycolic acid, citric acid, and tartaric acid), thioglycolic acid, ammonia, hydrazine, triethanolamine, glycine, o-aminophenol, and pyridine. Yes, but not limited to this. In addition, when using ethylenediamine, in order to obtain the effect as a complexing agent efficiently, it may be about 5-20 mL / L, but about 10 mL / L is more preferable.
また、金属膜の表面は平滑ではなく、粒状もしくは針状として粗にすることが重要である。したがって、表面活性剤と平滑化剤は、微量（５０ｐｐｍ）以下にするのが好ましい。これを超える量を添加すると、めっき層と基材との間の密着性は改善されるものの、平滑なめっき膜になってしまい、目的の金属粒子や針状金属膜が得られない。しかしながら、平滑なめっき膜を得たい場合には、平滑化剤を５０ｐｐｍよりも多く添加することを否定するものではない。尚、平滑化剤としては、例えばチオ二酢酸等を用いることができる。 Further, it is important that the surface of the metal film is not smooth but rough as a granular shape or needle shape. Therefore, it is preferable that the surface active agent and the leveling agent be in a trace amount (50 ppm) or less. If an amount exceeding this is added, the adhesion between the plating layer and the substrate is improved, but a smooth plating film is formed, and the target metal particles and needle-like metal film cannot be obtained. However, when it is desired to obtain a smooth plating film, the addition of more than 50 ppm of a smoothing agent is not denied. In addition, as a smoothing agent, thiodiacetic acid etc. can be used, for example.
ｐＨが安定化するように、緩衝剤を用いてもよい。緩衝剤としては、例えば、酢酸ナトリウムやクエン酸ナトリウム等のオキシカルボン酸系化合物、ホウ酸や炭酸等の無機酸でいずれも解離定数の小さい化合物、有機酸や無機酸のアルカリ塩等を採用することができるがこれらに限られるものではない。尚、酢酸ナトリウムを用いる際には緩衝剤としての効果を効率よく発揮するため、８〜３２ｇ／Ｌ程度とすればよく、１６ｇ／Ｌ程度とすることがより好ましい。また、副還元剤及び緩衝剤としてヒドラジンを用いることもできるが、ヒドラジンは、環境に悪影響を与えるので、近年用いなくなってきている。 A buffer may be used to stabilize the pH. As the buffering agent, for example, an oxycarboxylic acid compound such as sodium acetate or sodium citrate, an inorganic acid such as boric acid or carbonic acid, a compound having a small dissociation constant, an alkali salt of an organic acid or inorganic acid, or the like is employed. It is possible, but not limited to these. In addition, when using sodium acetate, in order to exhibit the effect as a buffering agent efficiently, it should just be about 8-32 g / L, and it is more preferable to set it as about 16 g / L. Hydrazine can also be used as an auxiliary reducing agent and buffer, but hydrazine has been deprecated in recent years because it adversely affects the environment.
また、ｐＨを所望の値に調整するためにｐＨ調整剤を用いてもよい。ｐＨ調整剤としては、例えば、水酸化ナトリウムや水酸化アンモニウム等の塩基性化合物、無機酸、有機酸等を採用することができるがこれらに限られるものではない。 Moreover, you may use a pH adjuster in order to adjust pH to a desired value. As a pH adjuster, for example, a basic compound such as sodium hydroxide or ammonium hydroxide, an inorganic acid, an organic acid, or the like can be used, but is not limited thereto.
ここで、無電解めっき法の工程における攪拌の効果について説明する。無電解めっき工程では、めっき金属の結晶を数多くめっき対象物にめっきする核形成と核の結晶成長を促す結晶成長の反応が起こっている。そのため、めっき浴を撹拌することにより、金属や還元剤などのイオン輸送率が高くなり、通常めっき金属の結晶の核形成と結晶成長の両方を促進することになる。一方、撹拌しない場合、あるいは攪拌が弱い場合、イオン輸送率が低いため、核形成と結晶成長のうち必要なエネルギーの小さい反応が優先的に（支配的に）起こりやすくなる。例えば、Ｎｉをめっき金属として用いた場合に、撹拌しなければ、結晶成長のエネルギーが小さいため核生成より結晶成長が優先的（支配的）になり、さらに、Ｎｉの結晶成長に異方性があるため、粒子ではなくＮｉ針状結晶になる。 Here, the effect of stirring in the process of the electroless plating method will be described. In the electroless plating process, a reaction of nucleation in which a large number of plated metal crystals are plated on an object to be plated and crystal growth that promotes crystal growth of the nuclei occurs. Therefore, stirring the plating bath increases the ion transport rate of metals, reducing agents, and the like, and usually promotes both nucleation and crystal growth of plated metal crystals. On the other hand, when the stirring is not performed or when the stirring is weak, the ion transport rate is low, so that a reaction with a small energy required between nucleation and crystal growth is likely to occur preferentially (dominantly). For example, when Ni is used as a plating metal, if it is not agitated, the crystal growth energy is small, so that crystal growth is preferential (dominant) over nucleation, and there is anisotropy in Ni crystal growth. Therefore, it becomes a Ni needle crystal instead of a particle.
撹拌強度については、撹拌装置による撹拌子の回転数の制御、撹拌子の大きさ、溶液量により調整することができる。例えば、撹拌子の回転数を高く、撹拌子を大きく、溶液量を少なくすれば、撹拌強度を強くすることができる。逆に、撹拌子の回転数を低く、撹拌子を小さく、溶液量を多くすることで、撹拌強度は小さくなる。例えば、本発明においては、溶液が泡立つ程度の撹拌強さを強い撹拌とした。 About stirring intensity, it can adjust with control of the rotation speed of the stirring bar by a stirring apparatus, the magnitude | size of a stirring bar, and the amount of solutions. For example, if the rotation speed of the stirrer is increased, the stirrer is increased, and the amount of the solution is decreased, the agitation strength can be increased. On the contrary, the stirring strength is reduced by lowering the rotation speed of the stirring bar, reducing the stirring bar, and increasing the amount of the solution. For example, in the present invention, the stirring strength at which the solution is foamed is defined as strong stirring.
なお、上述の形態は本発明の好適な形態の一例ではあるがこれに限定されるものではなく本発明の要旨を逸脱しない範囲において種々変形実施可能である。例えば、耐食性が低い鉄鋼材料を触媒活性と耐食性の高い金属であるパラジウム（Ｐｄ）、白金（Ｐｔ）、ルテニウム（Ｒｕ）、イリジウム（Ｉｒ）、ロジウム（Ｒｈ）、金（Ａｕ）、銀（Ａｇ）およびニッケル（Ｎｉ）等により全面的にコーティングすることで、耐食性を備えた電極が提供可能になる。 The above-described embodiment is an example of a preferred embodiment of the present invention, but is not limited thereto, and various modifications can be made without departing from the scope of the present invention. For example, steel (Pd), platinum (Pt), ruthenium (Ru), iridium (Ir), rhodium (Rh), gold (Au), silver (Ag), which are metals having high catalytic activity and corrosion resistance, are used for steel materials with low corrosion resistance. ) And nickel (Ni) or the like, it is possible to provide an electrode having corrosion resistance.
また、バイオ分野や有機合成分野における電気化学反応等にも本発明の金属−多孔質基材複合材料を応用可能である。 The metal-porous substrate composite material of the present invention can also be applied to electrochemical reactions in the bio field and organic synthesis field.
さらに、本発明の金属―多孔質基材複合材料は、全体に導電性が低いまたはなくてもよい。例えば、絶縁体であるアルミナや有機基板などの上に、分散している金属触媒粒子をコーティングした場合、電気化学反応の電極としてはなく、化学触媒としてＣＶＤやＰＶＤなどの化学反応や物理反応に応用しても良い。 Furthermore, the metal-porous substrate composite material of the present invention may or may not have low overall conductivity. For example, when dispersed metal catalyst particles are coated on an insulator such as alumina or an organic substrate, it is not used as an electrode for electrochemical reaction, but as a chemical catalyst for chemical reaction or physical reaction such as CVD or PVD. It may be applied.
以下に、上記実施形態に基づく実施例を示すが、本発明はこの内容に限られるものではない。
[実施例１]
＜１．材料合成＞
多孔質セラミックスであるＳｒＴｉＯ３を固相反応法により以下のようにして合成した。出発原料をＳｒＣＯ３（高純度化学製、９９．９％）、ＴｉＯ２（高純度化学製、９９．９％）として、ＳｒＣＯ３を１２．９７７７ｇ、ＴｉＯ２を７．０２２３ｇアルミナ乳鉢により混合し、１２００℃、１０時間仮焼した。その後、ジルコニア製遊星形ボールミルを用い、エタノール（ナカライテスク製９８％）で湿式混合した後、この粉体を直径３０ｍｍ、厚さ約５ｍｍのペレットに１００ＭＰａで加圧形成後、１５００℃、１０時間焼成した。この混合・焼成工程を２〜３回繰り返した。焼成したセラミックスの結晶構造は、粉末Ｘ線回折法（Ｘ−ｒａｙ Ｄｉｆｆｒａｃｔｍｅｔｒｙ、Ｍａｃ Ｓｃｉｅｎｃｅ、Ｍ１８ＸＨＦ２２）によりスキャンスピード０．０２°／秒で測定し、ＳｒＴｉＯ３が得られていることを確認した。
Examples based on the above embodiment will be described below, but the present invention is not limited to the contents.
[Example 1]
<1. Material synthesis>
SrTiO 3 , which is a porous ceramic, was synthesized by the solid phase reaction method as follows. The starting materials are SrCO 3 (manufactured by high-purity chemical, 99.9%), TiO 2 (manufactured by high-purity chemical, 99.9%), SrCO 3 is mixed by 12.2777 g, and TiO 2 is mixed by 7.0223 g alumina mortar. Calcination was performed at 1200 ° C. for 10 hours. Thereafter, using a planetary ball mill made of zirconia, wet-mixed with ethanol (98% made by Nacalai Tesque), and then formed into a pellet having a diameter of 30 mm and a thickness of about 5 mm by pressurizing at 100 MPa, 1500 ° C., 10 hours Baked. This mixing and baking process was repeated 2-3 times. The crystal structure of the fired ceramic was measured by a powder X-ray diffraction method (X-ray Diffractometry, Mac Science, M18XHF 22 ) at a scan speed of 0.02 ° / sec, and it was confirmed that SrTiO 3 was obtained.
＜２．前処理工程＞
上記により合成したＳｒＴｉＯ３を基材として、以下のようにして前処理を行った。まず、アセトン中にＳｒＴｉＯ３を浸漬し超音波洗浄を１０分間行って脱脂処理した後、１０％塩酸水溶液中に室温２５℃で１００ｋＨｚの超音波を２分間かけ、その後８分間浸漬して表面を酸性化処理した。次に、２５ｇ／Ｌの塩化スズ溶液と５０ｍＬ／Ｌの濃塩酸（３６％）溶液を塩化スズと濃塩酸の比が１ｇ：２ｍＬとなるように混合して感受性化処理液を作製し、酸性化処理したＳｒＴｉＯ３を室温２５℃で１００ｋＨｚの超音波を１分間かけ、その後５分間浸漬して感受性化処理を行った後、イオン交換処理した超純水に５秒間浸漬して純水浸漬処理を行った。次に、１．０ｇ／Ｌの塩化パラジウム溶液と２０ｍＬ／Ｌの濃塩酸（３６％）溶液を塩化スズと濃塩酸の比が１ｇ：２０ｍＬとなるように混合して活性化処理液を作製し、超音波感受性化処理と純水浸漬処理を行ったＳｒＴｉＯ３を室温２５℃で１００ｋＨｚの超音波を1０秒間かけ、その後１０分間浸漬した後、イオン交換処理した超純水に２分間浸漬して活性化処理をおこなった。
<2. Pretreatment process>
Using SrTiO 3 synthesized as described above as a base material, pretreatment was performed as follows. First, SrTiO 3 was immersed in acetone and ultrasonic cleaning was performed for 10 minutes for degreasing treatment. Then, 100 kHz ultrasonic waves were applied in a 10% hydrochloric acid aqueous solution at 25 ° C. for 2 minutes, and then immersed for 8 minutes. Acidified. Next, a 25 g / L tin chloride solution and a 50 mL / L concentrated hydrochloric acid (36%) solution were mixed so that the ratio of tin chloride to concentrated hydrochloric acid was 1 g: 2 mL to prepare a sensitizing treatment solution, which was acidic. The treated SrTiO 3 was subjected to sensitization treatment by applying ultrasonic waves of 100 kHz at room temperature of 25 ° C. for 1 minute and then immersed for 5 minutes, and then immersed in ultrapure water subjected to ion exchange treatment for 5 seconds. Went. Next, a 1.0 g / L palladium chloride solution and a 20 mL / L concentrated hydrochloric acid (36%) solution were mixed so that the ratio of tin chloride to concentrated hydrochloric acid was 1 g: 20 mL to prepare an activation treatment solution. SrTiO 3 subjected to ultrasonic sensitization treatment and pure water immersion treatment was subjected to 100 kHz ultrasonic waves at room temperature of 25 ° C. for 10 seconds, then immersed for 10 minutes, and then immersed in ultrapure water subjected to ion exchange treatment for 2 minutes. Activation processing was performed.
＜３．無電解めっき工程＞
めっき浴には、主塩として塩化パラジウム１０ｇ／Ｌ、還元剤として次亜リン酸ナトリウム１０ｇ／Ｌ、ｐＨ緩衝剤として酢酸ナトリウム１６ｇ／Ｌ、錯化剤としてエチレンジアミン１０ｍＬ／Ｌ、添加剤（平滑化剤、密着性改善剤）としてチオ二酢酸３０ｐｐｍ、ｐＨ調整剤および副還元剤としてヒドラジン１５ｍＬ／Ｌ用いた。これらを混合してｐＨ９、温度４７℃で撹拌しながら１５分間無電解めっきを行った。
<3. Electroless plating process>
In the plating bath, palladium chloride 10 g / L as the main salt, sodium hypophosphite 10 g / L as the reducing agent, sodium acetate 16 g / L as the pH buffering agent, ethylenediamine 10 mL / L as the complexing agent, additives (smoothing Thiodiacetic acid (30 ppm) as an agent and adhesion improver), and hydrazine (15 mL / L) as a pH adjuster and an auxiliary reducing agent. These were mixed and subjected to electroless plating for 15 minutes while stirring at pH 9 and a temperature of 47 ° C.
＜４．試料観察＞
上記により得られた試料を、ＦＥ−ＳＥＭ（日本電子、ＪＳＭ−６３４０Ｆ）により観察した。結果を図１に示す。１〜２μｍ程度の粒径をもつパラジウム粒子が均一に分布していることが確認された。
<4. Sample observation>
The sample obtained by the above was observed by FE-SEM (JEOL, JSM-6340F). The results are shown in FIG. It was confirmed that palladium particles having a particle diameter of about 1 to 2 μm were uniformly distributed.
[実施例２]
基材として、多孔質電子導電セラミックスであるＳｒ０．９Ｔｉ０．９Ｎb０．１Ｏ３を合成して用いた。合成方法は実施例１と同様であるが、出発原料をＳｒＣＯ３（高純度化学製、９９．９％）、Ｎｂ２Ｏ５（高純度化学製、９９．５％）、ＴｉＯ２（高純度化学製、９９．９％）として、ＳｒＣＯ３を３．０４６０ｇ、Ｎｂ２Ｏ５を０．３０５９ｇ、ＴｉＯ２を１．６４８１ｇ用いて合成した。前処理工程は実施例１と同様とした。無電解めっき工程については、ｐＨ８、４５℃とし、その他の条件は実施例１と同様とした。次に、得られた試料のＳｒ０．９Ｔｉ０．９Ｎb０．１Ｏ３とＰｄとの界面の状態をＥＰＭＡ（日本電子、ＪＳＭ−６３４０Ｆ）により観察した。観察結果を図２に示す。Ｓｒ０．９Ｔｉ０．９Ｎb０．１Ｏ３の微細孔内から開口部に至る領域まで粒子状パラジウム層が存在していることが確認された。したがって、本発明の金属−多孔質基材複合材料の製造方法により、多孔質基材の細孔底部から開口部を含む表面全体が金属により均一に被覆されることが確認された。
[Example 2]
As a base material, Sr 0.9 Ti 0 . 9 Nb 0 . 1 O 3 was synthesized and used. The synthesis method is the same as in Example 1, except that the starting materials are SrCO 3 (manufactured by high purity chemical, 99.9%), Nb 2 O 5 (manufactured by high purity chemical, 99.5%), TiO 2 (high purity). Chemical, 99.9%) was synthesized using 3.0460 g of SrCO 3 , 0.3059 g of Nb 2 O 5 and 1.6481 g of TiO 2 . The pretreatment process was the same as in Example 1. About the electroless-plating process, it was set as pH8 and 45 degreeC, and other conditions were the same as that of Example 1. FIG. Next, Sr 0 . 9 Ti 0 . 9 Nb 0 . The state of the interface between 1 O 3 and Pd was observed with EPMA (JEOL, JSM-6340F). The observation results are shown in FIG. Sr 0.9 Ti 0 . 9 Nb 0 . It was confirmed that the particulate palladium layer was present from the 1 O 3 fine pores to the region extending from the opening. Therefore, it was confirmed that the metal-porous substrate composite material manufacturing method of the present invention uniformly coats the entire surface including the opening from the pore bottom of the porous substrate with the metal.
[実施例３]
基材として、市販のアルミナセラミックス板（（株）鍋林、セラミックス角板（Ａｌ２Ｏ３、９９．５％）、ＳＳＡ−Ｔ）を用いた。前処理工程は実施例１と同様とした。無電解めっき工程については、めっき処理時間を２分間として、その他の条件は実施例１と同様とした。次に、得られた試料を、ＦＥ−ＳＥＭにより観察した。結果を図３に示す。８０〜１２０ｎｍの粒径をもつパラジウム粒子が均一に分布していることが確認された。
[Example 3]
A commercially available alumina ceramic plate (Nabebayashi Co., Ltd., ceramic square plate (Al 2 O 3 , 99.5%), SSA-T) was used as the substrate. The pretreatment process was the same as in Example 1. For the electroless plating step, the plating treatment time was 2 minutes, and the other conditions were the same as in Example 1. Next, the obtained sample was observed by FE-SEM. The results are shown in FIG. It was confirmed that palladium particles having a particle diameter of 80 to 120 nm were uniformly distributed.
[実施例４]
基材として、多孔質電子導電セラミックスＧｄ２Ｔｉ２Ｏ７を合成して用いた。合成方法は実施例１と同様であるが、出発原料をＧｄ２Ｏ３（高純度化学製、９９．９％）、ＴｉＯ２（高純度化学製、９９．９％）として、Ｇｄ２Ｏ３を１３．８８２１ｇ、ＴｉＯ２を６．１１７９ｇ用いて合成した。前処理工程は実施例１と同様とした。ただし、超音波感受性化処理工程〜活性化処理工程は２サイクルで、そのうち活性化処理工程は室温２５℃で１００ｋＨｚの超音波を1０秒間かけ、その後１分間浸漬をおこなった。無電解めっき工程については、ｐＨ７、３０℃、撹拌なし、めっき処理時間を１分間として、その他の条件は実施例１と同様とした。次に、得られた試料を、ＦＥ−ＳＥＭにより観察した。結果を図４に示す。８０〜３００ｎｍの粒径を持つパラジウム粒子が均一に分布していることが確認された。
[Example 4]
As the substrate, porous electronic conductive ceramic Gd 2 Ti 2 O 7 was synthesized and used. The synthesis method is the same as in Example 1, except that the starting materials are Gd 2 O 3 (high purity chemical, 99.9%), TiO 2 (high purity chemical, 99.9%), and Gd 2 O 3. Was synthesized using 13.8821 g and 6.1179 g of TiO 2 . The pretreatment process was the same as in Example 1. However, the ultrasonic sensitization treatment process to the activation treatment process were performed in 2 cycles, and in the activation treatment process, 100 kHz ultrasonic waves were applied for 10 seconds at 25 ° C., and then immersed for 1 minute. For the electroless plating step, pH 7, 30 ° C., no agitation, the plating treatment time was 1 minute, and other conditions were the same as in Example 1. Next, the obtained sample was observed by FE-SEM. The results are shown in FIG. It was confirmed that palladium particles having a particle diameter of 80 to 300 nm were uniformly distributed.
[実施例５]
基材として、多孔質電子導電セラミックスＳｒ０．８Ｌａ０．２ＴｉＯ３を合成して用いた。合成方法は実施例１と同様であるが、出発原料をＳｒＣＯ３（高純度化学製、９９．９％）、Ｌａ２Ｏ３（ナカライテスク製、９９．９％）、ＴｉＯ２（高純度化学製、９９．９％）として、ＳｒＣＯ３を１０．２４５０ｇ、Ｌａ２Ｏ３を２．８２６０ｇ、ＴｉＯ２を６．９２９０ｇ用いて合成した。Ｌａ２Ｏ３に関しては、１５００℃、１時間焼成した後、秤量している。前処理工程は実施例１と同様とした。無電解めっき工程については、主塩として塩化白金酸カリウム２ｇ／Ｌ、還元剤としてヒドラジン５０ｍｌ／Ｌ、次亜リン酸ナトリウム２ｇ／Ｌ，錯化剤として塩酸ヒドロキシルアミン５０ｍｌ／Ｌ、ｐＨ緩衝剤としてアンモニア水１００ｍｌ／Ｌを混合して得られた白金めっき浴を用いて、ｐＨ１３、５５℃で、強く撹拌しながら、めっき処理時間を１０分間として行った。次に、得られた試料を、ＦＥ−ＳＥＭにより観察した。結果を図５に示す。６〜１０ｎｍの粒径をもつ白金粒子が均一に分布していることが確認された。
[Example 5]
Porous electronic conductive ceramics Sr 0.8 La 0.2 TiO 3 was synthesized and used as the substrate. The synthesis method is the same as in Example 1, but the starting materials are SrCO 3 (manufactured by high purity chemical, 99.9%), La 2 O 3 (manufactured by Nacalai Tesque, 99.9%), TiO 2 (high purity chemical). The product was synthesized using 10.2450 g of SrCO 3 , 28260 g of La 2 O 3 and 6.9290 g of TiO 2 . La 2 O 3 is weighed after firing at 1500 ° C. for 1 hour. The pretreatment process was the same as in Example 1. For the electroless plating process, potassium chloroplatinate 2g / L as the main salt, hydrazine 50ml / L, sodium hypophosphite 2g / L as the reducing agent, hydroxylamine hydrochloride 50ml / L as the complexing agent, pH buffering agent Using a platinum plating bath obtained by mixing 100 ml / L of aqueous ammonia, the plating treatment time was 10 minutes at pH 13 and 55 ° C. with vigorous stirring. Next, the obtained sample was observed by FE-SEM. The results are shown in FIG. It was confirmed that platinum particles having a particle diameter of 6 to 10 nm were uniformly distributed.
[実施例６]
基材として、市販のアルミナセラミックス板（（株）鍋林、セラミックス角板（Ａｌ２Ｏ３、９９．５％）、ＳＳＡ−Ｔ）を用いた。前処理工程は実施例１と同様とした。無電解めっき工程については、主塩として塩化ニッケル３５ｇ／Ｌ、還元剤として次亜リン酸ナトリウム２０ｇ／Ｌ、ｐＨ緩衝剤として酢酸ナトリウム２２ｇ／Ｌを混合して得られためっき浴中にｐＨ４．５、４０℃、撹拌なしでめっき処理時間を２分間として行った。次に、得られた試料を、ＦＥ−ＳＥＭにより観察した。結果を図６に示す。８０〜１００ｎｍの粒径をもつ粒子状のニッケル粒子上に針状のニッケルが析出していることが確認された。Niは結晶成長のエネルギーが小さいため核生成より結晶成長が支配的になっていることが考えられ、さらに、Ｎｉの結晶成長に異方性があるため、粒子ではなくＮｉ針状結晶になることが示唆された。
[Example 6]
A commercially available alumina ceramic plate (Nabebayashi Co., Ltd., ceramic square plate (Al 2 O 3 , 99.5%), SSA-T) was used as the substrate. The pretreatment process was the same as in Example 1. Regarding the electroless plating step, nickel chloride 35 g / L as a main salt, sodium hypophosphite 20 g / L as a reducing agent, and sodium acetate 22 g / L as a pH buffering agent were mixed with a pH of 4. The plating process was performed at 5 and 40 ° C. without stirring for 2 minutes. Next, the obtained sample was observed by FE-SEM. The results are shown in FIG. It was confirmed that acicular nickel was deposited on particulate nickel particles having a particle diameter of 80 to 100 nm. Ni has low crystal growth energy, so it is thought that crystal growth is dominant over nucleation, and Ni crystal growth has anisotropy, so it becomes Ni needle crystals instead of particles. Was suggested.
[実施例７]
実施例１および実施例３で作製した試料と、ガラス上に析出させたパラジウム層をＸＲＤ（日本電子、ＪＤＸ８０３０）により分析して、パラジウムの結晶性を評価した。結果を図７に示す。ガラス上に析出させたパラジウム層のＸＲＤパターンと比較して、実施例１および実施例３で得られた試料のＸＲＤパターンの方がブロードであることが確認された。即ち、実施例１および実施例３におけるパラジウム膜は、微結晶状態で存在していることが明らかとなった。
[Example 7]
The samples prepared in Example 1 and Example 3 and the palladium layer deposited on the glass were analyzed by XRD (JEOL, JDX8030) to evaluate the crystallinity of palladium. The results are shown in FIG. Compared with the XRD pattern of the palladium layer deposited on the glass, it was confirmed that the XRD patterns of the samples obtained in Example 1 and Example 3 were broader. That is, it was revealed that the palladium films in Example 1 and Example 3 existed in a microcrystalline state.
［実施例８］
（ａ）アルミナ基材上にめっきしたパラジウム層（実施例３）、（ｂ）Ｓｒ０．９Ｔｉ０．９Ｎｂ０．１Ｏ３上にめっきしたパラジウム層（実施例２）、（ｃ）ＳｒＴｉＯ３上にめっきしたパラジウム層（実施例１）をＥＤＳ（日本電子、ＪＸＡ−８９００Ｒ）測定して、基材にめっきしたパラジウム層に含まれる元素を観察した。結果を図９に示す。パラジウムのＬａのピーク以外にも、りんのＫａのピークが見られたことから、パラジウム層にりん元素が含まれていることが確認された。即ち、次亜りん酸塩を還元剤とした場合、Ｐｄの還元と同時に、次亜りん酸イオンと水素との副反応によりりんも析出し、Ｐｄ−Ｐ合金が形成されることがわかった。また、Ｐｄ−Ｐ合金の中のりんの取り込み量を調査するため、ＥＰＭＡ（日本電子、ＪＸＡ−８９００Ｒ）により、めっきしたパラジウム層の元素定量分析した結果、次亜りん酸イオンとパラジウムイオンの濃度比及びめっき温度等により、めっきしたパラジウム膜中のりんの量が６〜１６ａｔｏｍｉｃ（原子）％の範囲で変動することが確認された。
[Example 8]
(A) Palladium layer plated on alumina substrate (Example 3), (b) Sr 0 . 9 Ti 0 . 9 Nb 0 . A palladium layer plated on 1 O 3 (Example 2), (c) a palladium layer plated on SrTiO 3 (Example 1) was measured by EDS (JEOL, JXA-8900R) and plated on the substrate. The elements contained in the palladium layer were observed. The results are shown in FIG. In addition to the La peak of palladium, a Ka peak of phosphorus was observed, confirming that the palladium layer contained phosphorus element. That is, it was found that when hypophosphite was used as the reducing agent, phosphorus was precipitated by the side reaction of hypophosphite ions and hydrogen simultaneously with the reduction of Pd, and a Pd—P alloy was formed. In addition, in order to investigate the amount of phosphorus incorporated in the Pd-P alloy, the elemental quantitative analysis of the plated palladium layer by EPMA (JEOL, JXA-8900R) revealed that the concentration of hypophosphite ion and palladium ion It was confirmed that the amount of phosphorus in the plated palladium film fluctuated in the range of 6 to 16 atomic (atomic)% depending on the ratio and the plating temperature.
[実施例９]
実施例１で作製した試料を、２５℃の５０重量％硫酸中で浸漬し、この試料を陰極として０．５〜４Ｖで電解（陽極は白金）したところ、陰極表面に大量のガスが発生した。ガスクロマトグラフィー（Agilent Technologies Micro GC-3000A）分析により、発生したガスは水素であることが判明した。したがって、パラジウム／多孔質基材複合材料は、硫酸電解法により水素製造に触媒電極として利用できることが確認されたことから、パラジウム以外の高触媒活性金属である白金（Ｐｔ)、ルテニウム（Ｒｕ）、イリジウム（Ｉｒ)、ロジウム（Ｒｈ)、金（Ａｕ）、銀（Ａｇ)およびニッケル（Ｎｉ）等を用いた金属／多孔質基材複合材料についても、硫酸電解法による水素製造用の触媒電極として利用可能である。
[Example 9]
When the sample prepared in Example 1 was immersed in 50% by weight sulfuric acid at 25 ° C. and electrolysis was performed at 0.5 to 4 V using this sample as a cathode (the anode was platinum), a large amount of gas was generated on the cathode surface. . Gas chromatography (Agilent Technologies Micro GC-3000A) analysis revealed that the generated gas was hydrogen. Therefore, since it was confirmed that the palladium / porous substrate composite material can be used as a catalyst electrode for hydrogen production by sulfuric acid electrolysis, platinum (Pt), ruthenium (Ru), which are highly catalytic active metals other than palladium, Metal / porous substrate composite materials using iridium (Ir), rhodium (Rh), gold (Au), silver (Ag), nickel (Ni), etc. are also used as catalyst electrodes for hydrogen production by sulfuric acid electrolysis. Is available.
［実施例１０］
実施例１で作製した試料を、２５℃の５０重量％硫酸中で浸漬し、この試料を陽極として０．５〜４Ｖで電解（陰極は白金）したところ、陽極表面に大量のガスが発生した。ガスクロマトグラフィー（Agilent Technologies Micro GC-3000A）分析により、発生したガスは酸素であることが判明した。したがって、本発明のパラジウム／多孔質基材複合材料は、硫酸電解法により酸素製造に触媒電極としても利用できることが確認されたことから、パラジウム以外の高触媒活性金属である白金（Ｐｔ)、ルテニウム（Ｒｕ）、イリジウム（Ｉｒ)、ロジウム（Ｒｈ)、金（Ａｕ）、銀（Ａｇ)およびニッケル（Ｎｉ）等を用いた金属／多孔質基材複合材料についても、硫酸電解法による水素製造用の触媒電極として利用可能である。
[Example 10]
When the sample prepared in Example 1 was immersed in 50% by weight sulfuric acid at 25 ° C. and electrolysis was performed at 0.5 to 4 V using the sample as an anode (cathode was platinum), a large amount of gas was generated on the anode surface. . Gas chromatography (Agilent Technologies Micro GC-3000A) analysis revealed that the generated gas was oxygen. Therefore, since it was confirmed that the palladium / porous substrate composite material of the present invention can also be used as a catalyst electrode for oxygen production by a sulfuric acid electrolysis method, platinum (Pt), ruthenium, which are highly catalytically active metals other than palladium. Metal / porous substrate composite materials using (Ru), iridium (Ir), rhodium (Rh), gold (Au), silver (Ag), nickel (Ni), etc. are also used for hydrogen production by sulfuric acid electrolysis. It can be used as a catalyst electrode.
［実施例１１］
アルミナ基材（実施例３と同様のアルミナ基材）上、ＳｒＴｉＯ３（実施例１で合成した多孔質セラミックス基材）上、Ｇｄ２Ｔｉ２Ｏ７（実施例４で合成した多孔質電子導電セラミックス基材）上、Ｓｒ０．８Ｌａ０．２ＴｉＯ３（実施例５で合成した多孔質電子導電セラミックス基材）上に、実施例２と同様の方法によりパラジウム層をめっきし、２５℃の５０重量％硫酸中で電解してサイクリックボルタンメトリー測定（北斗電工株式会社、電気化学測定システムＨＺ−３０００、Ｓｃａｎ ｓｐｅｅｄ：２０ｍＶ／ｓ。作用電極：パラジウムをめっきした電極、対電極：白金。参照電極：Ｈｇ／ＨｇＳＯ４）をおこない、対極に対して作用電極の電位を変化させることによる作用電極の電極反応のメカニズムについて調査した。得られたサイクリックボルタンメトリー曲線を図１０〜１３にそれぞれ示す。また、参考のため、実施例２にて合成した多孔質電子導電セラミックスであるＳｒ０．９Ｔｉ０．９Ｎｂ０．１Ｏ３をめっきせずに同じ条件でサイクリックボルタンメトリー測定を行い（図１４）、また、市販の純パラジウム板（９９．９％、三津和化学）（図１５）も同じ条件でサイクリックボルタンメトリー測定を行った。
[Example 11]
On alumina substrate (alumina substrate similar to Example 3), on SrTiO 3 (porous ceramic substrate synthesized in Example 1), Gd 2 Ti 2 O 7 (porous electronic conductivity synthesized in Example 4) A palladium layer was plated on the Sr 0.8 La 0.2 TiO 3 (porous electronic conductive ceramic substrate synthesized in Example 5) by the same method as in Example 2 and 25 ° C. In vol. 50% sulfuric acid by cyclic voltammetry measurement (Hokuto Denko Corporation, electrochemical measurement system HZ-3000, Scan speed: 20 mV / s. Working electrode: Palladium-plated electrode, counter electrode: Platinum. electrode: Hg / HgSO 4) perform, we investigated the mechanism of the electrode reaction of the working electrode by changing the potential of the working electrode based on the counter It was. The obtained cyclic voltammetry curves are shown in FIGS. For reference, Sr 0.9 Ti 0., Which is a porous electronic conductive ceramic synthesized in Example 2, was used. 9 Nb 0 . Cyclic voltammetry measurement was performed under the same conditions without plating 1 O 3 (FIG. 14), and a commercially available pure palladium plate (99.9%, Mitsuwa Chemical) (FIG. 15) was also subjected to cyclic voltammetry under the same conditions. Measurements were made.
図１０〜図１３に示される結果から、陽極側に電位を変化させた場合と陰極側に電位を変化させた場合の両方とも大電流が流れることが確認されたことから、めっきされた試料は優れた導電性が持つことが判明した。また、めっき層は、６Ｖまで電解しても溶解が起こらず、高い化学的安定性を有することが判明した。これらの結果から、めっきされた試料は、硫酸電解において陽極に限らず陰極としても利用できることがわかった。特に、サイクリックボルタンメトリーにより電位を変化させた場合、パラジウム金属の水素に対する高触媒性により水素の還元反応が促進されることに起因して、陰極は過電圧が低くなり、陽極より高電流が流れることが判明した。したがって、本発明の金属／多孔質基材複合材料を陰極として利用すればより高い水素製造効率を得られることが判明した。 From the results shown in FIGS. 10 to 13, it was confirmed that a large current flows both when the potential is changed to the anode side and when the potential is changed to the cathode side. It has been found that it has excellent conductivity. Further, it was found that the plated layer did not dissolve even when electrolyzed up to 6 V, and had high chemical stability. From these results, it was found that the plated sample can be used not only as an anode but also as a cathode in sulfuric acid electrolysis. In particular, when the potential is changed by cyclic voltammetry, the high catalytic property of palladium metal to hydrogen promotes the reduction reaction of hydrogen, resulting in a lower overvoltage at the cathode and a higher current flowing from the anode. There was found. Therefore, it has been found that if the metal / porous substrate composite material of the present invention is used as a cathode, higher hydrogen production efficiency can be obtained.
次に、導電性のある基材を用いた場合（図１２）と導電性のない基材を用いた場合（図１１）を比較すると、導電性のある基材を用いた場合（図１２）の方が同じ電位で大きい電流が流れることが確認されたことから、基材の導電性が電流値に大きく影響することが確認された。また、同じ電流密度（２００ｍＡ／ｃｍ２―電解法により工業的に水素製造を行う場合の電流密度）で比較すると、必要な電圧は基材の導電性の増加とともに減少していく傾向が見られた。また、めっきなしの多孔質電子導電セラミックス（図１４）と比較すると、めっきした多孔質電子導電セラミックスを用いたサイクリックボルタンメトリー測定の電流値がかなり大きくなることが確認された。したがって、パラジウムめっきにより導電性と触媒性が改善されることが判明した。 Next, when the case where a conductive base material is used (FIG. 12) and the case where a non-conductive base material is used (FIG. 11) are compared, the case where a conductive base material is used (FIG. 12). Since it was confirmed that a larger current flows at the same potential, it has been confirmed that the conductivity of the base material greatly affects the current value. In addition, when compared at the same current density (200 mA / cm 2 —current density when industrially producing hydrogen by an electrolysis method), the required voltage tends to decrease as the conductivity of the substrate increases. It was. Moreover, it was confirmed that the current value of the cyclic voltammetry measurement using the plated porous electronic conductive ceramic was considerably larger than that of the porous electronic conductive ceramic without plating (FIG. 14). Therefore, it has been found that palladium plating improves conductivity and catalytic properties.
また、多孔質電子導電セラミックス上にめっきしたパラジウムのサイクリックボルタンメトリー曲線（図１２、図１３）と市販の純パラジウム板のサイクリックボルタンメトリー曲線（図１５）とを比較すると、同じ電流密度（２００ｍA/cm2）で電気分解を行った場合、純パラジウム板の様なパラジウムバルク材料に比べて、パラジウムめっき層の膜厚は格段に薄いにも関わらず、基材の細孔内に均一にしかも粒子状にめっきされることによる表面積の増加の効果により、パラジウムめっき層の電位（過電圧）は純パラジウム板の電位（過電圧）に比べて若干大きい程度に過ぎず、しかも、陽極分極に関しては、純パラジウムよりめっきしたパラジウム膜の方が酸素の酸化還元反応に対する可逆特性が良いことが確認された。つまり、本発明により作製した金属／多孔質基材複合材料は、多孔質基材として電子導電セラミックスを用いた場合、パラジウムの様な貴金属を少量用いるだけでもバルク材料とそれほど遜色のない過電圧を得ることができるため低コスト化を図ることが可能であり、しかも硫酸中に陽極として電解する場合には、本発明のパラジウムめっき層は、パラジウムバルク材料より有利であることが判明した。 Further, when the cyclic voltammetry curves of palladium plated on the porous electronic conductive ceramic (FIGS. 12 and 13) and the cyclic voltammetry curves of commercially available pure palladium plates (FIG. 15) are compared, the same current density (200 mA / When the electrolysis is performed at cm 2 ), the palladium plating layer is much thinner than the palladium bulk material such as a pure palladium plate, but the particles are uniformly in the pores of the substrate. The potential of the palladium plating layer (overvoltage) is only slightly larger than the potential of the pure palladium plate (overvoltage) due to the effect of increasing the surface area by plating in the shape of a plate. It was confirmed that the more plated palladium film had better reversible characteristics for oxygen redox reaction. In other words, the metal / porous substrate composite material produced according to the present invention obtains an overvoltage comparable to that of the bulk material even when only a small amount of a noble metal such as palladium is used when an electroconductive ceramic is used as the porous substrate. Therefore, it is possible to reduce the cost, and it has been found that the palladium plating layer of the present invention is more advantageous than the palladium bulk material when electrolysis is performed as an anode in sulfuric acid.
１ 多孔質基材
２ 金属イオンＭ３
３ 金属Ｍ２のコロイド
４ 金属Ｍ１
1 Porous substrate 2 Metal ion M 3
3 Colloid of metal M 2 4 Metal M 1
Claims (8)
A step of supporting the metal ion M 3 to the porous substrate by immersing the porous substrate while applying ultrasonic waves to a solution containing low ionic metal M 3 redox potential than the metal M 2, the a step of immersing the porous substrate carrying the metal ions M 3 in pure water or dilute acid solution, the porous carrying the metal ion M 3 while applying ultrasonic waves to a solution containing ions of said metal M 2 a step of Shitsumotozai immersed in the supporting the colloidal metal M 2 to the porous substrate, the step of immersing the porous substrate carrying colloid of the metal ion M 2 in pure water or a dilute acid solution When, to include the electroless plating step of immersing the porous substrate by ion and carrying colloid of the concentration of the reducing agent include leveling agents in solution with 50ppm or less metal M 2 of a metal M 1 Characteristic claim Item 3. A method for producing a metal-porous substrate composite material according to Item 1 or 2.
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| JP2009068046A (en) * | 2007-09-11 | 2009-04-02 | Sekisui Chem Co Ltd | Metal porous structure |
| JP2009114522A (en) * | 2007-11-08 | 2009-05-28 | Toyota Motor Corp | Method for producing gold-plated structure |
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