JP6653877B2 - Pt-Zn-Ni core-shell particles - Google Patents
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- JP6653877B2 JP6653877B2 JP2016064650A JP2016064650A JP6653877B2 JP 6653877 B2 JP6653877 B2 JP 6653877B2 JP 2016064650 A JP2016064650 A JP 2016064650A JP 2016064650 A JP2016064650 A JP 2016064650A JP 6653877 B2 JP6653877 B2 JP 6653877B2
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- 239000002245 particle Substances 0.000 title claims description 98
- 239000011258 core-shell material Substances 0.000 title claims description 76
- 229910007567 Zn-Ni Inorganic materials 0.000 title claims description 36
- 229910007614 Zn—Ni Inorganic materials 0.000 title claims description 36
- 229910052759 nickel Inorganic materials 0.000 claims description 32
- 229910052697 platinum Inorganic materials 0.000 claims description 32
- 229910052725 zinc Inorganic materials 0.000 claims description 25
- 239000007771 core particle Substances 0.000 claims description 24
- 239000000446 fuel Substances 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 21
- 239000005518 polymer electrolyte Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 105
- 238000005259 measurement Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 16
- 238000013507 mapping Methods 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 13
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 238000004544 sputter deposition Methods 0.000 description 10
- 238000000151 deposition Methods 0.000 description 9
- 230000008021 deposition Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000004832 voltammetry Methods 0.000 description 5
- 229910018605 Ni—Zn Inorganic materials 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Powder Metallurgy (AREA)
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
- Catalysts (AREA)
Description
本発明は、Ｐｔ−Ｚｎ−Ｎｉ系コアシェル粒子に関するものである。 The present invention relates to Pt—Zn—Ni-based core-shell particles.
白金（Ｐｔ）は、固体高分子形燃料電池（ＰＥＦＣ）、アルカリ燃料電池（ＡＦＣ）及び金属空気電池における電極触媒材料として機能する。具体的には、固体高分子形燃料電池（ＰＥＦＣ）、アルカリ燃料電池（ＡＦＣ）及び金属空気電池の正極において、及び固体高分子形燃料電池（ＰＥＦＣ）及びアルカリ燃料電池（ＡＦＣ）の負極において、Ｐｔが触媒として使用される。 Platinum (Pt) functions as an electrode catalyst material in polymer electrolyte fuel cells (PEFC), alkaline fuel cells (AFC), and metal-air batteries. Specifically, at the positive electrode of a polymer electrolyte fuel cell (PEFC), an alkaline fuel cell (AFC) and a metal-air battery, and at the negative electrode of a polymer electrolyte fuel cell (PEFC) and an alkaline fuel cell (AFC), Pt is used as a catalyst.
ところで、Ｐｔは高価であるため、使用量の低減が求められている、近年、Ｐｔ使用量の低減を図るべく、非Ｐｔ原子で構成されるコア粒子の表面にＰｔ原子を覆ったコアシェル粒子の研究が行われている。これは、コア（核）を安価な元素である非Ｐｔ元素で構成し、かつ、触媒機能に必要な表面（シェル）をＰｔで構成することで、Ｐｔの使用量を低減させるというコンセプトに基づくものである。こうすることで、純Ｐｔ粒子よりも安価に、触媒活性の高い粒子を得ることができる。 By the way, since Pt is expensive, the amount of Pt used has been demanded to be reduced. In recent years, in order to reduce the amount of Pt used, core-shell particles composed of non-Pt atoms covered with Pt atoms Research is being done. This is based on the concept that the core (nucleus) is made of a non-Pt element, which is an inexpensive element, and the surface (shell) required for the catalytic function is made of Pt, thereby reducing the amount of Pt used. Things. By doing so, particles having high catalytic activity can be obtained at lower cost than pure Pt particles.
例えば、非特許文献１（Vojuslav R. Stamenkovic et al., Science, 315, 493-497, 2007）には、Ｐｔ３Ｎｉ（１１１）表面を有するコアシェル粒子が開示されている。そして、このＰｔ３Ｎｉ（１１１）表面がＰｔ（１１１）表面よりも酸素還元活性（ＯＲＲ）に関して１０倍以上の活性を有し、かつ、ポリマー電解質膜燃料電池（ＰＥＭＦＣ）用の現状のＰｔ／Ｃ触媒よりも９０倍以上の活性を有することが記載されている。また、非特許文献２（Peter Strasser et al., Nature Chemistry, 2, 454-460, 2010）には、脱合金化されたコアシェル燃料電池触媒における活性の格子歪制御が検討されており、Ｐｔリッチのシェルが、Ｐｔのバンド構造のシフトと酸化体種の化学吸着の弱化とをもたらす圧縮歪を呈し、この知見が電極触媒活性の調整に応用可能であることが示唆されている。 For example, Non-Patent Document 1 (Vojuslav R. Stamenkovic et al., Science, 315, 493-497, 2007) discloses core-shell particles having a Pt 3 Ni (111) surface. The Pt 3 Ni (111) surface has an oxygen reduction activity (ORR) ten times or more higher than the Pt (111) surface, and the current Pt / Pt / Ni for the polymer electrolyte membrane fuel cell (PEMFC). It is described as having 90 times or more the activity of the C catalyst. Non-Patent Document 2 (Peter Strasser et al., Nature Chemistry, 2, 454-460, 2010) discusses the control of lattice strain of the activity in a dealloyed core-shell fuel cell catalyst, and the Pt-rich. Exhibit a compressive strain that results in a shift in the band structure of Pt and a weakened chemisorption of oxidant species, suggesting that this finding can be applied to modulate electrocatalytic activity.
ところで、非特許文献３（Yuichiro Kurokawa et al., Journal of Applied Physics 113, 174302 (2013)）には、プラズマ・ガス凝縮クラスター堆積（ＰＧＣＣＤ）装置を用いてナノサイズのコアシェルクラスターを作製できることが述べられており、ＰＧＣＣＤ装置によりＳｎ１−ｘ／Ｓｉｘクラスター堆積フィルムを合成したことが開示されている。 By the way, Non-Patent Document 3 (Yuichiro Kurokawa et al., Journal of Applied Physics 113, 174302 (2013)) states that a nano-sized core-shell cluster can be produced using a plasma gas condensation cluster deposition (PGCCD) apparatus. is and, it is disclosed that by combining the Sn 1-x / Si x clusters deposited film by PGCCD device.
前述のとおり、従来のコアシェル粒子は、非Ｐｔ原子で構成されるコアを、Ｐｔ原子を含むシェルで覆ったものであった。しかしながら、より低いＰｔ使用量でありながら、より高い触媒活性の高い粒子が提供できればより望ましい。 As described above, the conventional core-shell particles have a core composed of non-Pt atoms covered with a shell containing Pt atoms. However, it would be more desirable to be able to provide particles with higher catalytic activity at lower Pt usage.
本発明者らは、今般、Ｐｔ、Ｚｎ及びＮｉの３元素を用いてコアシェル粒子を構成すること、とりわけシェル層を主としてＺｎ及びＮｉで構成し、かつ、コア粒子を主としてＰｔ及びＮｉで構成することで、低減されたＰｔ使用量でありながら、純Ｐｔ粒子と同等以上の触媒活性を呈することができるとの知見を得た。 The present inventors have recently constructed a core-shell particle using three elements of Pt, Zn and Ni, in particular, a shell layer is mainly composed of Zn and Ni, and a core particle is mainly composed of Pt and Ni. As a result, it has been found that it is possible to exhibit catalytic activity equal to or higher than that of pure Pt particles even though the amount of Pt used is reduced.
したがって、本発明の目的は、低減されたＰｔ使用量でありながら、純Ｐｔ粒子と同等以上の触媒活性を呈することが可能なコアシェル粒子を提供することにある。 Therefore, an object of the present invention is to provide core-shell particles capable of exhibiting a catalytic activity equal to or higher than that of pure Pt particles while using a reduced amount of Pt.
本発明の一態様によれば、
Ｐｔ及びＮｉを含むコア粒子と、
前記コア粒子を被覆する、Ｚｎ及びＮｉを含むシェル層と、
を備えた、Ｐｔ−Ｚｎ−Ｎｉ系コアシェル粒子が提供される。
According to one aspect of the present invention,
A core particle containing Pt and Ni;
A shell layer containing Zn and Ni, which covers the core particles;
And a Pt—Zn—Ni-based core-shell particle comprising:
Ｐｔ−Ｚｎ−Ｎｉ系コアシェル粒子
図１に本発明のＰｔ−Ｚｎ−Ｎｉ系コアシェル粒子１０（以下、コアシェル粒子１０という）の模式断面図を示す。図１に模式的に示されるように、コアシェル粒子１０は、コア粒子１２とコア粒子を被覆するシェル層１４とを備える。コア粒子１２はＰｔ及びＮｉを含む。また、シェル層１４はＺｎ及びＮｉを含む。したがって、コアシェル粒子１０は全体としてＰｔ−Ｚｎ−Ｎｉ系の基本組成を有する、すなわちＰｔ、Ｚｎ及びＮｉを基本成分として含む、典型的にはＰｔ、Ｚｎ及びＮｉで構成されるといえる。このようにＰｔ、Ｚｎ及びＮｉの３元素を用いてコアシェル粒子を構成すること、とりわけシェル層を主としてＺｎ及びＮｉで構成し、かつ、コア粒子を主としてＰｔ及びＮｉで構成することで、低減されたＰｔ使用量でありながら、純Ｐｔ粒子と同等以上の触媒活性を呈することができる。前述のとおり、従来のコアシェル粒子は、非Ｐｔ原子で構成されるコアを、Ｐｔ原子を含むシェルで覆ったものであった。これに対し、本発明のコアシェル粒子はＰｔ原子を、粒子表面を構成するシェルよりも、むしろシェルに取り囲まれたコア内にリッチに含有させる。こうすることで、予想外にも純Ｐｔ粒子と同等以上の触媒活性を呈することができる。しかも、Ｐｔ原子はシェルに必ずしも存在する必要はなく、コアにさえ存在していればよい。それ故、Ｐｔ使用量を低減でき、コスト的にも有利となる。つまり、本発明の粒子の特徴は、従来のコアシェル粒子とは異なりＰｔが表面に無くても触媒活性が高く、しかもその触媒活性が純Ｐｔと同等以上となることにある。
Pt—Zn—Ni-based core-shell particles FIG. 1 is a schematic cross-sectional view of the Pt—Zn—Ni-based core-shell particles 10 (hereinafter, referred to as core-shell particles 10) of the present invention. As schematically shown in FIG. 1, the core-shell particle 10 includes a core particle 12 and a shell layer 14 covering the core particle. The core particles 12 include Pt and Ni. The shell layer 14 contains Zn and Ni. Therefore, it can be said that the core-shell particles 10 have a Pt—Zn—Ni-based basic composition as a whole, that is, are typically composed of Pt, Zn, and Ni, containing Pt, Zn, and Ni as basic components. As described above, the core-shell particles are formed by using the three elements of Pt, Zn, and Ni, and in particular, the shell layer is mainly formed of Zn and Ni, and the core particles are mainly formed of Pt and Ni. Although the amount of Pt used is small, it can exhibit catalytic activity equal to or higher than that of pure Pt particles. As described above, the conventional core-shell particles have a core composed of non-Pt atoms covered with a shell containing Pt atoms. In contrast, the core-shell particles of the present invention contain Pt atoms richly in the core surrounded by the shell, rather than in the shell constituting the particle surface. This makes it possible to unexpectedly exhibit catalytic activity equal to or higher than that of pure Pt particles. Moreover, the Pt atom does not necessarily need to be present in the shell, but only needs to be present in the core. Therefore, the amount of Pt used can be reduced, which is advantageous in terms of cost. That is, the feature of the particles of the present invention is that, unlike conventional core-shell particles, the catalyst activity is high even if Pt is not present on the surface, and the catalyst activity is equal to or higher than pure Pt.
コア粒子１２はＰｔ及びＮｉを含み、典型的には主としてＰｔ及びＮｉで構成される。コア粒子１２はＺｎをさらに含むものであってよい。実際、プラズマ・ガス凝縮クラスター堆積（ＰＧＣＣＤ）装置を用いて作製されたコアシェル粒子１０においては、コア粒子１２はＺｎを不可避的に含有しうる。したがって、コア粒子１２単体に着目した場合、Ｚｎは不可避元素ないし不可避不純物ということもできる。コアシェル粒子１０の粒子径は１〜２０ｎｍが好ましく、より好ましくは１〜１５ｎｍ、さらに好ましくは１〜５ｎｍである。 The core particles 12 include Pt and Ni, and are typically mainly composed of Pt and Ni. The core particles 12 may further include Zn. In fact, in core-shell particles 10 made using a plasma gas condensation cluster deposition (PGCCD) apparatus, core particles 12 may inevitably contain Zn. Therefore, when attention is paid to the core particle 12 alone, Zn can be said to be an unavoidable element or an unavoidable impurity. The particle diameter of the core-shell particles 10 is preferably 1 to 20 nm, more preferably 1 to 15 nm, and still more preferably 1 to 5 nm.
シェル層１４は、コア粒子１２を被覆する層である。シェル層１４はコア粒子１２を完全に被覆していてよいし、部分的に被覆していてもよい。シェル層１４がコア粒子１２を完全でなくとも概ね全体的に被覆していれば十分である。シェル層１４の厚さは０．２５〜５ｎｍが好ましく、より好ましくは０．２５〜４ｎｍ、さらに好ましくは０．２５〜１．５ｎｍである。 The shell layer 14 is a layer that covers the core particles 12. The shell layer 14 may completely cover the core particle 12 or may partially cover the core particle 12. It is sufficient for the shell layer 14 to cover the core particle 12 if not completely. The thickness of the shell layer 14 is preferably from 0.25 to 5 nm, more preferably from 0.25 to 4 nm, even more preferably from 0.25 to 1.5 nm.
シェル層１４は、Ｚｎ及びＮｉを含む。したがって、Ｎｉはコア粒子１２及びシェル層１４の両方に含まれる。 The shell layer 14 contains Zn and Ni. Therefore, Ni is contained in both the core particles 12 and the shell layer 14.
シェル層１４はＰｔを含まないのが好ましい。あるいは、シェル層１４はＰｔを含むものであってもよいが、コア粒子１２がシェル層１４よりもＰｔに富んでいるものであればよい。いずれにしても、Ｐｔの使用量を大幅に低減しながらも、触媒活性を向上させることができる。 The shell layer 14 preferably does not contain Pt. Alternatively, the shell layer 14 may contain Pt, but may be any as long as the core particles 12 are richer in Pt than the shell layer 14. In any case, the catalytic activity can be improved while the amount of Pt used is significantly reduced.
コアシェル粒子１０の粒子径は１〜２０ｎｍが好ましく、より好ましくは１〜１５ｎｍ、さらに好ましくは１〜５ｎｍである。このような範囲内であると、ＰＧＣＣＤ装置等を用いたスパッタリング技術で作製しやすい上に、優れた触媒活性をより実現しやすい。 The particle diameter of the core-shell particles 10 is preferably 1 to 20 nm, more preferably 1 to 15 nm, and still more preferably 1 to 5 nm. Within such a range, it is easy to produce by a sputtering technique using a PGCCD apparatus and the like, and it is easier to realize excellent catalytic activity.
Ｐｔ−Ｚｎ−Ｎｉ系コアシェル粒子１０の全体量に対するＰｔの割合は３０〜７０原子％であるのが好ましく、より好ましくは３０〜６５原子％であり、さらに好ましくは３０〜５０原子％である。Ｐｔ−Ｚｎ−Ｎｉ系コアシェル粒子１０の全体量に対するＮｉの割合は２０〜７０原子％であるのが好ましく、より好ましくは２０〜６０原子％であり、さらに好ましくは２０〜５０原子％である。Ｐｔ−Ｚｎ−Ｎｉ系コアシェル粒子１０の全体量に対するＺｎの割合は１０〜５０原子％であるのが好ましく、より好ましくは１０〜４０原子％であり、さらに好ましくは１０〜３０原子％であり、特に好ましくは１０〜２０原子％である。 The ratio of Pt to the total amount of the Pt—Zn—Ni-based core-shell particles 10 is preferably 30 to 70 atomic%, more preferably 30 to 65 atomic%, and further preferably 30 to 50 atomic%. The ratio of Ni to the total amount of the Pt—Zn—Ni-based core-shell particles 10 is preferably 20 to 70 atomic%, more preferably 20 to 60 atomic%, and further preferably 20 to 50 atomic%. The ratio of Zn to the total amount of the Pt—Zn—Ni-based core-shell particles 10 is preferably 10 to 50 atomic%, more preferably 10 to 40 atomic%, further preferably 10 to 30 atomic%, Particularly preferably, it is 10 to 20 atomic%.
本発明のＰｔ−Ｚｎ−Ｎｉ系コアシェル粒子は、優れた触媒活性を発揮できることから、固体高分子形燃料電池の正極若しくは負極、アルカリ燃料電池の正極若しくは負極、又は金属空気電池の正極に触媒として用いられるのが好ましい。 Since the Pt-Zn-Ni-based core-shell particles of the present invention can exhibit excellent catalytic activity, they can be used as a catalyst in the cathode or anode of a polymer electrolyte fuel cell, the cathode or anode of an alkaline fuel cell, or the cathode of a metal-air battery. It is preferably used.
製造方法
本発明のＰｔ−Ｚｎ−Ｎｉ系コアシェル粒子はいかなる方法により製造されたものであってもよいが、好ましくは、プラズマ・ガス凝縮クラスター堆積（ＰＧＣＣＤ）装置を用いて製造することができる。ＰＧＣＣＤ装置は、後述する図２に例示されるように、直流マグネトロンスパッタリング方式の原料気化装置と、希ガス中凝縮装置とを組み合せたナノクラスター試料作製装置である。ＰＧＣＣＤ装置を用いたクラスターないし粒子の製造方法は公知であり、例えば非特許文献３（Yuichiro Kurokawa et al., Journal of Applied Physics 113, 174302 (2013)）に記載されており、この文献は参照により本明細書に組み込まれる。非特許文献３や図２に記載されるようなＰＧＣＣＤ装置を用いたクラスターないし粒子の製造において、Ｐｔターゲットと、Ｎｉ−Ｚｎ合金ターゲットとを対向させてスパッタリングチャンバ内に配置してスパッタリングを行い、基材上に膜状に堆積させることにより、本発明のコアシェル粒子を製造することができる。スパッタリングの方式は直流マグネトロンスパッタリングが好ましい。ＰＧＣＣＤ装置を用いた方法により本発明のＰｔ−Ｚｎ−Ｎｉ系コアシェル粒子が形成されるメカニズムは必ずしも明らかではないが、Ｐｔのように融点が高い元素は表面エネルギーが大きく、それ故、表面を減らすようにＰｔが粒子の内側に位置する傾向があるためではないかと推察される。
Manufacturing Method The Pt—Zn—Ni-based core-shell particles of the present invention may be manufactured by any method, but can be preferably manufactured using a plasma gas condensation cluster deposition (PGCCD) apparatus. The PGCCD apparatus is, as exemplified in FIG. 2 to be described later, a nanocluster sample preparation apparatus in which a DC magnetron sputtering type material vaporizer and a rare gas condensing apparatus are combined. A method for producing clusters or particles using a PGCCD apparatus is known, and is described, for example, in Non-Patent Document 3 (Yuichiro Kurokawa et al., Journal of Applied Physics 113, 174302 (2013)). Incorporated herein. In the production of clusters or particles using a PGCCD apparatus as described in Non-Patent Document 3 or FIG. 2, sputtering is performed by disposing a Pt target and a Ni—Zn alloy target in a sputtering chamber so as to face each other, The core-shell particles of the present invention can be produced by depositing them on a substrate in the form of a film. As the sputtering method, DC magnetron sputtering is preferable. The mechanism by which the Pt-Zn-Ni-based core-shell particles of the present invention are formed by a method using a PGCDD device is not necessarily clear, but an element having a high melting point, such as Pt, has a large surface energy and therefore reduces the surface. It is presumed that Pt tends to be located inside the particles as described above.
本発明を以下の例によってさらに具体的に説明する。 The present invention will be more specifically described by the following examples.
例１
本例ではコアシェル粒子を作製し、固体高分子形燃料電池の燃料極触媒としてのコアシェル粒子の特性を調べた。具体的には以下のとおりである。
Example 1
In this example, core-shell particles were produced, and the characteristics of the core-shell particles as a fuel electrode catalyst of a polymer electrolyte fuel cell were examined. The details are as follows.
（１）コアシェル粒子の製造
図２に示される構成を有するプラズマ・ガス凝縮クラスター堆積（ＰＧＣＣＤ）装置（株式会社日本ビーテック製）を用意した。このＰＧＣＣＤ装置１００は、スパッタリングチャンバ１０２と、クラスター成長室１０４と、堆積チャンバ１０６とを備える。スパッタリングチャンバ１０２は、Ａｒガス及び／又はＨｅガスを供給可能なガス供給口１０８と、上下に対向して配置される２つのターゲットホルダ１１２，１１４とを備える。クラスター成長室１０４は、スパッタリングチャンバ１０２と連通する成長ダクト１１６と、成長ダクト１１６の先端のノズル１１８と、ノズル１１８と対向して設けられるスキマー１２０とを備え、コンパウンド分子ポンプ（ＣＭＰ）とメカニカルブースターポンプ（ＭＢＰ）に連結され減圧可能とされる。堆積チャンバ１０６は、試料ホルダ１２２を備え、ターボ分子ポンプ（ＴＭＰ）に連結され減圧可能とされる。試料ホルダ１２２は、スキマー１２０から放射される原子が堆積可能な位置、すなわちスキマー１２０と対向しかつ所定距離離れた位置に設けられる。
(1) Production of Core-Shell Particles A plasma gas condensation cluster deposition (PGCCD) apparatus (manufactured by Japan Betec) having the configuration shown in FIG. 2 was prepared. The PGCCD apparatus 100 includes a sputtering chamber 102, a cluster growth chamber 104, and a deposition chamber 106. The sputtering chamber 102 includes a gas supply port 108 that can supply an Ar gas and / or a He gas, and two target holders 112 and 114 that are arranged vertically facing each other. The cluster growth chamber 104 includes a growth duct 116 communicating with the sputtering chamber 102, a nozzle 118 at the tip of the growth duct 116, and a skimmer 120 provided to face the nozzle 118, and includes a compound molecular pump (CMP) and a mechanical booster. It is connected to a pump (MBP) and can be depressurized. The deposition chamber 106 includes a sample holder 122, and is connected to a turbo-molecular pump (TMP) so that the pressure can be reduced. The sample holder 122 is provided at a position where atoms emitted from the skimmer 120 can be deposited, that is, at a position facing the skimmer 120 and separated by a predetermined distance.
スパッタリングチャンバ１０２内の上側のターゲットホルダ１１２にＰｔターゲットを、下側のターゲットホルダ１１４にＮｉ−Ｚｎ合金ターゲット（組成：Ｎｉ−４０原子％Ｚｎ）を固定した。こうしてＰｔターゲットとＮｉ−Ｚｎ合金ターゲットを対向させて配置した。ＰＧＣＣＤ装置１００内を減圧し、スパッタ出力：２５０Ｗ（Ｐｔターゲットに対して）及び１５０Ｗ（Ｎｉ−Ｚｎ合金ターゲットに対して）、Ａｒガス流量：４００ｓｃｃｍの条件で、マグネトロンスパッタリングを行い、試料ホルダ上にＰｔ原子、Ｎｉ原子及びＺｎ原子のナノ粒子を堆積させてコアシェル粒子を得た。 A Pt target was fixed to the upper target holder 112 and a Ni—Zn alloy target (composition: Ni-40 atomic% Zn) was fixed to the lower target holder 114 in the sputtering chamber 102. In this way, the Pt target and the Ni—Zn alloy target were arranged to face each other. The inside of the PGCCD apparatus 100 is depressurized, and magnetron sputtering is performed under the conditions of a sputter output: 250 W (for a Pt target) and 150 W (for a Ni—Zn alloy target), and an Ar gas flow rate: 400 sccm, and the sample is placed on a sample holder. Core-shell particles were obtained by depositing nanoparticles of Pt, Ni and Zn atoms.
試料ホルダ１２２上にセットしたＣｕグリッド上に堆積したコアシェル粒子をＴＥＭ観察用サンプルとした。ＳＴＥＭ−ＥＤＸ（走査透過型電子顕微鏡−エネルギー分散型Ｘ線分光分析器）（製品名：ＪＥＭ−ＡＲＭ２００Ｆ、日本電子社製）により、コアシェル粒子に対して組成分析を行った。その結果、Ｐｔ及びＮｉを含むコア粒子と、Ｚｎ及びＮｉを含むシェル層とが確認された。また、コアシェル粒子の全体組成はＰｔ６３Ｎｉ２５Ｚｎ１２であった。 The core-shell particles deposited on the Cu grid set on the sample holder 122 were used as TEM observation samples. The composition of core-shell particles was analyzed by STEM-EDX (scanning transmission electron microscope-energy dispersive X-ray spectrometer) (product name: JEM-ARM200F, manufactured by JEOL Ltd.). As a result, core particles containing Pt and Ni and a shell layer containing Zn and Ni were confirmed. The overall composition of the core-shell particles was Pt 63 Ni 25 Zn 12 .
（２）固体高分子形燃料電池の電流−電圧（Ｉ−Ｖ）特性
上記得られたＰｔ−Ｚｎ−Ｎｉ系コアシェル粒子（組成：Ｐｔ６３Ｎｉ２５Ｚｎ１２）を用いて、以下に示される燃料極（触媒及び集電体）、電解質及び空気極（触媒及び集電体）を用いて固体高分子形燃料電池の測定系を構成した。
＜測定系＞
‐燃料極
触媒：Ｐｔ−Ｚｎ−Ｎｉ系コアシェル粒子（組成：Ｐｔ６３Ｎｉ２５Ｚｎ１２）
集電体：カーボンペーパー（撥水加工が施されたもの）
‐電解質：Ｎａｆｉｏｎ（登録商標）（和光純薬工業社製）
‐空気極：
触媒：純Ｐｔ
集電体；カーボンペーパー（撥水加工が施されたもの）
(2) Current-Voltage (IV) Characteristics of Polymer Electrolyte Fuel Cell Using the Pt-Zn-Ni-based core-shell particles (composition: Pt 63 Ni 25 Zn 12 ) obtained above, the fuel shown below is used. The measurement system of the polymer electrolyte fuel cell was configured using the electrodes (catalyst and current collector), the electrolyte, and the air electrode (catalyst and current collector).
<Measurement system>
-Fuel electrode Catalyst: Pt-Zn-Ni-based core-shell particles (composition: Pt 63 Ni 25 Zn 12 )
Current collector: Carbon paper (water-repellent)
-Electrolyte: Nafion (registered trademark) (manufactured by Wako Pure Chemical Industries, Ltd.)
-Air electrode:
Catalyst: Pure Pt
Current collector; carbon paper (water-repellent)
上記測定系を用いて以下の条件で固体高分子形燃料電池を作動させ、電流−電圧（Ｉ−Ｖ）特性と電流−出力（Ｉ−Ｐ）特性を測定した。測定結果は図３Ａ及び３Ｂに示されるとおりであった。
＜測定条件＞
‐燃料極：純Ｈ２ガス／流量：１００ｓｃｃｍ
‐空気極：純Ｏ２／流量：１００ｓｃｃｍ
Using the above measurement system, the polymer electrolyte fuel cell was operated under the following conditions, and current-voltage (IV) characteristics and current-output (IP) characteristics were measured. The measurement results were as shown in FIGS. 3A and 3B.
<Measurement conditions>
-Fuel electrode: pure H 2 gas / flow rate: 100 sccm
- the air electrode: pure O 2 / flow rate: 100sccm
例２（比較）
Ｎｉ−４０原子％Ｚｎターゲットの代わりにＰｔターゲットを２５０Ｗのスパッタ出力で用いたこと以外は例１と同様にして、純Ｐｔ粒子（組成：Ｐｔ１００％）を作製した。次いで、燃料極触媒として上記純Ｐｔ粒子を用いたこと以外は例１と同様にして、固体高分子形燃料電池の電流−電圧特性（Ｉ−Ｖ）と電流−出力（Ｉ−Ｐ）特性の測定を行った。測定結果は図３Ａ及び３Ｂに示されるとおりであった。
Example 2 (comparison)
Pure Pt particles (composition: 100% Pt) were produced in the same manner as in Example 1, except that a Pt target was used at a sputtering output of 250 W instead of a Ni-40 atomic% Zn target. Next, in the same manner as in Example 1 except that the pure Pt particles were used as the anode catalyst, the current-voltage characteristics (IV) and the current-output (IP) characteristics of the polymer electrolyte fuel cell were measured. A measurement was made. The measurement results were as shown in FIGS. 3A and 3B.
図３Ａ及び３Ｂに示される結果から、Ｐｔ６３％の例１のコアシェル粒子は、Ｐｔ１００％の例２の粒子よりもＰｔ含有量が少ないにも関わらず、Ｉ−Ｖ特性及びＩ−Ｐ特性がＰｔ１００％の例２よりも良好であった（すなわち同じ電流密度でのセル電圧及び出力密度が同等以上であった）。 From the results shown in FIGS. 3A and 3B, the core-shell particles of Example 1 with 63% Pt have a lower Pt content than the particles of Example 2 with 100% Pt, but their IV and IP characteristics are Pt100. % (I.e., cell voltage and power density at the same current density were equal or better).
例３
本例ではコアシェル粒子を作製し、金属空気電池の正極触媒としてのコアシェル粒子の特性を調べた。具体的には以下のとおりである。
Example 3
In this example, core-shell particles were prepared, and the characteristics of the core-shell particles as a positive electrode catalyst of a metal-air battery were examined. The details are as follows.
（１）コアシェル粒子の製造
例１と同様にして、Ｐｔ−Ｚｎ−Ｎｉ系コアシェル粒子を製造した。試料ホルダ上に堆積したコアシェル粒子をサンプルとして採取し、例１と同様にしてコアシェル粒子に対して組成分析を行った。その結果、Ｐｔ及びＮｉを含むコア粒子と、Ｚｎ及びＮｉを含むシェル層とが確認された。また、コアシェル粒子の全体組成はＰｔ４０Ｎｉ４２Ｚｎ１８であった。
(1) Production of core-shell particles In the same manner as in Example 1, Pt-Zn-Ni-based core-shell particles were produced. The core-shell particles deposited on the sample holder were collected as a sample, and the composition of the core-shell particles was analyzed in the same manner as in Example 1. As a result, core particles containing Pt and Ni and a shell layer containing Zn and Ni were confirmed. The overall composition of the core-shell particles was Pt 40 Ni 42 Zn 18 .
（２）正極触媒の触媒活性の対流ボルタンメトリ測定
上記得られたＰｔ−Ｚｎ−Ｎｉ系コアシェル粒子（組成：Ｐｔ４０Ｎｉ４２Ｚｎ１８）を用いて、以下に示される作用極、電解質、対極及び参照極を用いて電気化学測定系を構成した。
＜測定系＞
‐作用極（正極触媒）：コアシェル粒子（組成：Ｐｔ４０Ｎｉ４２Ｚｎ１８）
‐電解質：１Ｍ ＫＯＨ水溶液
‐対極：Ｐｔ
‐参照極：Ｈｇ／ＨｇＯ
(2) Convective Voltammetry Measurement of Catalytic Activity of Positive Electrode Catalyst Using the obtained Pt—Zn—Ni-based core-shell particles (composition: Pt 40 Ni 42 Zn 18 ), a working electrode, an electrolyte, a counter electrode and a reference shown below An electrochemical measurement system was constructed using the poles.
<Measurement system>
-Working electrode (cathode catalyst): core-shell particles (composition: Pt 40 Ni 42 Zn 18 )
-Electrolyte: 1M KOH aqueous solution-Counter electrode: Pt
-Reference electrode: Hg / HgO
＜測定条件＞
上記測定系を用いて以下の条件で正極触媒の触媒活性の対流ボルタンメトリ測定を行った。測定結果は図４に示されるとおりであった。
‐電位範囲：＋０．１〜−０．８Ｖ（ｖｓＨｇ／ＨｇＯ）
‐作用極回転数：５００〜４０００ｒｐｍ（５００ｒｐｍ刻みで変化させた）
<Measurement conditions>
A convective voltammetry measurement of the catalytic activity of the positive electrode catalyst was performed under the following conditions using the above measurement system. The measurement results were as shown in FIG.
-Potential range: +0.1 to -0.8 V (vsHg / HgO)
-Working electrode rotation speed: 500 to 4000 rpm (changed in steps of 500 rpm)
例４（比較）
Ｎｉ−４０原子％Ｚｎターゲットの代わりにＰｔターゲットを２５０Ｗのスパッタ出力で用いたこと以外は例１と同様にして、純Ｐｔ粒子（組成：Ｐｔ１００％）を作製した。次いで、作用極（正極触媒）として上記純Ｐｔ粒子を用いたこと以外は例３と同様にして電気化学測定系を構成して、正極触媒の触媒活性の対流ボルタンメトリ測定を行った。測定結果は図５に示されるとおりであった。例３と同様の評価を行った。
Example 4 (comparison)
Pure Pt particles (composition: 100% Pt) were produced in the same manner as in Example 1, except that a Pt target was used at a sputtering output of 250 W instead of a Ni-40 atomic% Zn target. Subsequently, an electrochemical measurement system was configured in the same manner as in Example 3 except that the pure Pt particles were used as a working electrode (cathode catalyst), and convective voltammetry measurement of the catalyst activity of the cathode catalyst was performed. The measurement results were as shown in FIG. The same evaluation as in Example 3 was performed.
表１に示される結果から分かるように、Ｐｔ４０％の例３のコアシェル粒子は、Ｐｔ１００％の例４の粒子よりもＰｔ含有量が少ないにも関わらず、触媒活性はＰｔ１００％の例４と同程度であった。 As can be seen from the results shown in Table 1, the core-shell particles of Example 3 with 40% Pt have the same catalytic activity as Example 4 with 100% Pt, despite having a lower Pt content than the particles of Example 4 with 100% Pt. It was about.
例５
本例ではコアシェル粒子を作製し、そのＳＴＥＭ−ＥＤＸによる組成分析を行った。具体的には以下のとおりである。
Example 5
In this example, core-shell particles were prepared, and their composition was analyzed by STEM-EDX. The details are as follows.
（１）コアシェル粒子の製造
例１と同様にして、Ｐｔ−Ｚｎ−Ｎｉ系コアシェル粒子を製造した。
(1) Production of core-shell particles In the same manner as in Example 1, Pt-Zn-Ni-based core-shell particles were produced.
（２）ＳＴＥＭ−ＥＤＸによる組成分析
ＳＴＥＭ−ＥＤＸ（走査透過型電子顕微鏡−エネルギー分散型Ｘ線分光分析器）（製品名：ＪＥＭ−ＡＲＭ２００Ｆ、日本電子社製）により、コアシェル粒子に対して組成分析を行った。その結果、図６Ａ〜６Ｂ及び７Ａ〜７Ｅに示されるように、Ｐｔ及びＮｉを含むコア粒子と、Ｚｎ及びＮｉを含むシェル層とが確認された。また、コアシェル粒子の全体組成はＰｔ３１Ｎｉ５２Ｚｎ１７であった。図６Ａにコアシェル粒子のＳＴＥＭ−ＥＤＸ像を、図６Ｂ、６Ｃ、６Ｄ及び６Ｅに、図６Ａに示されるＳＴＥＭ像に対応する、Ｎｉ、Ｐｔ及びＺｎの元素マッピング像、Ｎｉ単独の元素マッピング像、Ｐｔ単独の元素マッピング像、及びＺｎ単独の元素マッピング像をそれぞれ示す。また、図７Ａにコアシェル粒子の別のＳＴＥＭ−ＥＤＸ像を、図７Ｂ、７Ｃ、７Ｄ及び７Ｅに、図７Ａに示されるＳＴＥＭ像に対応する、Ｎｉ、Ｐｔ及びＺｎの元素マッピング像、Ｎｉ単独の元素マッピング像、Ｐｔ単独の元素マッピング像、及びＺｎ単独の元素マッピング像をそれぞれ示す。
(2) Composition analysis by STEM-EDX Composition analysis of core-shell particles by STEM-EDX (scanning transmission electron microscope-energy dispersive X-ray spectrometer) (product name: JEM-ARM200F, manufactured by JEOL Ltd.) Was done. As a result, as shown in FIGS. 6A to 6B and 7A to 7E, a core particle containing Pt and Ni and a shell layer containing Zn and Ni were confirmed. The overall composition of the core-shell particles was Pt 31 Ni 52 Zn 17 . FIG. 6A shows STEM-EDX images of the core-shell particles, and FIGS. 6B, 6C, 6D, and 6E show element mapping images of Ni, Pt, and Zn, corresponding to the STEM images shown in FIG. An element mapping image of Pt alone and an element mapping image of Zn alone are shown, respectively. 7A shows another STEM-EDX image of the core-shell particles, and FIGS. 7B, 7C, 7D, and 7E show the elemental mapping images of Ni, Pt, and Zn corresponding to the STEM images shown in FIG. 7A. An element mapping image, an element mapping image of Pt alone, and an element mapping image of Zn alone are shown, respectively.
１０ コアシェル粒子
１２ コア粒子
１４ シェル層
Reference Signs List 10 core-shell particles 12 core particles 14 shell layer
Claims (8)
主としてＰｔ及びＮｉで構成されるコア粒子と、
前記コア粒子を被覆する、主としてＺｎ及びＮｉで構成されるシェル層と、
を備えた、Ｐｔ−Ｚｎ−Ｎｉ系コアシェル粒子。 Pt-Zn-Ni-based core-shell particles composed of Pt, Zn and Ni,
Core particles mainly composed of Pt and Ni;
A shell layer mainly composed of Zn and Ni, which covers the core particles;
Pt-Zn-Ni-based core-shell particles comprising:
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