JP6044016B2 - High-concentration cerium trivalent fluorite-type undoped cerium oxide nanoparticle layer with excellent atmospheric stability and method for producing the same - Google Patents
High-concentration cerium trivalent fluorite-type undoped cerium oxide nanoparticle layer with excellent atmospheric stability and method for producing the same Download PDFInfo
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本発明は、７５％以上の高濃度Ｃｅ３＋を形成し、大気中にて高濃度Ｃｅ３＋を維持できる蛍石型アンドープ酸化セリウムナノ粒子層及びその作製方法に関するものである。 The present invention relates to a fluorite-type undoped cerium oxide nanoparticle layer capable of forming a high concentration Ce 3+ of 75% or more and maintaining the high concentration Ce 3+ in the atmosphere, and a method for producing the same.
通常、大気中に放置したアンドープ酸化セリウムナノ粒子（ＣＮＰ）は、大気中でより安定なセリウム４価（Ｃｅ４＋）に支配的となるため、セリウム４価と３価の価数比（Ｃｅ４＋/Ｃｅ３＋）は、おおよそ８０/２０となる。合成されたＣＮＰにおいて、粒子径を２−３ｎｍ程度まで小さくすると、高濃度Ｃｅ３＋を含むＣＮＰが得られる。例えば、非特許文献１には、平均粒径３ｎｍで４４％（Ｘ線光電子分光（ＸＰＳ）測定後、全ピーク１０本のピークフィッティングから算出）、非特許文献２には、平均粒径２．２ｎｍで８４％（ＸＰＳ測定後、ピーク４本から算出）、非特許文献３には、平均粒径２．６ｎｍで７４％（格子膨張法）のＣｅ３＋を含むＣＮＰが得られたことがそれぞれ報告されている。しかし、これまでに、Ｃｅ３ｄ軌道のＸＰＳスペクトルにてＣｅ４＋のみのピーク（〜９１６ｃｍ−１）が検出されない程の高濃度Ｃｅ３＋を含むアンドープ酸化セリウムナノ粒子の報告はまだない。 Usually, undoped cerium oxide nanoparticles (CNP) left in the atmosphere are dominant in cerium tetravalent (Ce 4+ ), which is more stable in the atmosphere, and therefore the valence ratio of cerium tetravalent to trivalent (Ce 4+ / Ce 3+ ) is approximately 80/20. In the synthesized CNP, when the particle diameter is reduced to about 2-3 nm, CNP containing high concentration Ce 3+ is obtained. For example, Non-Patent Document 1 has an average particle size of 3 nm and 44% (calculated from peak fitting of all 10 peaks after X-ray photoelectron spectroscopy (XPS) measurement). 84% (calculated from 4 peaks after XPS measurement) at 2 nm, and Non-Patent Document 3 shows that CNP containing Ce 3+ with an average particle size of 2.6 nm and 74% (lattice expansion method) was obtained. It has been reported. However, there have been no reports of undoped cerium oxide nanoparticles containing Ce 3+ at such a high concentration that Ce 4+ only peak (˜916 cm −1 ) is not detected in the XPS spectrum of Ce 3d orbital.
一方、金属セリウム基板を酸化させ形成したナノオーダ厚さの酸化セリウムナノ薄膜（ナノ粒子の層ではない）において、表面をアルゴンイオン照射することにより、超真空中で９０％以上の高濃度Ｃｅ３＋が形成できることが報告されている。しかし、雰囲気の酸素分圧が高まると、酸化セリウムナノ薄膜では再び酸化が生じ、形成されたＣｅ３＋は安定なＣｅ４＋に変換される。酸素雰囲気中１５分後には、９０％のＣｅ３＋濃度は１５−４０％まで低下することが、非特許文献４において報告されている。 On the other hand, a nano-thick cerium oxide nano thin film (not a nanoparticle layer) formed by oxidizing a metal cerium substrate is irradiated with argon ions on the surface to form a high concentration Ce 3+ of 90% or more in an ultra vacuum. It has been reported that it can be done. However, when the oxygen partial pressure in the atmosphere is increased, oxidation occurs again in the cerium oxide nanofilm, and the formed Ce 3+ is converted to stable Ce 4+ . It is reported in Non-Patent Document 4 that after 15 minutes in an oxygen atmosphere, the 90% Ce 3+ concentration decreases to 15-40%.
同様に金属基板上に形成した酸化セリウムフィルムでは、１０００Ｋ／６０ｍｉｎの熱処理により、高濃度Ｃｅ３＋が得られている。しかし、７００Ｋの酸化雰囲気では、再酸化が生じＣｅ４＋への変換される（非特許文献５）。 Similarly, in the cerium oxide film formed on the metal substrate, high concentration Ce 3+ is obtained by the heat treatment of 1000 K / 60 min. However, in an oxidizing atmosphere of 700K, re-oxidation occurs and is converted to Ce 4+ (Non-patent Document 5).
マイクロ又はナノメートルオーダの粒子径をもつ酸化セリウムナノ粒子をペレット状に成形し（ＣＮＰ成形体）、超真空雰囲気にてアルゴンイオン照射した場合、わずかではあるがＣｅ３＋を形成できる（非特許文献６）。しかし、この場合、非特許文献３の酸化セリウムナノ薄膜にアルゴンイオンを照射した場合のように、高濃度Ｃｅ３＋を有するＸＰＳスペクトルは得られていない。 When cerium oxide nanoparticles having a particle diameter of the order of micrometer or nanometer are formed into pellets (CNP compact) and irradiated with argon ions in an ultra-vacuum atmosphere, Ce 3+ can be formed to a slight extent (Non-patent Document 6). ). However, in this case, an XPS spectrum having a high concentration Ce 3+ is not obtained as in the case of irradiating argon ions to the cerium oxide nanofilm of Non-Patent Document 3.
本発明のこのような実情に鑑み、７５％以上の高濃度Ｃｅ３＋を有し、かつ、高濃度Ｃｅ３＋の状態を大気中にて１ヵ月以上維持できる蛍石型アンドープ酸化セリウムナノ粒子層とその作製方法を提供することを課題とする。 In view of such circumstances of the present invention, a fluorite-type undoped cerium oxide nanoparticle layer having a high concentration of Ce 3+ of 75% or more and capable of maintaining a high concentration of Ce 3+ in the atmosphere for one month or more and its It is an object to provide a manufacturing method.
発明１の方法は、基板に酸化セリウムナノ粒子を吸着させてナノオーダ厚さの酸化セリウムナノ粒子層を形成した後、前記酸化セリウムナノ粒子層にアルゴンイオンを照射することにより、濃度７５％以上のＣｅ３＋を形成し、室温かつ湿度６０％以下、酸素を含む大気中にて、少なくとも１ヶ月以上、その濃度７５％以上のＣｅ ３＋ の状態を維持できる大気安定性を有する蛍石型構造のアンドープ酸化セリウム粒子層を作製することを特徴とする。 In the method of the invention 1, after the cerium oxide nanoparticles are adsorbed on the substrate to form a nano-order cerium oxide nanoparticle layer, the cerium oxide nanoparticle layer is irradiated with argon ions, whereby Ce 3+ having a concentration of 75% or more is obtained. Fluorite-type undoped cerium oxide particles having an atmospheric stability that can be formed and maintained in a Ce 3+ state with a concentration of 75% or more for at least one month or more in an atmosphere containing oxygen at room temperature and humidity of 60% or less It is characterized by producing a layer .
ここで、大気安定性とは、室温且つ湿度６０％以下、酸素を含む大気中にて、少なくとも１ヵ月以上、７５％以上の高濃度Ｃｅ３＋を酸化セリウムナノ粒子に維持できることをいう。 Here, atmospheric stability means that cerium oxide nanoparticles can maintain a high concentration of Ce 3+ of 75% or more for at least one month or more in an atmosphere containing oxygen at room temperature and 60% or less.
また、熱曝露後の大気安定性とは、３００℃/１０ｍｉｎの熱曝露の後、少なくとも１ヵ月以上大気中において、高濃度Ｃｅ３＋の状態を維持できることをいう。 The atmospheric stability after heat exposure means that a high concentration Ce 3+ state can be maintained in the air for at least one month after 300 ° C./10 min heat exposure.
発明２の方法は、上記方法において、酸化セリウムナノ粒子層（ＣＮＰＬ）の膜厚を５０ｎｍ以下とする。 The method of the invention 2 makes the film thickness of the cerium oxide nanoparticle layer (CNPL) 50 nm or less in the above method.
発明３の方法は、上記方法において、アルゴンイオン照射前のＣＮＰＬに含まれるＣｅ４＋濃度がＣｅ３＋濃度に対してリッチであるものを用いる。 The method of the invention 3 uses the above method in which the Ce 4+ concentration contained in CNPL before irradiation with argon ions is richer than the Ce 3+ concentration.
発明４のアンドープ酸化セリウムナノ粒子層は、蛍型結晶構造を維持しつつ、濃度７５％以上のＣｅ３＋ を有し、室温かつ湿度６０％以下、酸素を含む大気中にて、少なくとも１ヶ月以上、その濃度７５％以上のＣｅ ３＋ の状態を維持できる大気安定性を有する特徴を有する。 The undoped cerium oxide nanoparticle layer of the invention 4 has a Ce 3+ concentration of 75% or more while maintaining a firefly crystal structure , and at least one month or more in an atmosphere containing oxygen at room temperature and humidity of 60% or less, It has the characteristic of having atmospheric stability that can maintain a Ce 3+ state with a concentration of 75% or more .
発明１〜３により、基板上の酸化セリウムナノ粒子層(ＣＮＰＬ)の厚さを、イオン照射の侵入厚さと同程度にすることにより、アルゴンイオン照射後に高濃度の酸素欠陥をＣＮＰＬに形成できる。ＣＮＰの内部までに酸素欠陥が導入される結果、電荷補償によりＣＮＰを構成する多くのＣｅ４＋はＣｅ３＋に変換される。このため、粒子内部からの酸素拡散を極力抑えられることから、高濃度Ｃｅ３＋を大気圧下で安定して維持できるようになった。そして、室温かつ湿度６０％以下、酸素を含む大気中にて、少なくとも１ヵ月以上、７５％以上の高濃度Ｃｅ３＋を維持でき、かつ、３００℃/１０ｍｉｎの熱曝露の後、少なくとも２ヵ月以上安定してその高濃度状態を維持できるようになった。さらに、基板を用いることにより、アルゴンイオン照射面の裏側からの酸化も抑えられる。 According to the first to third aspects, by setting the thickness of the cerium oxide nanoparticle layer (CNPL) on the substrate to the same level as the penetration depth of the ion irradiation, a high concentration oxygen defect can be formed in the CNPL after the argon ion irradiation. As a result of introducing oxygen vacancies into the CNP, a large amount of Ce 4+ constituting the CNP is converted to Ce 3+ by charge compensation. For this reason, since oxygen diffusion from inside the particles can be suppressed as much as possible, a high concentration Ce 3+ can be stably maintained under atmospheric pressure. It can maintain a high concentration of Ce 3+ of 75% or more in an atmosphere containing oxygen at room temperature and humidity of 60% or less for at least one month, and after heat exposure at 300 ° C./10 min for at least two months or more. The high concentration state can be stably maintained. Furthermore, by using a substrate, oxidation from the back side of the argon ion irradiation surface can be suppressed.
発明４により、７５％以上の高濃度Ｃｅ３＋を有し、大気中にて１ヵ月以上高濃度Ｃｅ３＋を安定して維持できる蛍石型アンドープ酸化セリウムナノ粒子層の提供が可能となった。 The invention 4 has 75% or more of the high concentration Ce 3+, was possible to provide a fluorite undoped cerium oxide nanoparticles layer over a month in the atmosphere at a high concentration Ce 3+ can be maintained stably.
以下、本発明を実施形態に基づいて詳細に説明する。 Hereinafter, the present invention will be described in detail based on embodiments.
本発明の酸化セリウムナノ粒子（ＣＮＰ）は、７５％以上、好ましくは８０％以上のＣｅ３＋濃度を含み大気安定性を有する蛍石型構造（立方晶）のアンドープ酸化セリウムナノ粒子である。 The cerium oxide nanoparticles (CNP) of the present invention are undoped cerium oxide nanoparticles having a Ce 3+ concentration of 75% or more, preferably 80% or more and having atmospheric stability and cubic stability.
本明細書において、「Ｃｅ３＋大気安定性」とは、室温かつ湿度６０％以下、酸素を含む大気中にて、少なくとも１ヵ月以上、７５％以上の高濃度Ｃｅ３＋を酸化セリウムナノ粒子層に維持できることをいう。また、「熱曝露後のＣｅ３＋大気安定性」とは、３００℃/１０ｍｉｎの熱曝露の後、少なくとも１ヵ月以上大気中において、高濃度Ｃｅ３＋の状態を維持できることをいう。 In this specification, “Ce 3+ atmospheric stability” means maintaining a high concentration of Ce 3+ of 75% or more in a cerium oxide nanoparticle layer for at least 1 month or more in an atmosphere containing oxygen at room temperature and humidity of 60% or less. Say what you can do. Further, “Ce 3+ atmospheric stability after heat exposure” means that a high concentration Ce 3+ state can be maintained in the atmosphere for at least one month after 300 ° C./10 min heat exposure.
図１に、本発明によるアンドープ酸化セリウムナノ粒子層（ＣＮＰＬ）に高濃度Ｃｅ３＋を形成する方法の一例を概念図で示す。 FIG. 1 is a conceptual diagram showing an example of a method for forming a high concentration Ce 3+ in an undoped cerium oxide nanoparticle layer (CNPL) according to the present invention.
図1において、例えばディップ法により基板（１）に酸化セリウムナノ粒子（ＣＮＰ）（２）を吸着させ、酸化セリウムナノ粒子層（ＣＮＰＬ）（３）を形成した後、アルゴンイオン（４）を照射することにより、７５％以上、より好ましくは８０％以上の高濃度Ｃｅ３＋を含む酸化セリウムナノ粒子層（５）を得ることができる。ここで、基板（１）の材料及びＣＮＰ（２）のＣｅ４＋/Ｃｅ３＋比に関して特に限定はない。本例では基板にはポリ乳酸基板を用いた。ＣＮＰには、Ｃｅ４＋/Ｃｅ３＋比が８０/２０程度の４価支配の汎用ＣＮＰを用いることができる。ナノ粒子層（３）の膜厚は、吸着時間とアルゴンイオン照射時間により制御し、イオン照射侵入深さの観点から、５０ｎｍ以下、好ましくは１０ｎｍ以下であり、その下限はナノ粒子の直径の１ｎｍ程度である。イオン照射条件は、ナノ粒子の脱落と酸素欠陥形成との兼ね合いから、ＲＦ出力を３００Ｗ以下、照射時間を１分程度とすることが望ましい。 In FIG. 1, cerium oxide nanoparticles (CNP) (2) are adsorbed on a substrate (1) by, for example, a dip method to form a cerium oxide nanoparticle layer (CNPL) (3), and then irradiated with argon ions (4). Thus, a cerium oxide nanoparticle layer (5) containing a high concentration Ce 3+ of 75% or more, more preferably 80% or more can be obtained. Here, there is no particular limitation regarding the material of the substrate (1) and the Ce 4+ / Ce 3+ ratio of the CNP (2). In this example, a polylactic acid substrate was used as the substrate. As the CNP, a 4-valent CNP having a Ce 4+ / Ce 3+ ratio of about 80/20 can be used. The film thickness of the nanoparticle layer (3) is controlled by the adsorption time and the argon ion irradiation time, and is 50 nm or less, preferably 10 nm or less, from the viewpoint of ion irradiation penetration depth, and the lower limit is 1 nm of the diameter of the nanoparticle. Degree. As for the ion irradiation conditions, it is desirable that the RF output is 300 W or less and the irradiation time is about 1 minute in consideration of the dropping of the nanoparticles and the formation of oxygen defects.
上記方法によれば、基板（１）上の酸化セリウムナノ粒子層（３）の厚さを調節し、ナノ粒子層（３）の厚さを照射侵入厚さと同程度にすることにより、アルゴンイオン照射を用いて高濃度の酸素欠陥を酸化セリウムナノ粒子層（５）中に形成できるようになる。また、これにより作製されたアンドープ酸化セリウムナノ粒子は、ナノ粒子の内部までに高濃度のＣｅ３＋を形成できるため、粒子内部からの酸素拡散を極力抑えられる。さらに、基板（１）を用いることにより、アルゴンイオン照射面の裏側からの酸化も抑えられる。したがって、高濃度Ｃｅ３＋を大気圧下で安定して維持できるようになると考えられる。その結果、室温かつ湿度６０％以下、酸素を含む大気中にて、少なくとも１ヵ月以上、７５％以上、より好ましくは８０％以上のＣｅ３＋濃度を含む酸化セリウムナノ粒子を維持できる（Ｃｅ３＋大気安定性）。さらに、３００℃/１０ｍｉｎの熱曝露の後、２ヵ月以上安定してその高濃度Ｃｅ３＋状態が維持できるようになる（熱曝露後のＣｅ３＋大気安定性）。 According to the above method, argon ion irradiation is performed by adjusting the thickness of the cerium oxide nanoparticle layer (3) on the substrate (1) and making the thickness of the nanoparticle layer (3) comparable to the irradiation penetration thickness. Can be used to form a high concentration of oxygen defects in the cerium oxide nanoparticle layer (5). Moreover, since the undoped cerium oxide nanoparticles produced thereby can form a high concentration of Ce 3+ up to the inside of the nanoparticles, oxygen diffusion from the inside of the particles can be suppressed as much as possible. Furthermore, by using the substrate (1), oxidation from the back side of the argon ion irradiated surface can be suppressed. Therefore, it is considered that the high concentration Ce 3+ can be stably maintained under atmospheric pressure. As a result, cerium oxide nanoparticles having a Ce 3+ concentration of at least one month, 75% or more, more preferably 80% or more can be maintained in an atmosphere containing oxygen at room temperature and humidity of 60% or less (Ce 3+ atmospheric stability). sex). Furthermore, after the heat exposure at 300 ° C./10 min, the high concentration Ce 3+ state can be stably maintained for 2 months or longer (Ce 3+ atmospheric stability after heat exposure).
本発明の高濃度Ｃｅ３＋含有アンドープ酸化セリウムナノ粒子を高温で用いる場合には、大気環境温度を３００℃以下とすることが望ましい。 When the high-concentration Ce 3+ containing undoped cerium oxide nanoparticles of the present invention are used at a high temperature, it is desirable that the atmospheric environment temperature be 300 ° C. or lower.
次に、本発明の実施例を述べる。
（実施例１）
ポリ乳酸基板にディップ法により酸化セリウムナノ粒子層（ＣＮＰＬ）を形成した。酸化セリウムナノ粒子の平均粒径は３ｎｍ以下であり、アルゴンイオン照射前のＣＮＰＬの膜厚は１０−２０ｎｍであった。また、真空中のＸＰＳ測定の結果、Ａｒ照射前のＣＮＰＬのＣｅ４＋濃度は、約７０〜８０％、Ｃｅ３＋濃度は約２０〜３０％であった。
Next, examples of the present invention will be described.
Example 1
A cerium oxide nanoparticle layer (CNPL) was formed on a polylactic acid substrate by dipping. The average particle diameter of the cerium oxide nanoparticles was 3 nm or less, and the film thickness of CNPL before irradiation with argon ions was 10-20 nm. Further, as a result of XPS measurement in vacuum, the Ce 4+ concentration of CNPL before Ar irradiation was about 70 to 80%, and the Ce 3+ concentration was about 20 to 30%.
次に、上記のＣＮＰＬに、ＲＦ出力３００Ｗで１分間、アルゴンイオンを照射し、７５％以上の高濃度Ｃｅ３＋を含む本発明の実施例のＣＮＰＬを形成した。 Next, the CNPL was irradiated with argon ions at an RF output of 300 W for 1 minute to form a CNPL of an example of the present invention containing a high concentration of Ce 3+ of 75% or more.
図２に、アルゴンイオン照射前後のＣＮＰＬにおけるＣｅ３ｄスペクトルを示す。横軸が結合エネルギー（ｅＶ）、縦軸はスペクトル強度（任意単位）である。この図から、アルゴンイオン照射後にはＣｅ４＋のみに由来する９１６ｃｍ−１のピークが完全に消えており、高濃度Ｃｅ３＋を含むＣＮＰＬが形成されていることが確認できる。
（実施例２、比較例）
また、図３に、上記実施例１と同様にして作製した高濃度Ｃｅ３＋含有の酸化セリウムナノ粒子層（ＣＮＰＬ）を大気曝露させ、Ｃｅ３＋濃度の変化を観察した。横軸が大気曝露時間、縦軸はＸＰＳ測定結果より全ピーク１０本の強度から算出したＣｅ３＋濃度である。また、比較例として、実施例１において用いたアルゴンイオン照射前の酸化セリウムナノ粒子（ＣＮＰ）を用いて、直径４ｍｍ×厚さ１ｍｍのＣＮＰ成形体を作製し、上記実施例と同条件でアルゴンイオン照射し、比較例とした。このＣＮＰ成形体についても同様に大気曝露させ、Ｃｅ３＋濃度の変化を観察した。
FIG. 2 shows Ce3d spectra in CNPL before and after argon ion irradiation. The horizontal axis represents the binding energy (eV), and the vertical axis represents the spectral intensity (arbitrary unit). From this figure, it can be confirmed that the peak of 916 cm −1 derived only from Ce 4+ disappears completely after irradiation with argon ions, and CNPL containing high concentration Ce 3+ is formed .
(Example 2, comparative example)
Further, in FIG. 3, a high concentration Ce 3+ containing cerium oxide nanoparticle layer (CNPL) produced in the same manner as in Example 1 was exposed to the atmosphere, and the change in the Ce 3+ concentration was observed. The horizontal axis represents the atmospheric exposure time, and the vertical axis represents the Ce 3+ concentration calculated from the intensity of all 10 peaks from the XPS measurement result. As a comparative example, a CNP compact having a diameter of 4 mm and a thickness of 1 mm was produced using the cerium oxide nanoparticles (CNP) before irradiation with argon ions used in Example 1, and argon ions were formed under the same conditions as in the above examples. Irradiated and used as a comparative example. The CNP compact was exposed to the air in the same manner, and changes in Ce 3+ concentration were observed.
図３より、比較例のＣＮＰ成形体では、大気曝露２ｈ以降から再酸化が生じ、Ｃｅ３＋が減少しはじめ、遅くとも３日後にはＣｅ４＋が支配的（Ｃｅ４＋＞８０％）となった。一方、実施例１のＣＮＰＬでは、少なくとも４７日間は、８０％以上の高濃度Ｃｅ３＋が維持できることが確認された。
（実施例３）
また、図４に、上記実施例１と同様にして作製した高濃度Ｃｅ３＋含有のＣＮＰＬについてＸ線回折（ＸＲＤ）回折実験を行った結果を示す。この図から、上記実施例１で作製した高濃度Ｃｅ３＋含有のＣＮＰＬは、Ｃｅ２Ｏ３の結晶構造ではなく、ＣｅＯ２の蛍石型構造であることが確認された。
（実施例４）
また、図５に、上記実施例１と同様にして作製した高濃度Ｃｅ３＋含有のＣＮＰＬについて、大気中にて５００℃までの熱曝露試験を行い、試験後のＣｅ３＋濃度を調べた。熱曝露時間は１０ｍｉｎとした。
From FIG. 3, in the CNP molded body of the comparative example, re-oxidation occurred after exposure to the atmosphere for 2 h, Ce 3+ began to decrease, and Ce 4+ became dominant (Ce 4+ > 80%) after 3 days at the latest. On the other hand, in the CNPL of Example 1, it was confirmed that a high concentration Ce 3+ of 80% or more can be maintained for at least 47 days.
Example 3
FIG. 4 shows the results of X-ray diffraction (XRD) diffraction experiments performed on CNPL containing high concentration Ce 3+ produced in the same manner as in Example 1. From this figure, it was confirmed that the CNPL containing high concentration Ce 3+ produced in Example 1 has a CeO 2 fluorite structure, not a Ce 2 O 3 crystal structure.
Example 4
Further, in FIG. 5, a high-concentration Ce 3+ containing CNPL produced in the same manner as in Example 1 was subjected to a heat exposure test up to 500 ° C. in the atmosphere, and the Ce 3+ concentration after the test was examined. The heat exposure time was 10 min.
図５から、３００℃を超えると再酸化がはじまり、３００℃から３５０℃の温度範囲において、Ｃｅ３＋濃度が約２０％まで低下しはじめ、３５０℃以上の温度ではアルゴンイオン照射前のＣｅ３＋濃度の状態に戻った。
（実施例５）
さらに、図６に示すように、上記実施例１と同様にして作製した高濃度Ｃｅ３＋含有のＣＮＰＬについて、３００℃／１０ｍｉｎで熱曝露を行った後、大気曝露し、その後のＣｅ３＋濃度変化を調べた。その結果、高濃度Ｃｅ３＋の状態が少なくとも２ヵ月維持できることが確認された。
From FIG. 5, when the temperature exceeds 300 ° C., reoxidation starts, and in the temperature range from 300 ° C. to 350 ° C., the Ce 3+ concentration starts to decrease to about 20%, and at a temperature of 350 ° C. or higher, the Ce 3+ concentration before irradiation with argon ions. Returned to the state.
(Example 5)
Further, as shown in FIG. 6, the high concentration Ce 3+ containing CNPL produced in the same manner as in Example 1 was exposed to heat at 300 ° C./10 min, then exposed to the atmosphere, and then changed in Ce 3+ concentration. I investigated. As a result, it was confirmed that the high concentration Ce 3+ state could be maintained for at least 2 months.
本発明の「高濃度Ｃｅ３＋大気安定性を有する蛍石型アンドープ酸化セリウムナノ粒子層」は、燃料電池材料、酸素貯蔵材料、自動車用排気ガス触媒などへの応用の可能性が期待される。 The “fluorite-type undoped cerium oxide nanoparticle layer having high concentration Ce 3+ atmospheric stability” of the present invention is expected to be applicable to fuel cell materials, oxygen storage materials, automobile exhaust gas catalysts, and the like.
１ 基板
２ 酸化セリウムナノ粒子（ＣＮＰ）
３ 酸化セリウムナノ粒子層（ＣＮＰＬ）
４ アルゴンイオン
５ 高濃度Ｃｅ３＋を有する酸化セリウムナノ粒子層
1 Substrate 2 Cerium oxide nanoparticles (CNP)
3 Cerium oxide nanoparticle layer (CNPL)
4 Argon ions 5 Cerium oxide nanoparticle layer with high concentration of Ce 3+
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