JP4170930B2 - Anisotropic phase-separated bimetallic nanoparticles and production method thereof - Google Patents
Anisotropic phase-separated bimetallic nanoparticles and production method thereof Download PDFInfo
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- 239000002105 nanoparticle Substances 0.000 title claims description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 9
- 229920005862 polyol Polymers 0.000 claims description 9
- 150000003077 polyols Chemical class 0.000 claims description 9
- -1 thiol compound Chemical class 0.000 claims description 9
- 238000005191 phase separation Methods 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 7
- QJAOYSPHSNGHNC-UHFFFAOYSA-N octadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCCCS QJAOYSPHSNGHNC-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 229910000510 noble metal Inorganic materials 0.000 claims description 5
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- BTOOAFQCTJZDRC-UHFFFAOYSA-N 1,2-hexadecanediol Chemical compound CCCCCCCCCCCCCCC(O)CO BTOOAFQCTJZDRC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 229940031723 1,2-octanediol Drugs 0.000 claims description 2
- 159000000021 acetate salts Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 2
- AEIJTFQOBWATKX-UHFFFAOYSA-N octane-1,2-diol Chemical compound CCCCCCC(O)CO AEIJTFQOBWATKX-UHFFFAOYSA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 238000004220 aggregation Methods 0.000 claims 1
- 230000002776 aggregation Effects 0.000 claims 1
- 150000003568 thioethers Chemical class 0.000 claims 1
- 229910018936 CoPd Inorganic materials 0.000 description 15
- 239000012071 phase Substances 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 6
- 239000002082 metal nanoparticle Substances 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 230000005291 magnetic effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 2
- DWANEFRJKWXRSG-UHFFFAOYSA-N 1,2-tetradecanediol Chemical compound CCCCCCCCCCCCC(O)CO DWANEFRJKWXRSG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- BKFAZDGHFACXKY-UHFFFAOYSA-N cobalt(II) bis(acetylacetonate) Chemical compound [Co+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O BKFAZDGHFACXKY-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- YYGNTYWPHWGJRM-UHFFFAOYSA-N (6E,10E,14E,18E)-2,6,10,15,19,23-hexamethyltetracosa-2,6,10,14,18,22-hexaene Chemical compound CC(C)=CCCC(C)=CCCC(C)=CCCC=C(C)CCC=C(C)CCC=C(C)C YYGNTYWPHWGJRM-UHFFFAOYSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical class C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- BHEOSNUKNHRBNM-UHFFFAOYSA-N Tetramethylsqualene Natural products CC(=C)C(C)CCC(=C)C(C)CCC(C)=CCCC=C(C)CCC(C)C(=C)CCC(C)C(C)=C BHEOSNUKNHRBNM-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N dodecahydrosqualene Natural products CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 1
- ZITKDVFRMRXIJQ-UHFFFAOYSA-N dodecane-1,2-diol Chemical compound CCCCCCCCCCC(O)CO ZITKDVFRMRXIJQ-UHFFFAOYSA-N 0.000 description 1
- 238000001941 electron spectroscopy Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- IGMQODZGDORXEN-UHFFFAOYSA-N pentadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCS IGMQODZGDORXEN-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229940031439 squalene Drugs 0.000 description 1
- TUHBEKDERLKLEC-UHFFFAOYSA-N squalene Natural products CC(=CCCC(=CCCC(=CCCC=C(/C)CCC=C(/C)CC=C(C)C)C)C)C TUHBEKDERLKLEC-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、その物理的・化学的特性から磁性化学の分野や触媒化学の分野などでその用途が大いに期待される、異方的に相分離した二元金属ナノ粒子とその製造法に関する。 The present invention relates to an anisotropic phase-separated bimetallic nanoparticle and its production method, which are expected to be used in the fields of magnetic chemistry and catalytic chemistry because of its physical and chemical properties.
金属ナノ粒子は、物理的・化学的特性において、バルク金属では見られない特異な性質を発揮する。その中で、二種の金属種から成るものは二元金属ナノ粒子と呼ばれ、対応する単一金属ナノ粒子とは異なった磁気的、触媒的、電気的、光学的特性を示す点で非常に興味深い。
二元金属ナノ粒子の物理的・化学的特性には、粒子中の金属種の分布が大きな影響を及ぼす。有機配位子存在下で二種類の金属塩を還元する通常の化学合成法で得られる二元金属ナノ粒子は、一般に各金属種がランダムに配置した合金構造、或いは、一方の金属ナノ粒子を他方の金属種が包み込んだコア−シェル構造を持ち、相分離構造としては何れも等方的であり、異方的な相分離構造を有する二元金属ナノ粒子はこれまでに未だ合成されていない。
Metal nanoparticles exhibit unique properties that are not found in bulk metals in physical and chemical properties. Among them, those composed of two kinds of metal are called bimetallic nanoparticles, which are very different in that they exhibit different magnetic, catalytic, electrical, and optical properties than the corresponding single metal nanoparticles. Interesting.
The distribution of metal species in the particles greatly affects the physical and chemical properties of the bimetallic nanoparticles. Binary metal nanoparticles obtained by the usual chemical synthesis method that reduces two kinds of metal salts in the presence of organic ligands generally have an alloy structure in which each metal species is randomly arranged, or one metal nanoparticle. The other metal species has a core-shell structure and is isotropic as a phase separation structure, and bimetallic nanoparticles having an anisotropic phase separation structure have not yet been synthesized. .
本発明は、上記した如き現状に鑑みなされたもので、これまでに合成されたことのない、異方的な相分離構造を有する二元金属ナノ粒子とその製造法を提供することを目的とする。 The present invention has been made in view of the current situation as described above, and aims to provide a bimetallic nanoparticle having an anisotropic phase separation structure that has never been synthesized and a method for producing the same. To do.
本発明は、チオール化合物の存在下、２種の金属塩を高温でポリオール還元することを特徴とする、異方的に相分離した二元金属ナノ粒子の製造法に関する。 The present invention relates to a method for producing anisotropically phase-separated bimetallic nanoparticles, wherein two kinds of metal salts are polyol-reduced at a high temperature in the presence of a thiol compound.
また、本発明は、上記製造法等により得られる異方的に相分離した二元金属ナノ粒子に関する。 The present invention also relates to anisotropically phase-separated binary metal nanoparticles obtained by the above production method and the like.
本発明は、単純な液相合成反応により、これまでに得ることが出来なかった異方性相分離構造を有する二元金属ナノ粒子を容易に且つ大量に合成することができる点に顕著な効果を奏する。また、本発明の製造法において、チオール化合物の種類や量を変えることにより、ナノ粒子の粒径を制御することが可能であり、また、用いる金属の組み合わせを変えることにより、種々の異方性相分離構造を有する二元金属ナノ粒子の合成が可能となる点でもその効果は大きい。 The present invention has a remarkable effect in that bimetallic nanoparticles having an anisotropic phase separation structure that could not be obtained so far can be synthesized easily and in large quantities by a simple liquid phase synthesis reaction. Play. In the production method of the present invention, the particle size of the nanoparticles can be controlled by changing the type and amount of the thiol compound, and various anisotropies can be obtained by changing the combination of metals used. The effect is also great in that a bimetallic nanoparticle having a phase separation structure can be synthesized.
本発明の製造法において、チオール化合物は、硫黄供給源ならびに保護剤として用いられるが、そのような目的で用いられるチオール化合物の好ましい例としては、例えば、アルカンチオール等が挙げられる。
アルカンチオールの炭素数は、特に限定されるものではないが、例えば、高温での反応を高沸点溶媒中で行う場合等に、不安定で沈殿を生じる虞のある低級アルカンチオールは、あまり好ましくないので、通常は、当該高沸点溶媒に溶解し得る、炭素数８以上のアルカンチオールが好ましく用いられる。
好ましいアルカンチオールの具体例としては、例えば、１−オクタンチオール、１−ドデカンチオール、１−ペンタデカンチオール、１−オクタデカンチオール等が挙げられるが、勿論これらに限定されるものではない。
In the production method of the present invention, the thiol compound is used as a sulfur supply source and a protective agent. Preferred examples of the thiol compound used for such a purpose include alkanethiol and the like.
The number of carbons of the alkanethiol is not particularly limited. For example, when the reaction at a high temperature is performed in a high boiling point solvent, a lower alkanethiol that is unstable and may cause precipitation is not preferable. Therefore, usually an alkanethiol having 8 or more carbon atoms that can be dissolved in the high boiling point solvent is preferably used.
Specific examples of preferable alkanethiol include, but are not limited to, 1-octanethiol, 1-dodecanethiol, 1-pentadecanethiol, 1-octadecanethiol, and the like.
本発明の製造法において用いられる２種の金属塩としては、一方が３ｄ−遷移金属の金属塩で、他方が貴金属の金属塩であることが望ましい。
３ｄ−遷移金属としては、例えば、鉄、コバルト、ニッケル、銅等が挙げられ、貴金属としては、例えば、パラジウム、白金、金、銀等が挙げられる。
これらの金属の塩としては、特に限定されるものではないが、例えば、アセチルアセトナート塩や酢酸塩、塩化物等が好ましいものとして挙げられる。
As the two kinds of metal salts used in the production method of the present invention, it is desirable that one is a metal salt of a 3d-transition metal and the other is a metal salt of a noble metal.
Examples of the 3d-transition metal include iron, cobalt, nickel, and copper, and examples of the noble metal include palladium, platinum, gold, and silver.
These metal salts are not particularly limited, and preferred examples include acetylacetonate salts, acetate salts, and chlorides.
本発明の製造法において用いられるポリオールとしては、特に限定されるものではないが、反応温度より高い沸点を有するものが好ましい。そのようなポリオールの好ましい例としては、例えば、１，２−オクタンジオール、１，２−ドデカンジオール、１，２−テトラデカンジオール、１，２−ヘキサデカンジオール等が挙げられる。 Although it does not specifically limit as a polyol used in the manufacturing method of this invention, What has a boiling point higher than reaction temperature is preferable. Preferable examples of such polyols include 1,2-octanediol, 1,2-dodecanediol, 1,2-tetradecanediol, 1,2-hexadecanediol, and the like.
本発明の製造法におけるポリオール還元は高温で行われることを要するが、反応温度としては、通常１００℃以上、好ましくは１５０℃以上、より好ましくは２００℃以上である。
反応時間は、反応温度や用いる試薬の種類、その他の反応条件等により自ずから異なり一様ではないが、通常数十分〜数時間程度である。
反応は、通常、高沸点溶媒中で行われるが、使用可能な高沸点溶媒としては、沸点が１００℃以上、好ましくは１５０℃以上、より好ましくは２００℃以上であって、反応に用いる金属塩やポリオール類を溶解し得るものであることが望ましい。
本発明で用いられる高沸点溶媒の具体例としては、例えば、ジ−ｎ−オクチルエーテル、トリオクチルアミン、オクタデセン、スクアレン等が好ましいものとして挙げられるが、勿論これらに限定されるものではない。
本発明に係る反応は、窒素、アルゴン等の不活性ガス雰囲気中で行うのが好ましい。
The polyol reduction in the production method of the present invention needs to be performed at a high temperature, but the reaction temperature is usually 100 ° C. or higher, preferably 150 ° C. or higher, more preferably 200 ° C. or higher.
The reaction time varies depending on the reaction temperature, the type of reagent used, other reaction conditions, etc., and is not uniform, but is usually about several tens of minutes to several hours.
The reaction is usually carried out in a high boiling point solvent, and usable high boiling point solvents are those having a boiling point of 100 ° C. or higher, preferably 150 ° C. or higher, more preferably 200 ° C. or higher. It is desirable that it can dissolve polyols and polyols.
Specific examples of the high boiling point solvent used in the present invention include, for example, di-n-octyl ether, trioctylamine, octadecene, squalene, and the like, but it is not limited thereto.
The reaction according to the present invention is preferably carried out in an inert gas atmosphere such as nitrogen or argon.
本発明の製造法により得られた異方的に相分離した二元金属ナノ粒子は、２種の金属の硫化物を含んでなるものであるが、２種の金属としては、その一方がＦｅ、Ｃｏ、Ｎｉ、Ｃｕ等の３ｄ−遷移金属であり、他方がＰｄ、Ｐｔ、Ａｕ、Ａｇ等の貴金属であるものが好ましい。 The anisotropically phase-separated binary metal nanoparticles obtained by the production method of the present invention comprise two kinds of metal sulfides. One of the two kinds of metals is Fe. , Co, Ni, Cu and the like are preferable, and the other is a noble metal such as Pd, Pt, Au, and Ag.
本発明の製造法により得られた異方的に相分離した二元金属ナノ粒子、例えば、窒素雰囲気下、チオール存在下で、Ｃｏ（ａｃａｃ）２・２Ｈ２Ｏ及びＰｄ（ａｃａｃ）２（式中、ａｃａｃはアセチルアセトナート基の略）のポリオール還元により合成したＣｏＰｄ二元金属ナノ粒子のＨＲＴＥＭ（高分解能ＴＥＭ）像を図１に示す。この粒子は、その形状とコントラストの相違から本発明者らは“ナノどんぐり”と名付けた。
ＣｏＰｄナノどんぐりは、ＴＥＭ観察及びＥＤＸ分析から、粒子の明るい相にはＣｏが、また、暗い相にはＰｄが多く含まれていることが判った。また、ＸＲＤ（Ｘ線ダイオード）測定及びＸＰＳ（Ｘ線電子分光法）測定から、Ｃｏ相は結晶性Ｃｏ９Ｓ８、Ｐｄ相は未知の非結晶性ＰｄＳＸから成ることが分かった。更に、ＵＶ−ｖｉｓ（紫外・可視）測定及びＴＥＭ観察で生成過程を追跡した結果、まずＰｄ粒子が生成し、それを核としてＣｏ相が異方的に成長することが明らかになった。
本発明による成果は、異方性相分離二元金属ナノ粒子合成の世界で最初の例で、その結晶構造においても、結晶性Ｃｏ相と非晶質性Ｐｄ相の対照的な組み合わせとなっており、非常に興味深いものである。
Anisotropic phase separated bimetallic nanoparticles obtained by the production method of the present invention, for example, Co (acac) 2 .2H 2 O and Pd (acac) 2 (formula FIG. 1 shows an HRTEM (high resolution TEM) image of CoPd bimetallic nanoparticles synthesized by polyol reduction (acac is an abbreviation for acetylacetonate group). We named this particle “Nano Acorn” because of the difference in shape and contrast.
From the TEM observation and EDX analysis, the CoPd nano acorn was found to contain Co in the bright phase of the particles and Pd in the dark phase. Further, from XRD (X-ray diode) measurement and XPS (X-ray electron spectroscopy) measurement, it was found that the Co phase was made of crystalline Co 9 S 8 and the Pd phase was made of unknown amorphous PdS X. Furthermore, as a result of tracing the generation process by UV-vis (ultraviolet / visible) measurement and TEM observation, it was revealed that Pd particles were generated first, and the Co phase grew anisotropically using the Pd particles.
The result of the present invention is the first example in the world of anisotropic phase-separated bimetallic nanoparticles synthesis, and the crystal structure is a contrasting combination of a crystalline Co phase and an amorphous Pd phase. And very interesting.
以下、実施例により本発明をより具体的に説明するが、本発明はこれら実施例により何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited at all by these Examples.
ジ−ｎ−オクチルエーテル（１３．５ｍＬ）にコバルトアセチルアセトナート二水和物（Ｃｏ（ａｃａｃ）２・２Ｈ２Ｏ、０．５ｍｍｏｌ）、パラジウムアセチルアセトナート（Ｐｄ（ａｃａｃ）２、０．５ｍｍｏｌ）、及び１−オクタデカンチオール（Ｃ１８ＳＨ、１．０ｍｍｏｌ）を添加し、減圧にして酸素を除去した後、この溶液を窒素雰囲気中で２２０℃で１０分間加熱し、金属塩を完全に溶解させた。次いで、その溶液に還元剤の１，２−ヘキサデカンジオール（１．５ｍｍｏｌ）を添加し、約２４０℃で３０分間撹拌して、反応を完結させた。得られた黒色の溶液にエタノール（４０ｍＬ）を添加すると黒色の沈殿物が得られた。これを遠心分離し、ヘキサン（５０ｍＬ）中に再分散させることにより、異方性相分離した含硫黄ＣｏＰｄナノ粒子（ナノどんぐり）が得られた。得られた含硫黄ＣｏＰｄナノどんぐりの高分解能ＴＥＭ像から、Ｃｏ部は結晶性Ｃｏ９Ｓ８より、Ｐｄ部は非晶性ＰｄＳＸよりなることが判った。 Di-n-octyl ether (13.5 mL) to cobalt acetylacetonate dihydrate (Co (acac) 2 .2H 2 O, 0.5 mmol), palladium acetylacetonate (Pd (acac) 2 , 0.5 mmol) ), And 1-octadecanethiol (C 18 SH, 1.0 mmol) was added to remove oxygen by reducing the pressure, and the solution was heated at 220 ° C. for 10 minutes in a nitrogen atmosphere to completely dissolve the metal salt. I let you. Next, 1,2-hexadecanediol (1.5 mmol) as a reducing agent was added to the solution, and the mixture was stirred at about 240 ° C. for 30 minutes to complete the reaction. When ethanol (40 mL) was added to the resulting black solution, a black precipitate was obtained. This was centrifuged and redispersed in hexane (50 mL) to obtain anisotropic phase-separated sulfur-containing CoPd nanoparticles (nano acorns). From the high-resolution TEM image of the obtained sulfur-containing CoPd nanoacorn, it was found that the Co portion was made of crystalline Co 9 S 8 and the Pd portion was made of amorphous PdS X.
図２Ａに、平均サイズ約１４ｎｍ（長さ）×１０ｎｍ（幅）で、Ｃｏ／Ｐｄ原子比が４０／６０のＣ１８Ｓで保護したＣｏＰｄナノどんぐりの低分解能ＴＥＭ像を示す。大部分の粒子がドングリの形状で明るい相と暗い相の両方からできているのと同時に、少量成分として球状の暗い粒子が存在している。ＴＥＭの特性を考慮に入れれば、この明るい相と暗い相は、それぞれ、コバルト原子及びパラジウム原子で占められていると予想される。なお、挿入図はＴＥＭ像の拡大図である。
図２Ｂに、拡大したＴＥＭ像の中で丸印で示したナノどんぐり及びナノ粒子のエネルギー分散Ｘ線（ＥＤＸ）スペクトルを示す。２．８４ｋｅＶ（ＰｄＬα）、２．９９ｋｅＶ（ＰｄＬβ）、６．９３ｋｅＶ（ＣｏＫα）及び７．６５ｋｅＶ（ＣｏＫβ）のＥＤＸの結果から、図２Ｃに示すようにコバルト原子とパラジウム原子が位置していることが確認された。
FIG. 2A shows a low-resolution TEM image of a CoPd nanoacorn protected with C 18 S having an average size of about 14 nm (length) × 10 nm (width) and a Co / Pd atomic ratio of 40/60. While most of the particles are acorn-shaped and made of both bright and dark phases, there are spherical dark particles as minor components. Taking into account the properties of TEM, this bright and dark phase is expected to be occupied by cobalt and palladium atoms, respectively. The inset is an enlarged view of the TEM image.
FIG. 2B shows an energy dispersive X-ray (EDX) spectrum of nano acorns and nanoparticles indicated by circles in the enlarged TEM image. From the EDX results of 2.84 keV (PdL α ), 2.99 keV (PdL β ), 6.93 keV (CoK α ), and 7.65 keV (CoK β ), the cobalt atom and the palladium atom are positioned as shown in FIG. 2C. It was confirmed that
図３ＡにＣｏＰｄナノどんぐりの高分解能ＴＥＭ像を示す。ここで、Ｃｏ相は結晶性であるのに対し、Ｐｄ相は非晶性であることが読みとれる。
図３ＢにＡの長方形領域におけるコバルト相のフーリエ変換により得られた光学解析像を示す。得られた光学回折像は、［110］方向においてＣｏ９Ｓ８のそれとよい一致を示した
図３Ｃ及びＤに、ドデカンチオール存在下で合成したＣｏＰｄナノどんぐり及びナノ粒子のＸＲＤパターンをそれぞれ示す（図３Ｃ中の●は結晶性Ｃｏ９Ｓ８に、×は非晶性ＰｄＳＸに帰属される。）。
FIG. 3A shows a high-resolution TEM image of the CoPd nano acorn. Here, it can be read that the Co phase is crystalline while the Pd phase is amorphous.
FIG. 3B shows an optical analysis image obtained by Fourier transform of the cobalt phase in the rectangular region A. The obtained optical diffraction images showed good agreement with that of Co 9 S 8 in the [110] direction. FIGS. 3C and D show the XRD patterns of CoPd nano acorns and nanoparticles synthesized in the presence of dodecanethiol, respectively. In FIG. 3C, ● is assigned to crystalline Co 9 S 8 and x is assigned to amorphous PdS X ).
本発明に係る異方的に相分離した二元金属ナノ粒子の大きさ、形状、及び組成のみならず、その相分離の仕様を調節することは、２つの金属種の界面が、その電気的、光学的、磁気的及び触媒的性質に大きな役割を果たすことが多いために、基礎技術、応用技術の何れの面においても重要である。
本発明に係る異方的に相分離した二元金属ナノ粒子、例えば、今回合成した含硫黄ＣｏＰｄナノ粒子は、自発磁化の発現や、特異的な触媒反応など、予想できない物理的・化学的特性を有していると考えられるので、磁性化学の分野や触媒化学の分野などで種々の用途が期待出来、産業上の利用可能性は極めて大きいものと思われる。
Adjusting not only the size, shape, and composition of the anisotropically phase separated bimetallic nanoparticles according to the present invention, but also the phase separation specifications, the interface between the two metal species Often, it plays an important role in optical, magnetic and catalytic properties, and is important in both basic and applied technologies.
Anisotropic phase-separated bimetallic nanoparticles according to the present invention, for example, the sulfur-containing CoPd nanoparticles synthesized this time, have unforeseeable physical and chemical properties such as spontaneous magnetization and specific catalytic reactions. Therefore, various applications can be expected in the fields of magnetic chemistry and catalytic chemistry, and the industrial applicability is considered to be extremely large.
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