JP6481997B2 - Supported catalyst - Google Patents
Supported catalyst Download PDFInfo
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- JP6481997B2 JP6481997B2 JP2015039662A JP2015039662A JP6481997B2 JP 6481997 B2 JP6481997 B2 JP 6481997B2 JP 2015039662 A JP2015039662 A JP 2015039662A JP 2015039662 A JP2015039662 A JP 2015039662A JP 6481997 B2 JP6481997 B2 JP 6481997B2
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- 239000003054 catalyst Substances 0.000 title claims description 56
- 239000002245 particle Substances 0.000 claims description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 30
- 239000002105 nanoparticle Substances 0.000 claims description 28
- 229920000642 polymer Polymers 0.000 claims description 27
- 230000001681 protective effect Effects 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 7
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 241000003832 Lantana Species 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- 235000012255 calcium oxide Nutrition 0.000 claims description 3
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- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 229910052878 cordierite Inorganic materials 0.000 claims description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 3
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 3
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- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 229910052863 mullite Inorganic materials 0.000 claims description 3
- 239000002116 nanohorn Substances 0.000 claims description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 3
- -1 perovskite Chemical compound 0.000 claims description 3
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
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- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims 1
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- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 9
- RTZYCRSRNSTRGC-LNTINUHCSA-K (z)-4-oxopent-2-en-2-olate;ruthenium(3+) Chemical group [Ru+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O RTZYCRSRNSTRGC-LNTINUHCSA-K 0.000 description 8
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 2
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- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
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- Catalysts (AREA)
Description
本発明は、高分子保護材フリーの担持触媒に関する。 The present invention relates to a supported catalyst free of a polymer protective material.
従来、化学反応触媒又は燃料電池などでは、カーボン系の担体にナノ粒子を担持した不均一系触媒が用いられている。また、ボイラー又は排ガスの浄化などでは、セラミックス系の担体にナノ粒子を担持した不均一系触媒が用いられている。不均一系触媒に用いるナノ粒子として(fcc)Ruナノ粒子が開示されている(例えば、特許文献1、又は非特許文献1を参照。)。非特許文献1では、(fcc)Ruナノ粒子を担体に担持して不均一系触媒として使用する場合、ポリビニルピロリドンなどの高分子保護材を用いてナノ粒子を合成・精製した後に、得られたナノ粒子を担体に担持している。 Conventionally, in a chemical reaction catalyst or a fuel cell, a heterogeneous catalyst in which nanoparticles are supported on a carbon-based carrier has been used. In addition, in the purification of boilers or exhaust gases, heterogeneous catalysts in which nanoparticles are supported on a ceramic carrier are used. (Fcc) Ru nanoparticles are disclosed as nanoparticles used for heterogeneous catalysts (see, for example, Patent Document 1 or Non-Patent Document 1). In Non-Patent Document 1, when (fcc) Ru nanoparticles were supported on a carrier and used as a heterogeneous catalyst, the nanoparticles were synthesized and purified using a polymer protective material such as polyvinylpyrrolidone. Nanoparticles are supported on a carrier.
しかし、ナノ粒子の合成時に用いた高分子保護材が触媒中に残っていると、触媒の効果が十分に発揮されない場合がある。高分子保護材の除去を目的としてナノ粒子の精製を繰り返すと、精製回数が増加するにつれて得られるナノ粒子の収量が少なくなるという問題である。 However, if the polymer protective material used in the synthesis of the nanoparticles remains in the catalyst, the effect of the catalyst may not be sufficiently exhibited. If the purification of the nanoparticles is repeated for the purpose of removing the polymer protective material, the yield of nanoparticles obtained decreases as the number of purification increases.
本発明の目的は、触媒の性能を低下させる高分子保護材を用いず、触媒の効果を十分に発揮できる担持触媒を提供することである。 An object of the present invention is to provide a supported catalyst that can sufficiently exhibit the effect of the catalyst without using a polymer protective material that lowers the performance of the catalyst.
本発明に係る担持触媒は、ナノ粒子としてRu粒子が担持体に担持された担持触媒において、前記Ru粒子は、fcc構造を有しており、前記担持触媒の外表面に高分子保護材が存在しないことを特徴とする。hcp構造を有するRu粒子を担持させた触媒と比較し、異なる触媒活性を得ることができる。 The supported catalyst according to the present invention is a supported catalyst in which Ru particles are supported on a support as nanoparticles, and the Ru particles have an fcc structure, and a polymer protective material is present on the outer surface of the supported catalyst. It is characterized by not. Compared with a catalyst supporting Ru particles having an hcp structure, a different catalytic activity can be obtained.
本発明に係る担持触媒は、高分子保護材を含有しないことが好ましい。触媒活性をより高めることができる。 The supported catalyst according to the present invention preferably contains no polymer protective material. The catalytic activity can be further increased.
本発明に係る担持触媒では、前記ナノ粒子と前記担持体との間に前記高分子保護材が介在しないことが好ましい。触媒活性をより高めることができる。 In the supported catalyst according to the present invention, it is preferable that the polymer protective material is not interposed between the nanoparticles and the support. The catalytic activity can be further increased.
本発明に係る担持触媒では、前記担持体は、カーボン若しくはセラミックスのいずれか一方又は両方である形態を包含する。 In the supported catalyst according to the present invention, the support includes one or both of carbon and ceramics.
本発明に係る担持触媒では、前記担持体は、アルミナ、シリカ、シリカアルミナ、カルシア、マグネシア、チタニア、セリア、ジルコニア、セリアジルコニア、ランタナ、ランタナアルミナ、酸化スズ、酸化タングステン、アルミノシリケート、アルミノホスフェート、ボロシリケート、リンタングステン酸、ヒドロキシアパタイト、ハイドロタルサイト、ペロブスカイト、コージェライト、ムライト、シリコンカーバイド、活性炭、カーボンブラック、アセチレンブラック、カーボンナノチューブ及びカーボンナノホーンの中から選ばれる1種以上である形態を包含する。 In the supported catalyst according to the present invention, the support is alumina, silica, silica alumina, calcia, magnesia, titania, ceria, zirconia, ceria zirconia, lantana, lantana alumina, tin oxide, tungsten oxide, aluminosilicate, aluminophosphate, Includes one or more forms selected from borosilicate, phosphotungstic acid, hydroxyapatite, hydrotalcite, perovskite, cordierite, mullite, silicon carbide, activated carbon, carbon black, acetylene black, carbon nanotube and carbon nanohorn To do.
本発明は、触媒の性能を低下させる高分子保護材を用いず、触媒の効果を十分に発揮できる担持触媒を提供することができる。 The present invention can provide a supported catalyst that can sufficiently exhibit the effect of the catalyst without using a polymer protective material that lowers the performance of the catalyst.
次に本発明について実施形態を示して詳細に説明するが本発明はこれらの記載に限定して解釈されない。本発明の効果を奏する限り、実施形態は種々の変形をしてもよい。 Next, although an embodiment is shown and explained in detail about the present invention, the present invention is limited to these descriptions and is not interpreted. As long as the effect of the present invention is exhibited, the embodiment may be variously modified.
本実施形態に係る担持触媒は、ナノ粒子としてRu粒子が担持体に担持された担持触媒において、担持触媒の外表面に高分子保護材が存在しない。高分子保護材が担持触媒の外表面に存在しないことで、触媒の作用を十分の発揮させることができる。高分子保護材は、例えば、ポリビニルピロリドン(PVP)である。本実施形態に係る担持触媒では、高分子保護材がナノ粒子の外表面に付着していないことが好ましく、高分子保護材がナノ粒子の外表面及び担持体の外表面に付着していないことがより好ましい。 The supported catalyst according to this embodiment is a supported catalyst in which Ru particles are supported on a support as nanoparticles, and no polymer protective material is present on the outer surface of the supported catalyst. Since the polymer protective material is not present on the outer surface of the supported catalyst, the function of the catalyst can be sufficiently exerted. The polymer protective material is, for example, polyvinyl pyrrolidone (PVP). In the supported catalyst according to this embodiment, the polymer protective material is preferably not attached to the outer surface of the nanoparticle, and the polymer protective material is not attached to the outer surface of the nanoparticle and the outer surface of the support. Is more preferable.
本実施形態に係る担持触媒では、ナノ粒子と担持体との間に高分子保護材が介在しないことが好ましい。 In the supported catalyst according to the present embodiment, it is preferable that no polymer protective material is interposed between the nanoparticles and the support.
本実施形態に係る担持触媒は、高分子保護材を含有しないことが好ましい。担持触媒が高分子保護材を含有するか否かは、例えば、X線回折パターン(XRDパターン)によって確認できる。例えば高分子保護材がPVPであるとき、室温でλ=CuKαの測定条件で測定したXRDパターンにおいて、10°付近にPVP由来のパターンが確認されないことで、担持触媒が高分子保護材を含有しないことを確認することができる。 The supported catalyst according to this embodiment preferably does not contain a polymer protective material. Whether or not the supported catalyst contains a polymer protective material can be confirmed by, for example, an X-ray diffraction pattern (XRD pattern). For example, when the polymer protective material is PVP, the supported catalyst does not contain the polymer protective material because the PVP-derived pattern is not confirmed at around 10 ° in the XRD pattern measured at room temperature under the measurement condition of λ = CuKα. I can confirm that.
本実施形態に係る担持触媒は、従来の担持触媒の製造方法のように予め合成したナノ粒子を担持体に担持させる方法ではなく、ナノ粒子の合成とナノ粒子の担持体への担持とを同時に行う方法で製造することが好ましい。ナノ粒子の合成とナノ粒子の担持体への担持とを同時に行うことで、従来の製造方法と比較して製造工程を少なくすることができる。本明細書において、ナノ粒子とは、平均粒子径が100nm以下の微細粒子をいう。ナノ粒子の平均粒子径は、透過型電子顕微鏡(TEM)によって得られた粒子像から少なくとも100個以上の粒子の粒子径を計測し、その平均を求めることによって算出した値である。TEMの観察倍率は、例えば、120000倍又は150000倍であることが好ましい。ナノ粒子の平均粒子径の下限は、特に限定されないが、1nm以上であることが好ましい。 The supported catalyst according to the present embodiment is not a method in which nanoparticles synthesized in advance are supported on a support as in the conventional method for producing a supported catalyst, but the synthesis of nanoparticles and the support of nanoparticles on the support are simultaneously performed. It is preferable to manufacture by the method to perform. By simultaneously performing the synthesis of the nanoparticles and the loading of the nanoparticles on the carrier, the number of manufacturing steps can be reduced as compared with the conventional manufacturing method. In this specification, a nanoparticle means the fine particle whose average particle diameter is 100 nm or less. The average particle diameter of the nanoparticles is a value calculated by measuring the particle diameter of at least 100 particles from a particle image obtained by a transmission electron microscope (TEM) and obtaining the average. The observation magnification of TEM is preferably 120,000 times or 150,000 times, for example. Although the minimum of the average particle diameter of a nanoparticle is not specifically limited, It is preferable that it is 1 nm or more.
本実施形態に係る担持触媒の製造方法は、Ru粒子の合成原料となるRu化合物と、担持体と、炭素数が2以上の還元性をもつ有機溶媒と、を含有し、かつ、高分子保護材を含有しない混合物を加熱して、Ru粒子を合成するとともに、Ru粒子を担持体に担持させる工程1を有することが好ましい。 The method for producing a supported catalyst according to the present embodiment includes a Ru compound that is a raw material for the synthesis of Ru particles, a support, and an organic solvent having a reducing property having 2 or more carbon atoms, and is a polymer protective agent. It is preferable to have Step 1 of heating the mixture containing no material to synthesize Ru particles and supporting the Ru particles on the support.
次に、工程1で用いる各物質について説明する。 Next, each substance used in step 1 will be described.
(ナノ粒子の合成原料)
Ru粒子の合成原料となるRu化合物はRu有機化合物であることが好ましい。担持触媒をより効率的に得ることができる。Ru有機化合物は、ジケトナート又はアセテートを含有する化合物であることが好ましい。ジケトナートを含有するRu有機化合物は、例えば、トリス(アセチルアセナト)ルテニウム(III)(以降、Ru(acac)3という。)である。アセテートを含有するRu有機化合物は、例えば、酢酸ルテニウム(以降、酢酸Ruという。)である。このうち、Ru化合物はRu(acac)3又は酢酸Ruであることが好ましい。
(Nanoparticle synthesis raw material)
The Ru compound that is a raw material for the synthesis of Ru particles is preferably a Ru organic compound. A supported catalyst can be obtained more efficiently. The Ru organic compound is preferably a compound containing diketonate or acetate. An example of the Ru organic compound containing diketonate is tris (acetylacetonato) ruthenium (III) (hereinafter referred to as Ru (acac) 3 ). The Ru organic compound containing acetate is, for example, ruthenium acetate (hereinafter referred to as Ru acetate). Of these, the Ru compound is preferably Ru (acac) 3 or Ru acetate.
(担持体)
担持体は、カーボン若しくはセラミックスのいずれか一方又は両方である形態を包含する。セラミックスは、例えば、アルミナ、シリカ、シリカアルミナ、カルシア、マグネシア、チタニア、セリア、ジルコニア、セリアジルコニア、ランタナ、ランタナアルミナ、酸化スズ、酸化タングステン、アルミノシリケート、アルミノホスフェート、ボロシリケート、リンタングステン酸、ヒドロキシアパタイト、ハイドロタルサイト、ペロブスカイト、コージェライト、ムライト又はシリコンカーバイドである。カーボンは、例えば、活性炭、カーボンブラック、アセチレンブラック、カーボンナノチューブ又はカーボンナノホーンである。本実施形態では、これらの担持体の中から1種だけを使用するか、又は2種以上を併用してもよい。2種以上を併用する場合は、セラミックスから2種以上を組合せて用いるか、カーボンから2種以上を組合せて用いるか、又はセラミックスから1種以上及びカーボンから1種以上を組合せて用いてもよい。より好ましくは、アルミナ、シリカ、チタニア、セリア、ジルコニア、活性炭及びカーボンブラックの中から選ばれる1種以上を用いる。
(Carrier)
The support includes a form that is one or both of carbon and ceramics. Ceramics include, for example, alumina, silica, silica alumina, calcia, magnesia, titania, ceria, zirconia, ceria zirconia, lantana, lantana alumina, tin oxide, tungsten oxide, aluminosilicate, aluminophosphate, borosilicate, phosphotungstic acid, hydroxy Apatite, hydrotalcite, perovskite, cordierite, mullite or silicon carbide. The carbon is, for example, activated carbon, carbon black, acetylene black, carbon nanotube, or carbon nanohorn. In this embodiment, only 1 type may be used from these support bodies, or 2 or more types may be used together. When two or more types are used in combination, two or more types from ceramics may be used in combination, two or more types from carbon may be used in combination, or one or more types from ceramics and one or more types from carbon may be used in combination. . More preferably, at least one selected from alumina, silica, titania, ceria, zirconia, activated carbon and carbon black is used.
(有機溶媒)
有機溶媒は、炭素数が2以上であり、還元性をもつ。有機溶媒の炭素数は、4以上であることがより好ましい。有機溶媒の炭素数の上限は、特に限定されないが、常温において液体であることがより好ましい。
(Organic solvent)
The organic solvent has 2 or more carbon atoms and has reducibility. More preferably, the organic solvent has 4 or more carbon atoms. The upper limit of the carbon number of the organic solvent is not particularly limited, but is more preferably liquid at normal temperature.
有機溶媒の沸点は100℃以上であることが好ましい。取り扱い性に優れる。また、担持触媒をより安全に得ることができる。有機溶媒の沸点は、160℃以上であることがより好ましい。有機溶媒の沸点の上限は、特に限定されないが、担持触媒から溶媒をより容易に除去できる点で、300℃以下であることが好ましく、290℃以下であることがより好ましい。 The boiling point of the organic solvent is preferably 100 ° C. or higher. Excellent handleability. In addition, the supported catalyst can be obtained more safely. The boiling point of the organic solvent is more preferably 160 ° C. or higher. Although the upper limit of the boiling point of the organic solvent is not particularly limited, it is preferably 300 ° C. or lower, more preferably 290 ° C. or lower, from the viewpoint that the solvent can be more easily removed from the supported catalyst.
有機溶媒は、多価アルコール、ブタノール、イソブタノール、エトキシエタノール、ジメチルホルムアミド、キシレン、N−メチルピロリジノン、ジクロロベンゼン、トルエン、プロピレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテルアセテート、エチルラクテート、ジエチレングリコールジメチルエーテル、ジプロピレングリコールジメチルエーテル、ジエチレングリコールエチルメチルエーテル、ジエチレングリコールイソプロピルメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールブチルメチルエーテル、トリプロピレングリコールジメチルエーテル、トリエチレングリコールジメチルエーテル、ジエチレングリコールモノブチルエーテル、エチレングリコールモノフェニルエーテル、リエチレングリコールモノメチルエーテル、ジエチレングリコールジブチルエーテル、トリエチレングリコールブチルメチルエーテル、ポリエチレングリコールジメチルエーテル、テトラエチレングリコールジメチルエーテル及びポリエチレングリコールモノメチルエーテルの中から選ばれる1種以上であることが好ましい。担持触媒をより安全、かつ、より効率的に得ることができる。このうち、多価アルコールがより好ましい。 Organic solvents are polyhydric alcohol, butanol, isobutanol, ethoxyethanol, dimethylformamide, xylene, N-methylpyrrolidinone, dichlorobenzene, toluene, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethyl lactate, Diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl Ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether, reethylene glycol monomethyl ether, diethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, polyethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and polyethylene glycol monomethyl ether It is preferable that it is 1 or more types. The supported catalyst can be obtained more safely and more efficiently. Of these, polyhydric alcohols are more preferred.
多価アルコールは、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール及びブチレングリコールの中から選ばれる1種以上であることが好ましい。このうち、トリエチレングリコールがより好ましい。担持触媒をより安全、かつ、より効率的に得ることができる。 The polyhydric alcohol is preferably at least one selected from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and butylene glycol. Of these, triethylene glycol is more preferable. The supported catalyst can be obtained more safely and more efficiently.
次に、工程1について説明する。 Next, step 1 will be described.
工程1では、まず、Ru化合物と、担持体と、有機溶媒と、を含有する混合物を作製する。混合物中のRu化合物の濃度は、125mM(mmol/l)以下であることが好ましく、100mM以下であることがより好ましい。また、Ru化合物と担持体との割合は、担持触媒中のRu粒子の担持量が所定の範囲となるように調整する。担持触媒中のRu粒子の担持量は、0.001〜60質量%であることが好ましい。ここで、担持量は、乾燥状態の担持触媒の質量に対するナノ粒子の質量の割合であり、例えば高周波誘導結合プラズマ発光分光分析、原子吸光分光光度分析で測定することができる。 In step 1, first, a mixture containing a Ru compound, a support, and an organic solvent is prepared. The concentration of the Ru compound in the mixture is preferably 125 mM (mmol / l) or less, and more preferably 100 mM or less. The ratio between the Ru compound and the support is adjusted so that the amount of Ru particles supported in the supported catalyst falls within a predetermined range. The supported amount of Ru particles in the supported catalyst is preferably 0.001 to 60% by mass. Here, the supported amount is the ratio of the mass of the nanoparticles to the mass of the supported catalyst in the dry state, and can be measured by, for example, high frequency inductively coupled plasma emission spectrometry or atomic absorption spectrophotometry.
混合物の作製にあたり、Ru化合物及び担持体を有機溶媒中に懸濁させた後、例えば超音波などの分散機を用いて分散させることが好ましい。本発明は、各物質の添加順は特に限定されない。 In preparing the mixture, it is preferable to suspend the Ru compound and the support in an organic solvent and then disperse the mixture using a disperser such as an ultrasonic wave. In the present invention, the order of addition of each substance is not particularly limited.
次いで、混合物を加熱する。加熱方法は、特に限定されず、例えば、オイルバス、マントルヒーター、ブロックヒーター若しくは熱媒循環式ジャケットなどの外部加熱方式、又はマイクロ波照射方式である。加熱温度は、100〜300℃であることが好ましく、180〜230℃であることがより好ましい。目的とする加熱温度に到達させるまでの昇温速度は、4℃/分以上であることが好ましく、6℃/分以上であることがより好ましい。昇温速度を所定の範囲とすることで、fcc構造を有するRu粒子を形成することができる。また、目的とする加熱温度で保持する時間は、使用する化合物の種類、混合物の液量又は加熱温度などに依存するが、例えば、10〜300分であることが好ましく、120〜240分であることがより好ましい。 The mixture is then heated. The heating method is not particularly limited, and is, for example, an external heating method such as an oil bath, a mantle heater, a block heater or a heat medium circulation jacket, or a microwave irradiation method. The heating temperature is preferably 100 to 300 ° C, and more preferably 180 to 230 ° C. The rate of temperature rise until reaching the target heating temperature is preferably 4 ° C./min or more, and more preferably 6 ° C./min or more. By setting the temperature rising rate within a predetermined range, Ru particles having an fcc structure can be formed. Moreover, although the time to hold | maintain at the target heating temperature is dependent on the kind of compound to be used, the liquid quantity of a mixture, or heating temperature, it is preferable that it is 10 to 300 minutes, for example, and is 120 to 240 minutes. It is more preferable.
工程1では、Ru化合物が有機溶媒によって還元され、担持体の表面でRu粒子の核生成及び粒成長が起こる。そして、Ru粒子が担持体に担持された担持触媒が得られる。このRu粒子はfcc構造を有している。Ru粒子がfcc構造を有することで、hcp構造を有するRu粒子を担持させた触媒と比較し、異なる触媒活性を得ることができる。Ru粒子の結晶構造は、例えば、X線回折パターン(XRDパターン)によって確認できる。Ru粒子の平均粒子径は、30nm以下であることが好ましく、10nm以下であることがより好ましい。Ru粒子の平均粒子径の下限は、特に限定されないが、1nm以上であることが好ましい。 In step 1, the Ru compound is reduced by an organic solvent, and Ru particle nucleation and grain growth occur on the surface of the support. A supported catalyst in which Ru particles are supported on a support is obtained. The Ru particles have an fcc structure. Since the Ru particles have an fcc structure, different catalytic activity can be obtained as compared with a catalyst supporting Ru particles having an hcp structure. The crystal structure of the Ru particles can be confirmed by, for example, an X-ray diffraction pattern (XRD pattern). The average particle size of the Ru particles is preferably 30 nm or less, and more preferably 10 nm or less. The lower limit of the average particle diameter of the Ru particles is not particularly limited, but is preferably 1 nm or more.
工程1の後、担持触媒を溶媒から分離精製することが好ましい。担持触媒を分離精製する方法は、特に限定されないが、例えば、温度が下がった混合物をろ過し、洗浄・乾燥する方法である。 After step 1, the supported catalyst is preferably separated and purified from the solvent. The method for separating and purifying the supported catalyst is not particularly limited. For example, the method is a method of filtering, washing and drying a mixture having a lowered temperature.
以降、実施例を示しながら本発明についてさらに詳細に説明するが、本発明は実施例に限定して解釈されない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not construed as being limited to the examples.
(実施例1A)
フラスコにトリエチレングリコール(以下、TEG)を125mL投入した。トリス(アセチルアセトナト)ルテニウム(III)(以下、Ru(acac)3)を1.9918g(5mmol)と活性炭(FAM−50、日本エンバイロケミカルズ社製)を4.5031gとを秤とり前記TEG中に添加し、超音波で30min分散して混合液を作製した。混合液に高分子保護材は添加しなかった。この混合液を6℃/分の昇温速度で200℃まで加熱し、200℃で3hr加熱撹拌し、その後冷却した。冷却した混合液を減圧ろ過し、固体成分(濾物)をエタノールで十分に洗浄した後減圧乾燥を実施し、担持触媒を得た。
Example 1A
125 mL of triethylene glycol (hereinafter, TEG) was charged into the flask. In the TEG, 1.9918 g (5 mmol) of tris (acetylacetonato) ruthenium (III) (hereinafter referred to as Ru (acac) 3 ) and 4.5031 g of activated carbon (FAM-50, manufactured by Nippon Environment Chemicals) were weighed. And mixed with an ultrasonic wave for 30 minutes to prepare a mixed solution. The polymer protective material was not added to the mixed solution. The mixture was heated to 200 ° C. at a rate of temperature increase of 6 ° C./min, heated and stirred at 200 ° C. for 3 hours, and then cooled. The cooled mixture was filtered under reduced pressure, and the solid component (filtered material) was thoroughly washed with ethanol and then dried under reduced pressure to obtain a supported catalyst.
(実施例2A)
フラスコにTEGを40mL投入した。Ru(acac)3を1.9920g(5mmol)と活性炭(FAM−50)を4.5022gとを秤とり前記TEG中に添加し、超音波で30min分散して混合液を作製した。混合液に高分子保護材は添加しなかった。この混合液を6℃/分の昇温速度で200℃まで加熱し、200℃で3hr加熱撹拌し、その後冷却した。冷却した混合液を減圧ろ過し、固体成分(濾物)をエタノールで十分に洗浄した後減圧乾燥を実施し、担持触媒を得た。
(Example 2A)
40 mL of TEG was charged into the flask. 1.9920 g (5 mmol) of Ru (acac) 3 and 4.5022 g of activated carbon (FAM-50) were weighed and added to the TEG, and dispersed by ultrasonication for 30 min to prepare a mixed solution. The polymer protective material was not added to the mixed solution. The mixture was heated to 200 ° C. at a rate of temperature increase of 6 ° C./min, heated and stirred at 200 ° C. for 3 hours, and then cooled. The cooled mixture was filtered under reduced pressure, and the solid component (filtered material) was thoroughly washed with ethanol and then dried under reduced pressure to obtain a supported catalyst.
(実施例3A)
フラスコにTEGを185mL投入した。Ru(acac)3を5.9056g(14.8mmol)とケッチェンブラック(EC300J、ライオン社製)とを4.5022g秤とり前記TEG中に添加し、超音波で30minの間分散して混合液を作製した。混合液に高分子保護材は添加しなかった。この混合液を6℃/分の昇温速度で200℃まで加熱し、200℃で3hr加熱撹拌し、その後冷却した。冷却した混合液を減圧ろ過し、固体成分(濾物)をエタノールで十分に洗浄した後減圧乾燥を実施し、担持触媒を得た。
(Example 3A)
185 mL of TEG was charged into the flask. 5.9056 g (14.8 mmol) of Ru (acac) 3 and 4.5022 g of Ketjen Black (EC300J, manufactured by Lion Corporation) are weighed and added to the TEG, and dispersed by mixing with ultrasonic waves for 30 min. Was made. The polymer protective material was not added to the mixed solution. The mixture was heated to 200 ° C. at a rate of temperature increase of 6 ° C./min, heated and stirred at 200 ° C. for 3 hours, and then cooled. The cooled mixture was filtered under reduced pressure, and the solid component (filtered material) was thoroughly washed with ethanol and then dried under reduced pressure to obtain a supported catalyst.
(実施例4A)
フラスコにTEGを125mL投入した。Ru(acac)3を0.9869g(2.5mmol)と活性炭(FAM−50)を4.7496gとを秤とり前記TEG中に添加し、超音波で30minの間分散して混合液を作製した。混合液に高分子保護材は添加しなかった。この混合液を6℃/分の昇温速度で200℃まで加熱し、200℃で3hr加熱撹拌し、その後冷却した。遠心分離を用いて冷却後の混合液から固体成分を沈降させ上澄みを除去し、固体成分をエタノールで十分に洗浄した後減圧乾燥を実施し、担持触媒を得た。
(Example 4A)
125 mL of TEG was charged into the flask. 0.9869 g (2.5 mmol) of Ru (acac) 3 and 4.796 g of activated carbon (FAM-50) were weighed and added to the TEG, and dispersed for 30 min with ultrasound to prepare a mixed solution. . The polymer protective material was not added to the mixed solution. The mixture was heated to 200 ° C. at a rate of temperature increase of 6 ° C./min, heated and stirred at 200 ° C. for 3 hours, and then cooled. The solid component was precipitated from the cooled mixed solution using centrifugal separation, the supernatant was removed, the solid component was sufficiently washed with ethanol, and then dried under reduced pressure to obtain a supported catalyst.
(Ru粒子の平均粒子径)
実施例1A及び実施例2Aの担持触媒をTEMでそれぞれ倍率150000倍、200000倍で観察し、得られた粒子像から100個の粒子の粒子径を計測し、その平均を求め、Ru粒子の平均粒子径とした。図1に実施例1AのTEM像を、図2に実施例2AのTEM像を示す。実施例1Aの平均粒子径は3.34nm、実施例2Aの平均粒子径は3.14nmであった。また、図1及び図2から、凝集した粒子の存在は確認されなかった。
(Average particle diameter of Ru particles)
The supported catalysts of Example 1A and Example 2A were observed with a TEM at a magnification of 150,000 times and 200000 times, respectively, and the particle diameter of 100 particles was measured from the obtained particle images, the average was obtained, and the average of Ru particles The particle diameter was taken. FIG. 1 shows a TEM image of Example 1A, and FIG. 2 shows a TEM image of Example 2A. The average particle size of Example 1A was 3.34 nm, and the average particle size of Example 2A was 3.14 nm. Further, from FIG. 1 and FIG. 2, the presence of aggregated particles was not confirmed.
(結晶状態)
実施例1A及び実施例2Aの担持触媒について、XRD測定を行った。XRD測定条件は、室温でλ=CuKαである。図3に実施例1AのXRDパターンを、図4に実施例2AのXRDパターンを示す。図3において、Ruのパターンは(fcc)Ruのパターンを示しており、Ru粒子がfcc構造を有することが確認できた。図4において、Ruのパターンは(fcc)Ruのパターン及び(hcp)Ruのパターンを含むことが示されていた。
(Crystal state)
XRD measurement was performed on the supported catalysts of Example 1A and Example 2A. The XRD measurement condition is λ = CuKα at room temperature. FIG. 3 shows the XRD pattern of Example 1A, and FIG. 4 shows the XRD pattern of Example 2A. In FIG. 3, the Ru pattern shows the (fcc) Ru pattern, and it was confirmed that the Ru particles have the fcc structure. In FIG. 4, it was shown that the pattern of Ru includes a pattern of (fcc) Ru and a pattern of (hcp) Ru.
Claims (5)
前記Ru粒子は、fcc構造を有しており、
前記担持触媒の外表面に高分子保護材が存在しないことを特徴とする担持触媒。 In a supported catalyst in which Ru particles are supported on a support as nanoparticles,
The Ru particles have an fcc structure,
A supported catalyst characterized in that no polymer protective material is present on the outer surface of the supported catalyst.
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