JP5623070B2 - Supported catalyst - Google Patents
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- JP5623070B2 JP5623070B2 JP2009290000A JP2009290000A JP5623070B2 JP 5623070 B2 JP5623070 B2 JP 5623070B2 JP 2009290000 A JP2009290000 A JP 2009290000A JP 2009290000 A JP2009290000 A JP 2009290000A JP 5623070 B2 JP5623070 B2 JP 5623070B2
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- 239000003054 catalyst Substances 0.000 title claims description 34
- 239000007789 gas Substances 0.000 claims description 25
- 239000000126 substance Substances 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 229910000765 intermetallic Inorganic materials 0.000 claims description 17
- 238000004140 cleaning Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims 2
- 229910052745 lead Inorganic materials 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 36
- 229910004298 SiO 2 Inorganic materials 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 27
- 239000010936 titanium Substances 0.000 description 21
- 230000003197 catalytic effect Effects 0.000 description 14
- 239000010453 quartz Substances 0.000 description 14
- 239000002105 nanoparticle Substances 0.000 description 13
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 239000000446 fuel Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- 229920000742 Cotton Polymers 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004817 gas chromatography Methods 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
- 239000000843 powder Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- QLUMLEDLZDMGDW-UHFFFAOYSA-N sodium;1h-naphthalen-1-ide Chemical compound [Na+].[C-]1=CC=CC2=CC=CC=C21 QLUMLEDLZDMGDW-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910016523 CuKa Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000011086 high cleaning Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/02—Solids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
Description
本発明は、酸化物担持体の表面にナノ粒子の形状を持った触媒活性点が担持された担持触媒に関する。 The present invention relates to a supported catalyst in which a catalytically active site having a nanoparticle shape is supported on the surface of an oxide carrier.
この種の担持触媒は、特許文献１、２及び４に示されるように、主に自動車排気ガス清浄化を目的として開発されて来た。従来の担持触媒においては、高比表面積を備えた酸化物担持体に貴金属や希少元素等の貴重元素からなる触媒活性点を分散・担持させることによって、貴重元素の使用量低減が図られて来た。 This type of supported catalyst has been developed mainly for the purpose of purifying automobile exhaust gas, as shown in Patent Documents 1, 2, and 4 . In conventional supported catalysts, the amount of valuable elements used has been reduced by dispersing and supporting catalytic active sites composed of precious metals and rare elements on an oxide carrier having a high specific surface area. It was.
近年の排ガス規制強化に伴い、担持触媒の需要は爆発的に増加している。前記特許文献は、主として触媒活性点の高分散化あるいは酸化物坦持体の高比表面積化によってこの需要に応えようとする技術であるが、その効果には限界があった。これとは別に、触媒活性点として、規則型金属間化合物ナノ粒子または合金ナノ粒子を使用することにより、貴重元素の使用量を抑えながら高い排気ガス清浄化触媒活性を実現しようとする試みも報告されている。しかしながら、触媒活性点として従来開発されてきた規則型金属間化合物または合金ナノ粒子はすべて、取り扱いが容易な水溶液中での還元反応に基づいて合成されており、したがって、標準電極電位（Ｖ）が、水素よりも高い還元電位（Ｖ＞０）を持った金属元素を構成元素に持つ物質系に限定されてきた経緯がある。なお、規則型金属間化合物は燃料電池等の触媒として考慮されることがあった（特許文献３、及び非特許文献１〜３）。 With the recent tightening of exhaust gas regulations, the demand for supported catalysts has increased explosively. The above-mentioned patent document is a technique that attempts to meet this demand mainly by increasing the dispersion of the catalyst active sites or increasing the specific surface area of the oxide support, but its effect is limited. In addition to this, an attempt to achieve high exhaust gas cleaning catalytic activity while suppressing the amount of valuable elements by using regular intermetallic nanoparticles or alloy nanoparticles as catalytic active points is also reported. Has been. However, all the regular intermetallic compounds or alloy nanoparticles that have been conventionally developed as catalytic active sites are synthesized based on a reduction reaction in an aqueous solution that is easy to handle, and therefore the standard electrode potential (V) is There is a history of being limited to a substance system having a metal element having a reduction potential (V> 0) higher than that of hydrogen as a constituent element. In addition, the regular intermetallic compound may be considered as a catalyst for a fuel cell or the like (Patent Document 3 and Non-Patent Documents 1 to 3).
本発明は、このような実情に鑑み、標準電極電位（Ｖ）が、水素よりも低い（Ｖ＜０）金属元素を有する規則型金属間化合物を排気ガス清浄触媒として有用に用いる手段を提供することを目的とする。 In view of such circumstances, the present invention provides means for effectively using an ordered intermetallic compound having a metal element having a standard electrode potential (V) lower than that of hydrogen (V <0) as an exhaust gas cleaning catalyst. For the purpose.
発明１の担持触媒は、粒子状の酸化物担持体の表面に、当該酸化物担持体と比較して少量のナノ粒子状の触媒活性点が担持された担持触媒であって、前記触媒活性点が、下記化学式１に示す化学組成を有する規則型金属間化合物であることを特徴とする：
αｘβｙ …（化学式１）
（α：標準電極電位（Ｖ）が＜０である金属元素、β：標準電極電位（Ｖ）が＞０である金属元素。なお、水素（Ｈ）の標準電極電位は零とする。ｘ＋ｙ＝１００：モル比、１９≦ｙ≦２５）。
The supported catalyst of the invention 1 is a supported catalyst in which a small amount of nanoparticulate catalytically active sites are supported on the surface of a particulate oxide carrier, compared to the oxide carrier. Is an ordered intermetallic compound having a chemical composition represented by the following chemical formula 1:
α x β y ( Chemical formula 1)
(Α: metal element whose standard electrode potential (V) is <0, β: metal element whose standard electrode potential (V) is> 0. Note that the standard electrode potential of hydrogen (H) is zero. X + y = 100: molar ratio, 19 ≦ y ≦ 25) .
発明２は、発明１の担持触媒において、酸化物担持体がシリカ粒子であることを特徴とする。 Invention 2 is characterized in that, in the supported catalyst of Invention 1, the oxide support is silica particles.
発明３は、発明１又は２の担持触媒において、前記αがＰｔであって、前記βがＴｉであることを特徴とする。 Invention 3 is the supported catalyst of Invention 1 or 2, characterized in that α is Pt and β is Ti.
発明４は、発明１から３の担持触媒に用いた規則型金属間化合物の製造方法であって、水素よりも２．０Ｖ以上低い還元電位を持つアルカリ金属のラジカル体を還元剤として用いたプリカーサーの同時還元によることを特徴とする。 Invention 4 is a method for producing an ordered intermetallic compound used in the supported catalyst of Inventions 1 to 3, wherein a precursor using an alkali metal radical having a reduction potential lower than hydrogen by 2.0 V or more as a reducing agent is used. It is characterized by the simultaneous reduction of.
発明５は、発明４の製造方法において、前記アルカリ金属のラジカル体が、以下の化学式２に示す組成を有することを特徴とする：
ＮａＣ１０Ｈ８ …（化学式２）。
Invention 5 is the production method of Invention 4, wherein the alkali metal radical has a composition represented by the following chemical formula 2 :
NaC 10 H 8 (chemical formula 2).
本発明は、前記化学式１を満たす化学組成を有する触媒活性点が、排ガス清浄化技術において最も重要な化学反応の一つである一酸化炭素清浄化反応（ＣＯ（一酸化炭素）→ＣＯ２（二酸化炭素）転換反応）に対して高い触媒活性を発現するという新知見に基づく。本発明は、当該知見に基づき、独自のナノ粒子合成・分散・担持技術を駆使して、当該反応に対して高い触媒活性を備えた担持触媒を実現した点に特徴がある。 In the present invention, a carbon monoxide cleaning reaction (CO (carbon monoxide) → CO 2 (CO 2 )) in which a catalytic active point having a chemical composition satisfying the chemical formula 1 is one of the most important chemical reactions in the exhaust gas cleaning technology. Based on the new finding that high catalytic activity for carbon dioxide) conversion reaction). The present invention is characterized in that a supported catalyst having high catalytic activity for the reaction is realized by making full use of the unique nanoparticle synthesis / dispersion / support technology based on the knowledge.
本発明は、酸化物担持体の表面に、ナノ粒子の形状を持つ触媒活性点である規則型金属間化合物を担持した担持触媒に関するものである。 The present invention relates to a supported catalyst in which a regular intermetallic compound that is a catalytic active point having a nanoparticle shape is supported on the surface of an oxide carrier.
規則型金属間化合物としては、前記化学式１を満たすものであれば有用であるが、特に、αの金属元素として、Ｃｕ，Ｈｇ、Ａｓ、Ｐｔ、Ａｕのいずれか、βの金属元素として、Ｐｂ，Ｓｎ，Ｎｉ，Ｆｅ，Ｚｎ，Ａｌ、Ｔｉ、Ｍｇのいずれかを用いるのが望ましい。 The regular intermetallic compound is useful as long as it satisfies the above chemical formula 1, but in particular, any of Cu, Hg, As, Pt, and Au as a metal element of α, and Pb as a metal element of β , Sn, Ni, Fe, Zn, Al, Ti, and Mg are preferably used.
また、本実施例では、この規則型金属間化合物を、水素よりも２．０Ｖ以上低い還元電位を持つアルカリ金属のラジカル体を還元剤として使用することにより、水素よりも低い還元電位を備えた金属元素（α）を構成元素に持つ規則型金属間化合物を合成した。特に、前記化学式（２）に示すＳｏｄｉｕｍ Ｎａｐｈｉｔｈａｌｉｄｅをアルカリ金属ラジカル体として用いたプリカーサーの同時還元により、規則型金属間化合物のナノ粒子を合成した。 In this example, this ordered intermetallic compound was provided with a reduction potential lower than that of hydrogen by using, as a reducing agent, an alkali metal radical having a reduction potential of 2.0 V or more lower than that of hydrogen. A regular intermetallic compound having a metal element (α) as a constituent element was synthesized. In particular, nanoparticles of ordered intermetallic compounds were synthesized by simultaneous reduction of a precursor using sodium naphthalide represented by the chemical formula (2) as an alkali metal radical.
本発明は、強力な還元剤の使用により、遷移金属元素と貴金属元素それぞれのプリカーサーを同時に還元することを可能にする。そのため、貴金属元素と遷移金属元素の原子割合が特定の数値である規則型金属間化合物を還元析出法で製造しようとする際、狙った組成のナノ粒子を析出させることができる。規則型金属間化合物ナノ粒子は、酸化物担持体表面上に高い分散度を保ちながら析出されるため、ナノ粒子同士の凝集および粒径の粗大化を抑制することができる。 The present invention makes it possible to simultaneously reduce the precursors of the transition metal element and the noble metal element by using a strong reducing agent. Therefore, when an ordered intermetallic compound in which the atomic ratio between the noble metal element and the transition metal element is a specific numerical value is to be produced by the reduction deposition method, nanoparticles having a targeted composition can be deposited. Since the regular intermetallic compound nanoparticles are deposited on the surface of the oxide carrier while maintaining a high degree of dispersion, aggregation of the nanoparticles and coarsening of the particle diameter can be suppressed.
この酸化物担持体の比表面積は１〜１００ｍ２ｇ−１程度、好ましくは１０〜１００ｍ２ｇ−１程度とすることが望ましい。また、この酸化物担持体の表面に保持される触媒活性点の平均粒子径は５０ｎｍ以下、好ましくは１〜５ｎｍとすることが望ましい。触媒活性点の重量は、前記担持体の重量の０．１〜１％とすることが望ましい。また、ＰｔｘＴｉｙ（ｘ＋ｙ＝１００：モル比）のｙは、１９≦ｙ≦２５とすることが望ましい。ｙが少なすぎた場合、目的反応に対する触媒活性は低下する。ｙが多すぎた場合にも、触媒活性点の相分離により、触媒活性は低下する。 The specific surface area of the oxide carrier is 1 to 100 m 2 g -1, preferably about desirably about 10 to 100 m 2 g -1. Further, the average particle diameter of the catalytically active sites held on the surface of the oxide carrier is preferably 50 nm or less, preferably 1 to 5 nm. The weight of the catalyst active site is preferably 0.1 to 1% of the weight of the support. Further, it is desirable that y of Pt x Ti y (x + y = 100: molar ratio) is 19 ≦ y ≦ 25. If y is too small, the catalytic activity for the target reaction decreases. Even if y is too much, the catalytic activity is lowered due to phase separation of the catalytic active point.
以下、実施例に基づき、本発明の内容を明らかにする。 Hereinafter, based on an Example, the content of this invention is clarified.
１．合成
合成操作は、すべて常温・常圧の不活性ガス雰囲気下（酸素・水分濃度＜５ｐｐｍ）で行った。
1. Synthesis All synthesis operations were performed in an inert gas atmosphere at normal temperature and pressure (oxygen / water concentration <5 ppm).
Ｐｔ（白金）および金属元素Ｔｉ（チタン）それぞれを含有する有機金属プリカーサー：Ｐｔ（１，５−ｃｙｃｌｏｏｃｔａｄｉｅｎｃｅ）Ｃｌ２およびＴｉＣｌ４（ｔｅｔｒａｈｙｄｒｏｆｕｒａｎ）２を、それぞれ０．０４２ｍｍｏｌおよび０．１７ｍｍｏｌ当量秤量し、２５ｍｌのｔｅｔｒａｈｙｄｒｏｆｕｒａｎ（ＴＨＦ）中に溶解した。この溶液中に０．１５ｇのシリカ（ＳｉＯ２）微粒子粉末を加え、３０分間攪拌し、薄黄色の懸濁溶液を得た（これをＡ液と記す。）。 Organometallic precursors containing Pt (platinum) and the metal element Ti (titanium) respectively: Pt (1,5-cyclotadience) Cl 2 and TiCl 4 (tetrahydrofuran) 2 are weighed 0.042 mmol and 0.17 mmol respectively, Dissolved in 25 ml tetrahydrofuran (THF). In this solution, 0.15 g of silica (SiO 2 ) fine particle powder was added and stirred for 30 minutes to obtain a pale yellow suspension solution (this is referred to as “A solution”).
別途、５０ｍｌのＴＨＦ溶媒中に、１．５ｍｍｏｌ当量の金属ナトリウムおよびナフタリンを加え、一晩攪拌し、黒緑色透明の溶液を得た（これは、組成式がＮａＣ１０Ｈ８のＳｏｄｉｕｍ Ｎａｐｈｔｈａｌｉｄｅ溶液である。以下Ｂ液と記す。）。 Separately, 1.5 mmol equivalents of sodium metal and naphthalene were added to 50 ml of THF solvent and stirred overnight to obtain a black-green transparent solution (this was a sodium Naphthalide solution having a composition formula of NaC 10 H 8. (Hereinafter referred to as “Liquid B”).
（Ａ液）と（Ｂ液）を混合したのち一晩攪拌し、プリカーサーの同時還元を行って、黒褐色の懸濁溶液を得た（これをＣ液と記す。）。 (Liquid A) and (Liquid B) were mixed and then stirred overnight, and the precursor was simultaneously reduced to obtain a black-brown suspension (this is referred to as liquid C).
減圧蒸留によって（Ｃ液）からＴＨＦを除去し、沈殿物として黒褐色固体を得た（これをＤ体と記す。）。 THF was removed from (C liquid) by distillation under reduced pressure, and a black-brown solid was obtained as a precipitate (this is referred to as Form D).
（Ｄ体）に３０ｍｌのヘキサンを加え、超音波を２分間印加した（超音波洗浄器を使用）。 30 ml of hexane was added to (D-form), and ultrasonic waves were applied for 2 minutes (using an ultrasonic cleaner).
６０００回転／分で１０分間遠心分離を施し、上澄みと黒色沈殿物（これをＥ体と記す。）を分離したのち、上澄みを除去した。 Centrifugation was performed at 6000 rpm for 10 minutes to separate the supernatant and the black precipitate (this is referred to as E-form), and then the supernatant was removed.
（Ｅ体）に３０ｍｌのメタノールを加え、超音波を２分間印加した。６０００回転／分で１０分間遠心分離を施し、上澄みと黒色沈殿物（これをＦ体と記す。）を分離したのち、上澄みを除去した。 30 ml of methanol was added to (E body), and ultrasonic waves were applied for 2 minutes. Centrifugation was performed at 6000 rpm for 10 minutes to separate the supernatant and the black precipitate (this is referred to as Form F), and then the supernatant was removed.
上記メタノール添加・超音波印加・遠心分離・上澄み除去の一連の洗浄プロセスを総計４回行い、副反応物を除去した。 The series of washing processes including methanol addition, ultrasonic application, centrifugation, and supernatant removal were performed a total of four times to remove side reactants.
洗浄プロセス終了後、（Ｆ体）を真空乾燥した。乾燥に従い、（Ｆ体）の色は黒から灰白色へ変化した。 (F body) was vacuum-dried after completion | finish of a washing process. According to drying, the color of (F body) changed from black to grayish white.
乾燥後、（Ｆ体）を不活性ガス雰囲気から大気中に取り出した。大気中で安定な灰白色粉末試料（これを試料Ａと記す。）を得た。 After drying, (F form) was taken out from the inert gas atmosphere into the air. A grayish white powder sample (this is referred to as Sample A) stable in the air was obtained.
２．試料同定
粉末Ｘ線回折（ｐＸＲＤ）、ＩＣＰ分析、透過電子顕微鏡および透過電子顕微鏡付属のエネルギー分散型Ｘ線分析（ＥＤＳ）によって、試料Ａの同定を行った。
2. Sample Identification Sample A was identified by powder X-ray diffraction (pXRD), ICP analysis, transmission electron microscope and energy dispersive X-ray analysis (EDS) attached to the transmission electron microscope.
（２．１）ｐＸＲＤ
図１に、試料ＡのｐＸＲＤ測定結果（ＣｕＫａ線を使用）を示す。ＳｉＯ２（１１１）反射に該当する２ｑ〜２１°のピークの他に回折線を認めることはできない。試料Ａの主相は、結晶性の低いＳｉＯ２である。
(2.1) pXRD
FIG. 1 shows the pXRD measurement result of sample A (using CuKa line). In addition to the 2q to 21 ° peak corresponding to SiO 2 (111) reflection, no diffraction lines can be observed. The main phase of sample A is SiO 2 having low crystallinity.
（２．２）ＩＣＰ分析
０．０５ｇの粉末試料を酸溶解し、５００ｍｌに定容後、ＩＣＰ分析法による化学組成評価を行った。試料Ａは、Ｐｔ、ＴｉおよびＳｉを、重量比Ｐｔ：Ｔｉ：Ｓｉ＝１：１：１００で含有することが分かった。ｐＸＲＤの結果と併せて、試料Ａは、０．５重量％のＰｔ、およびＴｉを含有したＳｉＯ２であると結論される。
(2.2) ICP analysis A 0.05 g powder sample was acid-dissolved and the volume was adjusted to 500 ml, and then the chemical composition was evaluated by ICP analysis. Sample A was found to contain Pt, Ti and Si in a weight ratio Pt: Ti: Si = 1: 1: 100. Together with the pXRD results, it is concluded that Sample A is SiO 2 containing 0.5 wt% Pt and Ti.
（２．３）透過電子顕微鏡
試料Ａをメタノール溶媒に超音波分散して懸濁溶液を得た。懸濁溶液に透過電子顕微鏡用グリッド（コロジオン膜附き銅（Ｃｕ）グリッド）を浸潤・乾燥し、透過電子顕微鏡用試料を得た。図２−１に、透過電子顕微鏡像（Ｂｒｉｇｈｔ ｆｉｅｌｄ像）を示す。コントラストの低い直径１０〜１００ｎｍ程度の球状物質と共に、直径２〜３ｎｍの黒色粒子が観察される。図２−２は、図２−１と同じ視野をＡｎｎｕｌａｒ ｄａｒｋ ｆｉｅｌｄ（ＡＤＦ）モードで観察した画像である。図２−１の黒色粒子は、ＡＤＦモードにおいては白く明るい輝点として観察されることから、球状物質の構成元素に比べて重い元素を含有している相であることが分かる。
(2.3) Transmission Electron Microscope Sample A was ultrasonically dispersed in a methanol solvent to obtain a suspension solution. A transmission electron microscope grid (copper (Cu) grid-attached copper (Cu) grid) was infiltrated into the suspension solution and dried to obtain a transmission electron microscope sample. FIG. 2-1 shows a transmission electron microscope image (Bright field image). Black particles having a diameter of 2 to 3 nm are observed together with a spherical substance having a low contrast of about 10 to 100 nm in diameter. FIG. 2-2 is an image obtained by observing the same field of view as in FIG. 2-1 in an annular dark field (ADF) mode. The black particles in FIG. 2-1 are observed as white bright bright spots in the ADF mode, and thus it is understood that the black particles are phases containing heavier elements than the constituent elements of the spherical substance.
（２．４）ＥＤＳ分析
図２−１に示された２種類の相：球状物質と黒色粒子それぞれに電子線を収束させ、発生する特性Ｘ線のエネルギーと強度を測定することにより、化学組成を評価した（ＥＤＳ分析）。図３−１および図３−２に、球状物質および黒色粒子それぞれから得られたＥＤＳプロファイルを示す。球状物質のＥＤＳプロファイルには、グリッド由来のＣｕ以外にＳｉ由来の信号のみが認められる。
(2.4) EDS analysis The two types of phases shown in Fig. 2-1. Chemical composition by focusing the electron beam on each of the spherical material and black particles and measuring the energy and intensity of the generated characteristic X-rays. Was evaluated (EDS analysis). FIGS. 3A and 3B show EDS profiles obtained from the spherical material and the black particles, respectively. In the EDS profile of the spherical material, only signals derived from Si are recognized in addition to Cu derived from the grid.
球状物質は、ＥＤＳ分析結果、ｐＸＲＤおよびＩＣＰ分析の結果を総合して、球状のＳｉＯ２粒子であると結論できる。一方、黒色粒子のＥＤＳプロファイルには、Ｃｕ、Ｓｉ以外に、ＰｔおよびＴｉの信号が認められる。ＰｔおよびＴｉの信号強度からそれぞれの元素の存在比率を計算した結果、黒色粒子はＰｔ：Ｔｉ＝３：１（モル比）を備えた金属間化合物相：Ｐｔ３Ｔｉであることが分かった。 It can be concluded that the spherical substance is a spherical SiO 2 particle by combining the results of EDS analysis, pXRD and ICP analysis. On the other hand, in the EDS profile of black particles, signals of Pt and Ti are recognized in addition to Cu and Si. As a result of calculating the abundance ratio of each element from the signal intensities of Pt and Ti, it was found that the black particles had an intermetallic compound phase with Pt: Ti = 3: 1 (molar ratio): Pt 3 Ti.
以上の同定結果から、試料Ａは、粒子径２〜３ｎｍのＰｔ３Ｔｉナノ粒子が粒子径１０〜１００ｎｍの球状ＳｉＯ２担持体表面に分散・担持された担持触媒（以降、Ｐｔ３Ｔｉ／ＳｉＯ２と呼ぶ）であるものと結論される。 From the above identification results, Sample A is a supported catalyst in which Pt 3 Ti nanoparticles having a particle diameter of 2 to 3 nm are dispersed and supported on the surface of a spherical SiO 2 support having a particle diameter of 10 to 100 nm (hereinafter referred to as Pt 3 Ti / SiO 2 ).
３．ＣＯ清浄化触媒活性評価
ＣＯ清浄化反応に対するＰｔ３Ｔｉ／ＳｉＯ２の触媒活性を測定した。垂直に配置した長さ４００ｍｍ、内径φ８ｍｍの石英反応管中央部に、１０ｍｍほどの厚みに石英綿を詰めた。石英反応管上部開口部から総量５０ｍｇの試料を導入し、石英綿の上面に均一に敷き詰めた。別の石英綿を、石英反応管上部開口部から、試料に接触するまで挿入した。これにより、試料は、厚み約１０ｍｍの石英綿で上下から挟み込まれる形になった。石英反応管を管状電気炉炉心に挿入した。石英反応管下部開口部から熱電対を挿入、熱電対先端を試料直下の石英綿に接触させ、試料の温度をモニターした。石英反応管下部開口部をＣＯ・Ｏ２（酸素）・Ｈｅ（ヘリウム）混合ガスラインに接続した。石英反応管上部開口部をガスクロマトグラフィのガスインレットポートに接続した。
3. Evaluation of CO cleaning catalyst activity The catalytic activity of Pt 3 Ti / SiO 2 for the CO cleaning reaction was measured. Quartz cotton was packed in a thickness of about 10 mm in a central part of a quartz reaction tube having a length of 400 mm and an inner diameter of 8 mm arranged vertically. A sample having a total amount of 50 mg was introduced from the upper opening of the quartz reaction tube, and was uniformly spread on the upper surface of quartz cotton. Another quartz cotton was inserted from the top opening of the quartz reaction tube until it contacted the sample. As a result, the sample was sandwiched from above and below by quartz cotton having a thickness of about 10 mm. A quartz reaction tube was inserted into the tubular electric furnace core. A thermocouple was inserted from the lower opening of the quartz reaction tube, and the tip of the thermocouple was brought into contact with quartz cotton directly under the sample, and the temperature of the sample was monitored. The lower opening of the quartz reaction tube was connected to a CO / O 2 (oxygen) / He (helium) mixed gas line. The upper opening of the quartz reaction tube was connected to the gas inlet port of gas chromatography.
石英反応管に、ＣＯ・Ｏ２・Ｈｅ混合ガス（体積比２：１：９７）を、１気圧下、毎分１００ｍｌで流した。インレットガスとして石英反応管下部開口部から導入された混合ガスは、試料部を通過した後、アウトレットガスとして上部開口部から排出され、ガスクロマトグラフィのガスインレットポートに達する。混合ガスを流しながら、管状電気炉に通電し、常温から３４０℃まで試料温度を上昇させた。２５℃ごとに温度上昇を止め、定常温度とした。それぞれの定常温度で、ガスクロマトグラフィによるアウトレットガスの組成分析を行った。 A CO / O 2 / He mixed gas (volume ratio 2: 1: 97) was allowed to flow through the quartz reaction tube at a rate of 100 ml per minute at 1 atmosphere. The mixed gas introduced from the lower opening of the quartz reaction tube as the inlet gas passes through the sample portion, and is then discharged from the upper opening as the outlet gas and reaches the gas inlet port of the gas chromatography. While flowing the mixed gas, the tubular electric furnace was energized to raise the sample temperature from room temperature to 340 ° C. The temperature rise was stopped every 25 ° C. to obtain a steady temperature. The composition analysis of the outlet gas was performed by gas chromatography at each steady temperature.
比較のため、Ｐｔ３Ｔｉ／ＳｉＯ２と同じ球状ＳｉＯ２粒子表面に、Ｐｔ３Ｔｉナノ粒子と同じ粒子径を持った純Ｐｔナノ粒子を、ＳｉＯ２に対して０．２５、０．５、１．０重量％で分散・担持させた３種類の標準試料（以降それぞれ、Ｐｔ０．２５％／ＳｉＯ２、Ｐｔ０．５０％／ＳｉＯ２、Ｐｔ１．０％／ＳｉＯ２と呼ぶ）を用いて、同じ測定を行った。 For comparison, the same spherical SiO 2 particle surface and Pt 3 Ti / SiO 2, the pure Pt nanoparticles having the same particle diameter as Pt 3 Ti nanoparticles, relative to SiO 2 0.25, 0.5, Using three types of standard samples dispersed and supported at 1.0% by weight (hereinafter referred to as Pt 0.25% / SiO 2 , Pt 0.50% / SiO 2 , Pt 1.0% / SiO 2 ), The same measurement was performed.
測定結果を表１と図４に示す。 The measurement results are shown in Table 1 and FIG.
図４は、アウトレットガス中のＣＯ２とインレットガス中のＣＯの体積比（転換率：ｃｏｎｖｅｒｓｉｏｎｒａｔｅ）を、温度の関数としてプロットしたものである。 FIG. 4 is a plot of the volume ratio of CO 2 in the outlet gas to CO in the inlet gas (conversion rate) as a function of temperature.
Ｐｔ０．２５％／ＳｉＯ２の場合、転換率は常温から２２５℃まで０％である。試料温度を上げると、転換率は２５０℃近傍で有限の値となった後に増加し、３００℃で約７０％に達する。 In the case of Pt 0.25% / SiO 2 , the conversion rate is 0% from normal temperature to 225 ° C. When the sample temperature is raised, the conversion rate increases after reaching a finite value near 250 ° C., and reaches about 70% at 300 ° C.
Ｐｔ０．５０％／ＳｉＯ２の場合、転換率は常温から２００℃まで０％を保つ。試料温度を上げると、転換率は２５０℃近傍から増加しはじめ、２９０℃で約７０％に達する。 In the case of Pt 0.50% / SiO 2 , the conversion rate keeps 0% from normal temperature to 200 ° C. When the sample temperature is raised, the conversion rate starts to increase from around 250 ° C. and reaches about 70% at 290 ° C.
２５０℃で転換率を比較すると、Ｐｔ０．２５％／ＳｉＯ２、Ｐｔ０．５０％／ＳｉＯ２、Ｐｔ１．０％／ＳｉＯ２それぞれに対する転換率は、４．３、１２、３２％と、Ｐｔの含有量に伴って単調に増加する。 When the conversion rate is compared at 250 ° C., the conversion rates for Pt 0.25% / SiO 2 , Pt 0.50% / SiO 2 and Pt 1.0% / SiO 2 are 4.3, 12, 32%, respectively. Monotonically increases with content.
一方Ｐｔ３Ｔｉ／ＳｉＯ２の場合、１２５℃においてすでに有意の転換率を示す。転換率は温度上昇とともに増加し、２５０℃で３９％を示したのち、３００℃で１００％に達する。 On the other hand, in the case of Pt 3 Ti / SiO 2, a significant conversion rate is already exhibited at 125 ° C. The conversion rate increases with increasing temperature, reaching 39% at 250 ° C and then reaching 100% at 300 ° C.
Ｐｔ３Ｔｉ／ＳｉＯ２は、当量のＰｔを含有したＰｔ０．５０％／ＳｉＯ２と比較して、１００℃以上低い温度で触媒活性を発現するだけでなく、２５０℃で転換率を比較した場合には３倍以上の転換率を示す。またＰｔ３Ｔｉ／ＳｉＯ２は、重量比で２倍のＰｔを含有するＰｔ１．０％／ＳｉＯ２と同じ温度で比較した場合、常にこれを上回る転換率を示す。 Pt 3 Ti / SiO 2 not only exhibits catalytic activity at a temperature lower by 100 ° C. or more than Pt 0.50% / SiO 2 containing an equivalent amount of Pt, but also when the conversion rate is compared at 250 ° C. Indicates a conversion rate of 3 times or more. Further, Pt 3 Ti / SiO 2 always shows a conversion rate exceeding this when compared at the same temperature as Pt 1.0% / SiO 2 containing Pt twice as much by weight.
本発明の担持触媒は、化石燃料排気ガスの主要毒性成分であるＣＯに対して高い清浄化触媒活性を発揮することから、以下の３例の産業利用が考えられる。 Since the supported catalyst of the present invention exhibits high cleaning catalytic activity for CO, which is a main toxic component of fossil fuel exhaust gas, the following three examples of industrial use are conceivable.
１． 自動車排気ガス清浄化触媒材料
本発明の担持触媒は、駆動直後のガソリンエンジンから燃料の不完全燃焼に伴って排出されるＣＯガスの清浄化に有効である。
1. Automotive Exhaust Gas Cleaning Catalyst Material The supported catalyst of the present invention is effective for cleaning CO gas discharged from a gasoline engine immediately after driving due to incomplete combustion of fuel.
２． ガスタービン排出ガス清浄化触媒材料
本発明の担持触媒は、発電所で利用されるガスタービン機関からの排出ガスの清浄化に有効である。
2. Gas turbine exhaust gas cleaning catalyst material The supported catalyst of the present invention is effective for cleaning exhaust gas from a gas turbine engine used in a power plant.
３． 燃料電池燃料中の不純物除去
本発明の担持触媒は、水素燃料駆動型の燃料電池において問題とされる燃料中不純物の酸化除去に有効である。
3. Removal of Impurities in Fuel Cell Fuel The supported catalyst of the present invention is effective for oxidizing and removing impurities in fuel, which is a problem in hydrogen fuel-driven fuel cells.
Claims (6)
αｘβｙ …（化学式１）
（α：Ｐｔ、
β：Ｐｂ、Ｓｎ、Ｎｉ、Ｆｅ、Ｚｎ、Ａｌ、及びＴｉのいずれか、
ｘ＋ｙ＝１００、かつ
１９≦ｙ≦２５）。 On the surface of the particulate oxide carrier, a small amount of grain child like catalyst active sites as compared with the oxide carrier is a carrying exhaust gas cleaning supported catalyst, wherein the catalyst active sites, the following A supported catalyst for cleaning exhaust gas, characterized in that it is particles of a regular intermetallic compound having a chemical composition represented by Chemical Formula 1 :
α x β y ( Chemical formula 1)
(Α: Pt ,
β: any of Pb, Sn, Ni, Fe, Zn, Al, and Ti,
x + y = 100 and 19 ≦ y ≦ 25) .
α ｘ β ｙ …（化学式１）
（α：標準電極電位（Ｖ）が＜０である金属元素、β：標準電極電位（Ｖ）が＞０である金属元素。なお、水素（Ｈ）の標準電極電位は零とする。ｘ＋ｙ＝１００：モル比、１９≦ｙ≦２５）。 A method for producing a supported catalyst in which particles of an ordered intermetallic compound are supported on the surface of a particulate oxide support , wherein the ordered intermetallic compound has a chemical composition represented by the following chemical formula 1; the rule type particles of the intermetallic compound, the particulate oxide carrier surface it by the simultaneous reduction of the precursor was used as the reducing agent to a radical of an alkali metal having a low reduction potential than 2.0V than hydrogen characterized Rukoto precipitate above process for production of a supported catalyst:
α x β y (Chemical formula 1)
(Α: metal element whose standard electrode potential (V) is <0, β: metal element whose standard electrode potential (V) is> 0. Note that the standard electrode potential of hydrogen (H) is zero. X + y = 100: molar ratio, 19 ≦ y ≦ 25).
ＮａＣ１０Ｈ８ …（化学式２）。 Radical body before Symbol alkali metal, and having a composition shown in the following chemical formula 2, the manufacturing method according to claim 5:
NaC 10 H 8 (chemical formula 2).
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