JP6099238B2 - Nano single crystal plate integrated catalyst - Google Patents
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- 239000013078 crystal Substances 0.000 title claims description 205
- 239000003054 catalyst Substances 0.000 title claims description 148
- 239000000463 material Substances 0.000 claims description 119
- 230000003197 catalytic effect Effects 0.000 claims description 51
- 238000009825 accumulation Methods 0.000 claims description 38
- 238000006555 catalytic reaction Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 68
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 46
- 229960004643 cupric oxide Drugs 0.000 description 34
- 230000002776 aggregation Effects 0.000 description 25
- 238000004220 aggregation Methods 0.000 description 24
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical group NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 238000003795 desorption Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
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- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
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- 239000011259 mixed solution Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
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- 238000005452 bending Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical group [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
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- 231100000252 nontoxic Toxicity 0.000 description 2
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Description
本発明は、ナノ単結晶板材集積触媒に関する。特に、熱凝集による触媒活性の低下を抑制でき、触媒活性が高く、ＮＯｘ清浄化触媒活性の高いナノ単結晶板材集積触媒に関する。
The present invention relates to a nano single crystal plate material accumulation catalyst . In particular, the present invention relates to a nano single crystal plate material accumulation catalyst that can suppress a decrease in catalytic activity due to thermal aggregation, has high catalytic activity, and has high NOx purification catalytic activity.
近年、環境問題の観点から、自動車の排ガスの毒性を低下させることが可能な触媒が注目されている。
図２７は、触媒装置の一例を示す模式図である。筒状の触媒装置の筒内には、触媒が充填されている。ＣＯ、ＨＣ、ＮＯｘ等の有害なガスを前記触媒装置の筒内を通過させることにより、ＣＯ２、Ｈ２Ｏ、Ｎ２等の有害ではないガスに変換できる。
In recent years, from the viewpoint of environmental problems, a catalyst capable of reducing the toxicity of automobile exhaust gas has attracted attention.
FIG. 27 is a schematic diagram illustrating an example of a catalyst device. The cylinder of the cylindrical catalyst device is filled with a catalyst. CO, HC, by passing the cylinder of the catalytic converter harmful gases such as NO x, CO 2, H 2 O, can be converted into not harmful gas such as N 2.
触媒としては、例えば、Ｐｔ、Ｐｄ、Ｒｈ等の貴金属が用いられる。しかし、これらは高価であるとともに、資源の制約があり、流通量が少ない等の問題がある。
そこで、少量で触媒活性を向上させるために、触媒反応を生じさせる表面の面積（表面積）を増大させる微細化（ｍｉｎｉａｔｕｒｉｚａｔｉｏｎ）の手法が検討された。すなわち、バルク（ｂｕｌｋ）の金属触媒を、粉末（ｐｏｗｄｅｒ）からμ結晶（ｍｉｃｒｏｃｒｙｓｔａｌ）へ、更にナノ粒子（ｎａｎｏｐａｒｔｉｃｌｅ）へと径を小さくして、単位量当たりの表面積（ｍ２／ｇ）を増加させることにより、表面での触媒反応の発生確率を高め、触媒活性を向上させることができる。Ｐｔ（白金）からなるナノシートやナノ粒子などのナノ材料が報告されている（非特許文献１〜４）。
As the catalyst, for example, a noble metal such as Pt, Pd, or Rh is used. However, these are expensive, have resource limitations, and have problems such as a small amount of distribution.
Therefore, in order to improve the catalytic activity with a small amount, a miniaturization technique for increasing the surface area (surface area) that causes a catalytic reaction has been studied. That is, the diameter of the bulk metal catalyst is reduced from powder to microcrystal and then to nanoparticle, and the surface area per unit amount (m 2 / g) is increased. As a result, the probability of occurrence of a catalytic reaction on the surface can be increased and the catalytic activity can be improved. Nanomaterials such as nanosheets and nanoparticles made of Pt (platinum) have been reported (Non-Patent Documents 1 to 4).
しかし、ナノ粒子には互いに凝集してダマ（塊）になりやすいという問題があった。ダマ（塊）になった場合には、単位量当たりの表面積がバルクの金属触媒とほぼ同じになり、触媒活性も同程度となった。 However, the nanoparticles have a problem that they tend to aggregate and become lumps. In the case of lumps, the surface area per unit amount was almost the same as that of the bulk metal catalyst, and the catalytic activity was comparable.
ダマ（塊）の問題を解決するために、ＳｉＯ２等からなる粒子状基体の表面にＰｔ等の貴金属からなるナノ粒子を分散させた媒体も検討された。しかし、この場合も、表面上で熱凝集した。
図２８は、このような媒体上の触媒の熱凝集の一例を説明する図である。例えば、図２８（ａ）に示すように、粒子状基体の表面にナノ粒子を分散させても、高熱下で使用すると、図２８（ｂ）に示すように、表面上で熱凝集（ｔｈｅｒｍａｌ ａｇｇｌｏｍｅｒａｔｉｏｎ）して、単位量当たりの表面積がバルクの金属触媒とほぼ同じになり、触媒活性も同程度となるという問題が発生した。
In order to solve the problem of lumps (lumps), a medium in which nanoparticles made of a noble metal such as Pt are dispersed on the surface of a particulate substrate made of SiO 2 or the like has been studied. However, also in this case, heat aggregation occurred on the surface.
FIG. 28 is a diagram for explaining an example of thermal aggregation of the catalyst on such a medium. For example, as shown in FIG. 28 (a), even when nanoparticles are dispersed on the surface of a particulate substrate, if they are used under high heat, as shown in FIG. 28 (b), thermal aggregation is performed on the surface. ), The surface area per unit amount is almost the same as that of the bulk metal catalyst, and the catalyst activity is also comparable.
本発明は、熱凝集による触媒活性の低下を抑制でき、触媒活性が高い、ナノ単結晶板材集積触媒を提供することを課題とする。
An object of the present invention is to provide a nano single crystal plate material integrated catalyst that can suppress a decrease in catalytic activity due to thermal aggregation and has high catalytic activity.
本発明者は、試行錯誤して、ナノ粒子を用いた触媒の研究を進め、特定の単結晶の特定な面の触媒活性が高いことを発見した。この単結晶の触媒活性面を一面とし、触媒不活性面を側面とするナノ単結晶板材を作成し、通常のナノ粒子より単位量当たりの触媒活性を高められることを見出した。このナノ単結晶板材は、熱凝集により触媒活性面同士をスタッキングして、触媒活性を低下させたが、ハイドロサーマル反応を用いて新規に形成したナノ単結晶板材集積触媒（ナノフラワー）はこのナノ単結晶板材がランダムに触媒活性面同士を接面させることなく集積された構成を有し、熱凝集しても各ナノ単結晶板材間のスペース（空隙部）が保持され、触媒活性の低下を抑制し、前記問題を解決できることを見出し、特にＮＯｘ清浄化触媒として有効であることを見出し、本研究を完成した。
本発明は、以下の構成を有する。
The present inventor conducted research on catalysts using nanoparticles through trial and error, and discovered that the catalytic activity of a specific surface of a specific single crystal is high. A nano-single crystal plate with the catalytically active surface of the single crystal as one side and the catalytically inactive surface as a side surface was created, and it was found that the catalytic activity per unit amount can be increased compared to normal nanoparticles. This nano-single-crystal plate stacked the catalytic active surfaces by thermal aggregation and reduced the catalytic activity. However, the nano-single-crystal plate integrated catalyst (nanoflower) newly formed using hydrothermal reaction Single crystal plates have a structure in which the catalyst active surfaces are randomly integrated without contacting each other, and even when thermally aggregated, the spaces (voids) between the nano single crystal plates are maintained, reducing the catalyst activity. suppressing, it can solve the above problems, in particular found to be effective as a NO x purification catalyst, and completed the study.
The present invention has the following configuration.
（１） 単結晶の触媒活性面を一面とし、触媒不活性面を側面とするナノ単結晶板材が、隣接するナノ単結晶板材間で前記触媒活性面同士を接面させることなく集積されていると共に、前記ナノ単結晶板材がＣｕＯであり、前記触媒活性面が（００１）面であることを特徴とするナノ単結晶板材集積触媒。
（２） 隣接するナノ単結晶板材間で一方の一面に他方の側面が接するように集積されていることを特徴とする（１）に記載のナノ単結晶板材集積触媒。
(1) Nano single crystal plate materials having a single crystal catalytic active surface as one surface and a catalyst inactive surface as a side surface are integrated between adjacent nano single crystal plate materials without bringing the catalytic active surfaces into contact with each other. In addition, the nano single crystal plate material accumulation catalyst , wherein the nano single crystal plate material is CuO, and the catalytic active surface is a (001) surface .
(2) The nano-single crystal plate accumulation catalyst according to (1), wherein the nano-single crystal plate accumulation catalysts are stacked so that one side of the nano-single crystal plate is adjacent to the other side.
（３） 前記ナノ単結晶板材が一面側に凹となるように屈曲又は屈折されていることを特徴とする（１）又は（２）に記載のナノ単結晶板材集積触媒。
（４） 前記ナノ単結晶板材の一面の最小径が１０ｎｍ以上１μｍ未満であり、厚さが前記最小径の１／１０以下であることを特徴とする（１）〜（３）のいずれかに記載のナノ単結晶板材集積触媒。
（５） 前記ナノ単結晶板材の数が３枚以上１０００枚以下であることを特徴とする（１）〜（４）のいずれかに記載のナノ単結晶板材集積触媒。
(3) The nano single crystal plate material accumulation catalyst according to (1) or (2), wherein the nano single crystal plate material is bent or refracted so as to be concave on one side.
(4) The minimum diameter of one surface of the nano single crystal plate material is 10 nm or more and less than 1 μm, and the thickness is 1/10 or less of the minimum diameter. The nano-single crystal plate material accumulation catalyst as described.
(5) The nano single crystal plate material accumulation catalyst according to any one of (1) to (4), wherein the number of the nano single crystal plate materials is 3 or more and 1000 or less.
（６） 前記ナノ単結晶板材の触媒反応は、以下の化学反応式で示されることを特徴とする（１）〜（５）のいずれかに記載のナノ単結晶板材集積触媒。(6) The nano single crystal plate material accumulation catalyst according to any one of (1) to (5), wherein the catalytic reaction of the nano single crystal plate material is represented by the following chemical reaction formula.
本発明のナノ単結晶板材集積触媒は、単結晶の触媒活性面を一面とし、触媒不活性面を側面とするナノ単結晶板材が、隣接するナノ単結晶板材間で前記触媒活性面同士を接面させることなく集積されている構成なので、熱凝集しても、触媒活性面同士が接面されることがなく、触媒活性面の前にスペース（空隙部）が確保され、熱凝集による触媒活性の低下を抑制でき、触媒活性が高くすることができる。 The nano single crystal plate-integrated catalyst of the present invention has a single crystal catalytic active surface as one surface, and a nano single crystal plate material having a catalyst inactive surface as a side surface, and the catalytic active surfaces are in contact with each other between adjacent nano single crystal plate materials. As the structure is integrated without facing, the catalyst active surfaces are not in contact with each other even if they are thermally agglomerated, and a space (void) is secured in front of the catalyst active surfaces. Can be suppressed, and the catalytic activity can be increased.
以下、添付図面を参照しながら、本発明の実施形態であるナノ単結晶板材集積触媒及びその製造方法について説明する。 Hereinafter, a nano single crystal plate material accumulation catalyst and a method for producing the same according to embodiments of the present invention will be described with reference to the accompanying drawings.
（本発明の実施形態）
＜ナノ単結晶板材集積触媒＞
図１は、本発明の実施形態であるナノ単結晶板材集積触媒（ナノフラワー）の一例を示す斜視図である。
図１に示すように、本発明の実施形態であるナノ単結晶板材集積触媒１０１は、複数のナノ単結晶板材１１が集積されて概略構成されている。
なお、ナノ単結晶板材集積触媒１０１は、電子顕微鏡で、花びらのようなナノ単結晶板材１１が集められ、花のような形状で観測されたので、ナノフラワーとも呼称し、それを構成するナノ単結晶板材をナノペタルとも呼称する。
(Embodiment of the present invention)
<Nano-single crystal plate integrated catalyst>
FIG. 1 is a perspective view showing an example of a nano single crystal plate material integrated catalyst (nanoflower) according to an embodiment of the present invention.
As shown in FIG. 1, a nano single crystal plate material integrated catalyst 101 according to an embodiment of the present invention is schematically configured by a plurality of nano single crystal plate materials 11 being integrated.
The nano single crystal plate material accumulation catalyst 101 is also called a nano flower because the nano single crystal plate materials 11 such as petals are collected and observed in a flower-like shape with an electron microscope. Single crystal plate material is also called nanopetal.
ナノ単結晶板材（ナノぺタル）１１は、一面１１ａの大きさに対し、側面１１ｃの厚さが薄い板状部材である。
ナノ単結晶板材（ナノぺタル）１１の一面１１ａ側には、隣接するナノ単結晶板材との間にスペース（空隙部）２１が形成されている。
The nano-single crystal plate material (nano-petal) 11 is a plate-like member having a thin side surface 11c with respect to the size of one surface 11a.
On one surface 11 a side of the nano single crystal plate (nanopetal) 11, a space (gap portion) 21 is formed between adjacent nano single crystal plates.
結晶の触媒活性面を一面とし、触媒不活性面を側面とするナノ単結晶板材が、隣接するナノ単結晶板材間で前記触媒活性面同士を接面させることなく集積されている。これにより、熱凝集させても、隣接するナノ単結晶板材１１間で触媒活性面同士をほとんど接面せず、触媒活性面の前にスペース（空隙部）が確保でき、熱凝集による触媒活性の低下を抑制でき、触媒活性を高く保つことができる。
隣接するナノ単結晶板材間で一方の一面に他方の側面が接するように集積されていることが好ましい。これにより、熱凝集させても、隣接するナノ単結晶板材１１間で触媒活性面同士をほとんど接面せず、触媒活性面の前にスペース（空隙部）が確保できる。
Nano single crystal plate materials having a catalytic active surface of a crystal as one surface and a catalyst inactive surface as a side surface are integrated between adjacent nano single crystal plate materials without bringing the catalytic active surfaces into contact with each other. Thereby, even if it heat-aggregates, the catalyst active surface is hardly contacted between the adjacent nano single-crystal board | plate materials 11, A space (gap part) can be ensured in front of a catalyst active surface, and catalyst activity by heat aggregation is ensured. The decrease can be suppressed and the catalytic activity can be kept high.
It is preferable that the adjacent nano-single crystal plates are integrated such that one side is in contact with the other side. Thereby, even if it heat-aggregates, the catalyst active surface is hardly contacted between the adjacent nano single crystal board | plate materials 11, and a space (gap part) can be ensured in front of a catalyst active surface.
図２は、ナノ単結晶板材（ナノぺタル）の一例を示す図であって、（ａ）は斜視図であり、（ｂ）は構造拡大図であり、（ｃ）は（ｂ）のＡ部の図であり、（ｄ）は（ｃ）の矢印方向からの平面図である。
図２（ｂ）に示すように、ナノ単結晶板材（ナノぺタル）の一例として、ＣｕＯ単結晶を用いている。
図２（ａ）に示すように、ナノ単結晶板材（ナノぺタル）１１の一面１１ａは、単結晶の００１−ａｘｉｓに垂直な面であり、図２（ｃ）の矢印に垂直な面であり、図２（ｄ）に示すように、ＣｕＯ単結晶の４つのＣｕを構成単位とする面である。
FIG. 2 is a diagram showing an example of a nano single crystal plate (nanopetal), in which (a) is a perspective view, (b) is an enlarged view of the structure, and (c) is an A of (b). It is a figure of a part, (d) is a top view from the arrow direction of (c).
As shown in FIG. 2B, a CuO single crystal is used as an example of a nano single crystal plate (nanopetal).
As shown in FIG. 2A, one surface 11a of the nano-single crystal plate (nano-petal) 11 is a surface perpendicular to 001-axis of the single crystal, and a surface perpendicular to the arrow in FIG. Yes, as shown in FIG. 2 (d), it is a surface having four CuO of the CuO single crystal as a structural unit.
図３は、本発明のナノ単結晶板材集積触媒の触媒反応を説明する図である。
図３に示すように、ナノ単結晶板材（ナノぺタル）１１の一面１１ａは、次の化学反応式（１）の触媒反応を行う触媒活性面である。すなわち、ＣＯ、ＮＯの有害なガスをＣＯ２、Ｎ２の有害ではないガスに変換する。これに限られるものではなく、ＣＯ、ＨＣ、ＮＯｘ等の有害なガスをすべて、ＣＯ２、Ｈ２Ｏ、Ｎ２等の有害ではないガスに変換する。
FIG. 3 is a view for explaining the catalytic reaction of the nano-single crystal plate accumulation catalyst of the present invention.
As shown in FIG. 3, one surface 11a of the nano single crystal plate (nanopetal) 11 is a catalytically active surface that performs a catalytic reaction of the following chemical reaction formula (1). That is, harmful gases such as CO and NO are converted into non-toxic gases such as CO 2 and N 2 . However, the present invention is not limited to this, and all harmful gases such as CO, HC, and NO x are converted into non-toxic gases such as CO 2 , H 2 O, and N 2 .
一方、ナノ単結晶板材（ナノぺタル）１１の側面１１ｃは次の化学反応式（２）の触媒反応を行う触媒不活性面である。すなわち、ＣＯ、ＮＯをＮ２Ｏ、ＣＯ、ＣＯ２に変換する。ＣＯ、ＨＣ、ＮＯｘ等の有害なガスがすべて、ＣＯ２、Ｈ２Ｏ、Ｎ２等の有害ではないガスに変換されるわけではなく、例えば、１／２モルのＣＯが変換されない。 On the other hand, the side surface 11c of the nano single crystal plate material (nanopetal) 11 is a catalyst inactive surface that performs the catalytic reaction of the following chemical reaction formula (2). That is, CO and NO are converted into N 2 O, CO, and CO 2 . Not all harmful gases such as CO, HC, NO x are converted into non-hazardous gases such as CO 2 , H 2 O, N 2 , for example, ½ mole of CO is not converted.
図４は、本発明のナノ単結晶板材集積触媒の熱凝集を説明する図である。
図４に示すように、本発明のナノ単結晶板材集積触媒１０１は、熱凝集させても、隣接するナノ単結晶板材１１間で触媒活性面同士をほとんど接面せず、触媒活性面の前にスペース（空隙部）が確保でき、熱凝集による触媒活性の低下を抑制でき、触媒活性を高く保つことができる。
FIG. 4 is a diagram for explaining thermal aggregation of the nano-single crystal plate accumulation catalyst of the present invention.
As shown in FIG. 4, even when the nano single crystal plate material integrated catalyst 101 of the present invention is thermally agglomerated, the catalytic active surfaces hardly contact each other between adjacent nano single crystal plate materials 11, and the catalyst active surface is in front of each other. In addition, a space (void) can be ensured, a decrease in catalytic activity due to thermal aggregation can be suppressed, and the catalytic activity can be kept high.
図５は、ナノ単結晶板材の熱凝集を説明する図である。
図５に示すように、ナノ単結晶板材１１は、熱凝集させると、隣接するナノ単結晶板材１１間で触媒活性面同士を接面するように集積され、触媒活性面の前のスペース（空隙部）を確保できず、熱凝集による触媒活性の低下を抑制できず、触媒活性を高く保つことができない。
FIG. 5 is a diagram illustrating thermal aggregation of the nano single crystal plate material.
As shown in FIG. 5, when the nano single crystal plate material 11 is thermally aggregated, the nano single crystal plate materials 11 are accumulated so that the catalytic active surfaces are in contact with each other between the adjacent nano single crystal plate materials 11. Part) cannot be ensured, a decrease in catalytic activity due to thermal aggregation cannot be suppressed, and the catalytic activity cannot be kept high.
ナノ単結晶板材（ナノぺタル）１１の一面１１ａの最小径が１０ｎｍ以上１μｍ未満であり、厚さが前記最小径の１／１０以下であることが好ましい。これにより、ナノ単結晶板材（ナノぺタル）１１の一面１１ａの面積を側面１１ｃの面積に比べて約１０倍以上広くでき、単位量当たりの触媒活性をナノ粒子に比べて高めることができる。
前記最小径を１μｍ以上とすると、ナノ単結晶板材（ナノぺタル）１１を高密度で集積させることができない。逆に、前記最小径を１０ｎｍ未満とすると、熱凝集させた場合、隣接するナノ単結晶板材１１間で触媒活性面同士を接面する場合が生じる。
厚さは１ｎｍ以上とすることが好ましい。厚さを１ｎｍ未満とすると、膜厚方向の剛性が低下するので、熱凝集させた場合、割れるおそれが生じる。
It is preferable that the minimum diameter of one surface 11a of the nano single crystal plate (nanopetal) 11 is 10 nm or more and less than 1 μm, and the thickness is 1/10 or less of the minimum diameter. Thereby, the area of one surface 11a of the nano single crystal plate material (nanopetal) 11 can be made about 10 times or more larger than the area of the side surface 11c, and the catalytic activity per unit amount can be increased compared to the nanoparticles.
When the minimum diameter is 1 μm or more, the nano single crystal plate material (nanopetal) 11 cannot be integrated at a high density. On the other hand, when the minimum diameter is less than 10 nm, the catalyst active surfaces may be brought into contact with each other between the adjacent nano-single crystal plates 11 when thermally aggregated.
The thickness is preferably 1 nm or more. If the thickness is less than 1 nm, the rigidity in the film thickness direction is lowered, so that when heat aggregation is performed, there is a risk of cracking.
図１では、１２枚のナノ単結晶板材１１が集積されてなるナノ単結晶板材集積触媒１０１を示したが、ナノ単結晶板材（ナノぺタル）１１の枚数は１２枚に限られる訳ではない。
ナノ単結晶板材（ナノぺタル）１１の枚数は、３枚以上１０００枚以下とすることが好ましい。３枚未満では、熱凝集させた場合、隣接するナノ単結晶板材１１間で触媒活性面同士を接面する場合が生じる。このように複数のナノ単結晶板材１１がスタッキングされた場合は、全触媒活性面の面積が小さくなるので、触媒活性を低下させる。１０００枚超の場合には、ナノ単結晶板材集積触媒１０１の大きさが大きくなりすぎ、触媒としての取り扱いが困難になる場合が生じる。
In FIG. 1, the nano single crystal plate material accumulation catalyst 101 in which twelve nano single crystal plate materials 11 are integrated is shown, but the number of nano single crystal plate materials (nanopetals) 11 is not limited to twelve. .
The number of nano-single crystal plates (nanopetals) 11 is preferably 3 or more and 1000 or less. If the number is less than 3, the catalyst active surfaces may be in contact with each other between the adjacent nano-single crystal plates 11 when thermally aggregated. Thus, when the several nano single crystal board | plate material 11 is stacked, since the area of all the catalyst active surfaces becomes small, catalyst activity is reduced. In the case of more than 1000 sheets, the size of the nano-single crystal plate integrated catalyst 101 becomes too large, and handling as a catalyst may become difficult.
ナノ単結晶板材１１がＣｕもしくはその合金又これらの化合物であることが好ましい。これらの材料を用いることにより、有用な触媒を形成できる。化合物とは、窒化物、酸化物等である。特に、Ｃｕは低価格であるので製造コストを低下させることができるとともに、資源量も豊富であるので、容易に入手して、触媒として製造することができる。
It is preferable that the nano single crystal plate material 11 is Cu, an alloy thereof, or a compound thereof. Useful catalysts can be formed by using these materials. The compound is a nitride, an oxide or the like. In particular, since Cu is low in price, the manufacturing cost can be reduced, and the amount of resources is abundant, so that it can be easily obtained and manufactured as a catalyst.
ナノ単結晶板材としてＣｕＯを用いることが好ましい。ＣｕＯを用いた場合には、触媒活性面として（００１）面を用いる。これにより、先に記載の化学反応式（１）で示される触媒反応を効率的に行わせることができる。製造コストも低下させることができる。 It is preferable to use CuO as the nano single crystal plate. When CuO is used, the (001) plane is used as the catalyst active plane. Thereby, the catalytic reaction shown by the chemical reaction formula (1) described above can be performed efficiently. Manufacturing costs can also be reduced.
＜ナノ単結晶板材集積触媒の製造方法＞
図６は、本発明のナノ単結晶板材集積触媒の製造工程の一例を説明するフローチャート図である。ＣｕＯナノフラワーを製造する場合を一例としている。
図６に示すように、本発明の実施形態であるナノ単結晶板材集積触媒１１の製造方法は、混合工程Ｓ１と、温度・圧力印加工程Ｓ２と、を有する。
<Manufacturing Method of Nano Single Crystal Plate Integrated Catalyst>
FIG. 6 is a flow chart for explaining an example of the manufacturing process of the nano single crystal plate material accumulation catalyst of the present invention. The case where a CuO nanoflower is manufactured is taken as an example.
As shown in FIG. 6, the manufacturing method of the nano single crystal plate material integrated catalyst 11 according to the embodiment of the present invention includes a mixing step S1 and a temperature / pressure applying step S2.
（混合工程Ｓ１）
混合工程は、所定量の貴金属又はその合金のハロゲン化物と炭酸ジアミド骨格を有する有機化合物を水溶液に溶かす工程である。Ｃｕ又はその合金のハロゲン化物としては、例えば、ＣｕＣｌ2を挙げることができる。炭酸ジアミド骨格を有する有機化合物としては、例えば、尿素を挙げることができる。
(Mixing step S1)
The mixing step is a step of dissolving a predetermined amount of a noble metal halide or an alloy thereof and an organic compound having a carbonate diamide skeleton in an aqueous solution. An example of the halide of Cu or its alloy is CuCl 2 . Examples of the organic compound having a carbonic acid diamide skeleton include urea.
なお、前記水溶液に有機溶媒を添加してから、Ｃｕ又はその合金のハロゲン化物と尿素を混合することが好ましい。有機溶媒としてはエチレングリコール等を用いる。水溶液に対して５０モル％以下の濃度となるように有機溶媒を添加することが好ましい。これにより、溶質の分散性を高めることができる。
In addition, it is preferable to add the organic solvent to the aqueous solution and then mix Cu or its alloy halide with urea. Ethylene glycol or the like is used as the organic solvent. It is preferable to add the organic solvent so that the concentration is 50 mol% or less with respect to the aqueous solution. Thereby, the dispersibility of a solute can be improved.
（温度・圧力印加工程Ｓ２）
混合溶液に所定温度・圧力を印加して、所定時間、放置する工程である。
１００℃以上３００℃以下で加熱することが好ましい。１００℃未満では、尿素と金属ハロゲン化物との反応を完了させることができない。３００℃超では、発生する高蒸気圧に反応容器が耐えられない。
前記温度で１０時間以上加熱することが好ましい。１０時間未満では、未反応の材料が残留する場合が生じる。
所定の圧力とは、１００℃における水の蒸気圧（１気圧）以上の圧力とすることが好ましい。
なお、所定の温度・圧力を印加するためには、例えば、圧力釜で加熱する方法を用いることができる。
(Temperature / pressure application step S2)
In this step, a predetermined temperature and pressure are applied to the mixed solution and left for a predetermined time.
It is preferable to heat at 100 ° C. or higher and 300 ° C. or lower. Below 100 ° C., the reaction between urea and the metal halide cannot be completed. Above 300 ° C., the reaction vessel cannot withstand the high vapor pressure generated.
It is preferable to heat at the said temperature for 10 hours or more. If it is less than 10 hours, unreacted material may remain.
The predetermined pressure is preferably a pressure equal to or higher than the vapor pressure of water at 100 ° C. (1 atm).
In addition, in order to apply predetermined temperature and pressure, the method of heating with a pressure cooker can be used, for example.
例えば、ＣｕＣｌ２と尿素から、次の化学反応式（３）のように、ＣｕＯナノフラワーを製造することができる。 For example, CuO nanoflowers can be produced from CuCl 2 and urea as shown in the following chemical reaction formula (3).
以上の工程により、本発明の実施形態であるナノ単結晶板材集積触媒１１を製造することができる。 Through the above steps, the nano-single crystal plate material integrated catalyst 11 according to the embodiment of the present invention can be manufactured.
図７は、ナノ単結晶板材の別の一例を示す斜視図である。
ナノ単結晶板材１２は、一面１２ａ側に凹となるように屈折線１２ｄで屈折されている。
このようにナノ単結晶板材１２が一面１２ａ側に凹となるように屈曲又は屈折されていることが好ましい。このようなナノ単結晶板材１２を、単結晶の触媒活性面を一面とし、触媒不活性面を側面とするナノ単結晶板材が、隣接するナノ単結晶板材間で前記触媒活性面同士を接面させることなく集積されたナノ単結晶板材集積触媒を用いれば、熱凝集させても、隣接するナノ単結晶板材１２間で触媒活性面同士をより接面させず、触媒活性面の前にスペース（空隙部）が確保でき、熱凝集による触媒活性の低下を抑制でき、触媒活性を高く保つことができる。
また、剛性を高くすることができる。
FIG. 7 is a perspective view showing another example of a nano single crystal plate material.
The nano single crystal plate material 12 is refracted by the refraction line 12d so as to be concave on the one surface 12a side.
Thus, it is preferable that the nano single crystal plate material 12 is bent or refracted so as to be concave on the one surface 12a side. In such a nano single crystal plate 12, the nano single crystal plate having the catalyst active surface of the single crystal as one surface and the catalyst inactive surface as the side surface is in contact with the catalytic active surfaces between adjacent nano single crystal plates. If the nano-single crystal plate-integrated catalyst integrated without being used is used, the catalyst active surfaces are not more closely contacted between the adjacent nano-single crystal plate members 12 even when thermally aggregated, and a space (in front of the catalyst active surface ( Voids) can be secured, a decrease in catalytic activity due to thermal aggregation can be suppressed, and the catalytic activity can be kept high.
Further, the rigidity can be increased.
本発明の実施形態であるナノ単結晶板材集積触媒は、単結晶の触媒活性面を一面とし、触媒不活性面を側面とするナノ単結晶板材が、隣接するナノ単結晶板材間で前記触媒活性面同士を接面させることなく集積されている構成なので、熱凝集しても、触媒活性面同士が接面されることがなく、触媒活性面の前にスペース（空隙部）が確保され、熱凝集による触媒活性の低下を抑制でき、触媒活性が高くすることができる。 The nano single crystal plate-integrated catalyst according to an embodiment of the present invention has a catalyst active surface of a single crystal as one surface and a nano single crystal plate material having a catalyst inactive surface as a side surface. Since the surfaces are integrated without contacting each other, even if the heat is agglomerated, the catalytically active surfaces are not contacted with each other, and a space (void) is secured in front of the catalytically active surfaces. A decrease in catalytic activity due to aggregation can be suppressed, and the catalytic activity can be increased.
本発明の実施形態であるナノ単結晶板材集積触媒は、隣接するナノ単結晶板材間で一方の一面に他方の側面が接するように集積されている構成なので、熱凝集しても、触媒活性面同士が接面されることがほとんどなく、触媒活性面の前にスペース（空隙部）が確保され、熱凝集による触媒活性の低下を抑制でき、触媒活性が高くすることができる。 The nano-single crystal plate material accumulation catalyst according to the embodiment of the present invention has a configuration in which the other side surface is in contact with one side surface between adjacent nano-single crystal plate materials. They are hardly contacted with each other, a space (void) is ensured in front of the catalyst active surface, a decrease in catalyst activity due to thermal aggregation can be suppressed, and the catalyst activity can be increased.
本発明の実施形態であるナノ単結晶板材集積触媒は、前記ナノ単結晶板材が一面側に凹となるように屈曲又は屈折されている構成なので、熱凝集しても、触媒活性面同士が接面されることがなく、触媒活性面の前にスペース（空隙部）が確保され、熱凝集による触媒活性の低下を抑制でき、触媒活性が高くすることができる。 The nano single crystal plate material integrated catalyst according to an embodiment of the present invention has a configuration in which the nano single crystal plate material is bent or refracted so as to be concave on one surface side. Therefore, a space (void) is secured in front of the catalyst active surface, a decrease in the catalyst activity due to thermal aggregation can be suppressed, and the catalyst activity can be increased.
本発明の実施形態であるナノ単結晶板材集積触媒は、前記ナノ単結晶板材の一面の最小径が１０ｎｍ以上１μｍ未満であり、厚さが前記最小径の１／１０以下である構成なので、熱凝集しても、触媒活性面同士が接面されることがなく、触媒活性面の前にスペース（空隙部）が確保され、熱凝集による触媒活性の低下を抑制でき、触媒活性が高くすることができる。 Since the nano single crystal plate-integrated catalyst according to an embodiment of the present invention has a configuration in which the minimum diameter of one surface of the nano single crystal plate is 10 nm or more and less than 1 μm and the thickness is 1/10 or less of the minimum diameter, Even if agglomeration occurs, the catalyst active surfaces are not brought into contact with each other, a space (void) is ensured in front of the catalyst active surfaces, a decrease in catalyst activity due to thermal aggregation can be suppressed, and the catalyst activity is increased. Can do.
本発明の実施形態であるナノ単結晶板材集積触媒は、前記ナノ単結晶板材の数が３枚以上１０００枚以下である構成なので、熱凝集しても、触媒活性面同士が接面されることがなく、触媒活性面の前にスペース（空隙部）が確保され、熱凝集による触媒活性の低下を抑制でき、触媒活性が高くすることができる。 Since the nano single crystal plate-integrated catalyst according to an embodiment of the present invention has a configuration in which the number of the nano single crystal plate materials is 3 or more and 1000 or less, the catalytic active surfaces are in contact with each other even when thermally aggregated. In this case, a space (void) is ensured in front of the catalyst active surface, a decrease in the catalyst activity due to thermal aggregation can be suppressed, and the catalyst activity can be increased.
本発明の実施形態であるナノ単結晶板材集積触媒は、前記ナノ単結晶板材が貴金属もしくはその合金又はこれらの化合物である構成なので、高触媒活性の触媒とすることができる。 The nano single crystal plate material integrated catalyst according to the embodiment of the present invention can be a catalyst with high catalytic activity because the nano single crystal plate material is a noble metal, an alloy thereof, or a compound thereof.
本発明の実施形態であるナノ単結晶板材集積触媒は、前記ナノ単結晶板材がＣｕＯであり、前記触媒活性面が（００１）面である構成なので、低価格で、ＮＯｘの高触媒活性の触媒とすることができる。 Nano single crystal plate integrated catalyst which is an embodiment of the invention, the a nano single crystal plate is CuO, since the catalytic active surface is configured a (001) plane, at low cost, high catalytic activity of the NO x It can be a catalyst.
本発明の実施形態であるナノ単結晶板材集積触媒において、実施例に示した製造方法によれば、Ｃｕ又はその合金のハロゲン化物と炭酸ジアミド骨格を有する有機化合物を水溶液中で圧力を印加して加熱するハイドロサーマル反応させる構成なので、単結晶の触媒活性面を一面とし、触媒不活性面を側面とするナノ単結晶板材が、隣接するナノ単結晶板材間で前記触媒活性面同士を接面させることなく集積され、熱凝集による触媒活性の低下を抑制でき、触媒活性が高いナノ単結晶板材集積触媒を容易に製造することができる。低価格の貴金属を用いた場合には、触媒の材料コストを低減できる。
In the nano single crystal plate-integrated catalyst according to the embodiment of the present invention , according to the production method shown in the examples , Cu or an alloy halide thereof and an organic compound having a carbonic acid diamide skeleton are applied in an aqueous solution. Since the structure is a hydrothermal reaction that heats, a single crystal catalytic active surface is a single surface, and a nano single crystal plate material having a catalytic inactive surface as a side surface contacts the catalytic active surfaces between adjacent nano single crystal plate materials. Therefore, it is possible to easily produce a nano-single crystal plate-integrated catalyst that can be accumulated without any deterioration of the catalytic activity due to thermal aggregation and has high catalytic activity. When low-priced noble metals are used, the material cost of the catalyst can be reduced.
本発明の実施形態であるナノ単結晶板材集積触媒は、水溶液に有機溶媒を添加してから、前記ハイドロサーマル反応をさせる構成なので、溶質の分散性を高め、ナノ単結晶板材集積触媒を容易に製造することができる。 Since the nano single crystal plate-integrated catalyst according to an embodiment of the present invention is configured to perform the hydrothermal reaction after adding an organic solvent to an aqueous solution, the dispersibility of the solute is improved, and the nano single crystal plate-integrated catalyst is easily formed. Can be manufactured.
本発明の実施形態であるナノ単結晶板材集積触媒は、１００℃以上３００℃以下で加熱する構成なので、溶質の分散性を高め、ナノ単結晶板材集積触媒を容易に製造することができる。 Since the nano single crystal plate material accumulation catalyst according to the embodiment of the present invention is heated at 100 ° C. or more and 300 ° C. or less, the dispersibility of the solute can be improved and the nano single crystal plate material accumulation catalyst can be easily produced.
本発明の実施形態であるナノ単結晶板材集積触媒は、前記温度で１０時間以上加熱する構成なので、溶質の分散性を高め、ナノ単結晶板材集積触媒を容易に製造することができる。 Since the nano single crystal plate material accumulation catalyst which is an embodiment of the present invention is configured to be heated at the above temperature for 10 hours or more, the dispersibility of the solute can be improved and the nano single crystal plate material accumulation catalyst can be easily produced.
本発明の実施形態であるナノ単結晶板材集積触媒及びその製造方法は、上記実施形態に限定されるものではなく、本発明の技術的思想の範囲内で、種々変更して実施することができる。本実施形態の具体例を以下の実施例で示す。しかし、本発明はこれらの実施例に限定されるものではない。 The nano single crystal plate material accumulation catalyst and the production method thereof according to the embodiment of the present invention are not limited to the above embodiment, and can be implemented with various modifications within the scope of the technical idea of the present invention. . Specific examples of this embodiment are shown in the following examples. However, the present invention is not limited to these examples.
（実施例１）
＜試料作成＞
（混合工程Ｓ１）
まず、ＣｕＣｌ２（アルドリッチ製）を用意した。
次に、尿素（アルドリッチ製）を用意した。
次に、水溶液に５０モル％以下の濃度のエチレングリコールを混合して、混合溶液を調整した。
Example 1
<Sample preparation>
(Mixing step S1)
First, CuCl 2 (manufactured by Aldrich) was prepared.
Next, urea (manufactured by Aldrich) was prepared.
Next, ethylene glycol having a concentration of 50 mol% or less was mixed with the aqueous solution to prepare a mixed solution.
（温度・圧力印加工程Ｓ２）
次に、混合溶液を圧力釜の内部に配置した。
次に、１４０℃に加熱して、１４時間、放置した。
次に、室温に戻し、圧力釜から混合溶液を取り出した。混合溶液中に沈殿物（実施例１試料）が形成されていた。
(Temperature / pressure application step S2)
Next, the mixed solution was placed inside the pressure cooker.
Next, it was heated to 140 ° C. and left for 14 hours.
Next, the temperature was returned to room temperature, and the mixed solution was taken out from the pressure cooker. A precipitate (Example 1 sample) was formed in the mixed solution.
（比較例１）
実施例１試料を粉砕して、粉末（比較例１試料）を作製した。
(Comparative Example 1)
The sample of Example 1 was pulverized to produce a powder (Comparative Example 1 sample).
（比較例２）
市販の酸化銅ナノ粒子（Ｃｏｍｍｅｒｃｉａｌ ＣｕＯ ＮＰｓ）を用意して、これを比較例２試料とした。
(Comparative Example 2)
Commercially available copper oxide nanoparticles (Commercial CuO NPs) were prepared and used as Comparative Example 2 samples.
＜試料評価＞
図８は、実施例１試料（ナノ単結晶板材集積触媒（ナノフラワー））のＨＩＢ−ＳＥＭ像である。
実施例１試料（ナノ単結晶板材集積触媒（ナノフラワー））は、ナノ単結晶板材（ナノぺタル）１３に代表されるナノ単結晶板材（ナノぺタル）が集積されて形成されていた。
図９は、図８のＢ部拡大図（ａ）及びナノ単結晶板材（ナノぺタル）の一例を示す模式図（ｂ）である。図１０は、ナノ単結晶板材（ナノぺタル）の一例を示す図であって、（ａ）は平面図であり、（ｂ）は（ａ）のＣ−Ｃ’線における断面図である。
ナノ単結晶板材（ナノぺタル）１３は、板材であり、一端側と他端側がそれぞれ反対側に曲げられていた。一面１３ａと他面１３ｂの面積はほぼ等しく、一面１３ａの面積に対して、側面１３ｃの面積は約１／２０であった。一端側は屈曲線１３ｄで一面側に凹となるように曲げられていた。
ナノ単結晶板材（ナノぺタル）１３の周りには、少なくとも２３ａ〜２３ｅまでのスペース（空隙部）が存在していた。
<Sample evaluation>
FIG. 8 is an HIB-SEM image of the sample of Example 1 (nano-single crystal plate integrated catalyst (nanoflower)).
Example 1 The sample (nano-single crystal plate integrated catalyst (nanoflower)) was formed by integrating nano-single crystal plates (nanopetals) represented by nano-single crystal plate (nanopetal) 13.
FIG. 9 is a schematic diagram (b) showing an example of an enlarged view of part B of FIG. 8 and an example of a nano single crystal plate (nanopetal). 10A and 10B are diagrams showing an example of a nano single crystal plate (nanopetal), where FIG. 10A is a plan view and FIG. 10B is a cross-sectional view taken along the line CC ′ in FIG.
The nano single crystal plate material (nanopetal) 13 was a plate material, and one end side and the other end side were bent to opposite sides. The area of the one surface 13a and the other surface 13b is substantially equal, and the area of the side surface 13c is about 1/20 with respect to the area of the one surface 13a. One end side was bent so as to be concave on one surface side by a bending line 13d.
Around the nano-single crystal plate (nano-petal) 13, there were at least spaces (voids) from 23 a to 23 e.
図１１は、実施例１のナノ単結晶板材集積触媒の断面ＨＩＢ−ＳＥＭ像である。
複数のナノ単結晶板材（ナノぺタル）が、スペース（空隙部）を保ちながら、集積されていた。
FIG. 11 is a cross-sectional HIB-SEM image of the nano-single crystal plate-integrated catalyst of Example 1.
A plurality of nano single crystal plate materials (nanopetals) were accumulated while maintaining a space (void portion).
図１２は、実施例１のナノ単結晶板材集積触媒のＳＥＭ像である。また、図１３は、図１２のＤ部拡大図である。
複数のナノ単結晶板材（ナノぺタル）が、スペース（空隙部）を保ちながら、集積されていた。
12 is an SEM image of the nano-single crystal plate-integrated catalyst of Example 1. FIG. FIG. 13 is an enlarged view of a portion D in FIG.
A plurality of nano single crystal plate materials (nanopetals) were accumulated while maintaining a space (void portion).
図１４は、実施例１のナノ単結晶板材集積触媒のＴＥＭ像（ａ）と、（ａ）のＥ部ＥＤ像（ｂ）と、（ａ）のＦ部ＥＤ像（ｃ）である。また、図１５は、図１４のＦ部拡大図である。
ナノ単結晶板材集積触媒を構成するナノ単結晶板材（ナノぺタル）は単結晶であり、００１−ａｘｉｓを有していた。
FIG. 14 is a TEM image (a) of the nano-single crystal plate accumulation catalyst of Example 1, an E part ED image (b) of (a), and an F part ED image (c) of (a). FIG. 15 is an enlarged view of a portion F in FIG.
The nano single crystal plate material (nanopetal) constituting the nano single crystal plate material accumulation catalyst was a single crystal and had 001-axis.
図１６は、実施例１のナノ単結晶板材集積触媒（ＣｕＯ ｎａｎｏｆｌｏｗｅｒ）のＸＲＤと、比較例１のナノ単結晶板材（ＣｕＯ ｐｅｔａｌｓ：ナノぺタル）のＸＲＤである。
同一の２θの位置にピークが見られた。
16 is an XRD of the nano single crystal plate accumulation catalyst (CuO nanoflower) of Example 1 and an XRD of the nano single crystal plate material (CuO petals) of Comparative Example 1. FIG.
A peak was observed at the same 2θ position.
図１７は、実施例１のナノ単結晶板材集積触媒のＸＰＳである。これにより、ナノ単結晶板材集積触媒の表面のＣｕの化学状態（ＣｕＯ−Ｆ：グラフ上側）が酸化第二銅（ＣｕＯ）内部のＣｕの化学状態（ＣｕＯ Ｓｔａｎｄａｒｄ：グラフ下側）と同一であることが分かった。 FIG. 17 is an XPS of the nano single crystal plate material accumulation catalyst of Example 1. Thereby, the chemical state (CuO-F: upper side of the graph) of Cu on the surface of the nano-single crystal plate integrated catalyst is the same as the chemical state of Cu inside the cupric oxide (CuO) (CuO Standard: lower side of the graph). I understood that.
図１８は、実施例１のナノ単結晶板材集積触媒の一酸化窒素（ＮＯ）の昇温脱離（Ｔｅｍｐｅｒａｔｕｒｅ ｐｒｏｇｒａｍｍｅｄ ｄｅｓｏｒｐｔｉｏｎ：ＴＰＤ）信号強度（Ｓｉｇｎａｌ Ｉｎｔｅｎｓｉｔｙ）と温度の関係を示すグラフである。室温・１０ｋＰａのＮＯガスに試料を曝し、試料表面にＮＯ分子を吸着させたのち、１℃／分の割合で試料温度を上昇させた。図の昇温脱離信号強度（Ｓｉｇｎａｌ Ｉｎｔｅｎｓｉｔｙ）は、温度上昇に伴って試料表面から熱脱離してくるＮＯ分子の単位時間あたりの個数に比例しており、四重極子質量分析計により測定した。
昇温脱離信号は、３７９Ｋピークと、３７９Ｋピーク強度より小さなピーク強度を有する４２２Ｋピークの２つのピークが合成されたものであることが分かった。
図１９は、実施例１のナノ単結晶板材集積触媒におけるＮＯの昇温脱離信号強度（Ｓｉｇｎａｌ Ｉｎｔｅｎｓｉｔｙ）と温度の関係を説明する模式図である。
室温（３００Ｋ）では、ＮＯはナノ単結晶板材（ＣｕＯ ｐｅｔａｌｓ：ナノぺタル）の表面に吸着する。３７９Ｋ（１００℃）で、ナノ単結晶板材（ＣｕＯ ｐｅｔａｌｓ：ナノぺタル）の一面からＮＯは脱離するが、側面からは脱離しない。４２２Ｋ（１４３℃）で、ナノ単結晶板材（ＣｕＯ ｐｅｔａｌｓ：ナノぺタル）からすべてのＮＯが脱離する
FIG. 18 is a graph showing the relationship between the temperature programmed desorption (TPD) signal intensity (Signal Intensity) of nitrogen monoxide (NO) and the temperature of the nano-single crystal plate accumulation catalyst of Example 1. After exposing the sample to NO gas at room temperature and 10 kPa to adsorb NO molecules on the sample surface, the sample temperature was increased at a rate of 1 ° C./min. The temperature desorption signal intensity (Signal Intensity) in the figure is proportional to the number of NO molecules thermally desorbed from the sample surface as the temperature rises, and was measured by a quadrupole mass spectrometer. .
The temperature-programmed desorption signal was found to be a combination of two peaks, a 379K peak and a 422K peak having a peak intensity smaller than the 379K peak intensity.
FIG. 19 is a schematic diagram for explaining the relationship between the temperature-programmed desorption signal intensity (Signal Intensity) of NO and the temperature in the nano-single crystal plate accumulation catalyst of Example 1.
At room temperature (300K), NO is adsorbed on the surface of the nano single crystal plate (CuO petals). At 379 K (100 ° C.), NO desorbs from one side of the nano single crystal plate (CuO petals), but does not desorb from the side. At 422K (143 ° C), all NO is desorbed from the nano single crystal plate (CuO petals).
図２０は、比較例１のナノ単結晶板材（ＣｕＯ ｐｅｔａｌｓ：ナノぺタル：Ｃｒｕｓｈｅｄ ２Ｄ−Ｃｒｙｓｔａｌｌｉｎｅ ＣｕＯ）のＳＥＭ像である。
ナノ単結晶板材が、隣接するナノ単結晶板材間で触媒活性面同士を接面させて集積されるものが存在した。
FIG. 20 is an SEM image of the nano single crystal plate material of Comparative Example 1 (CuO petals: Nanopetal: Crushed 2D-Crystalline CuO).
There exist some in which nano single crystal plates are accumulated with adjacent catalytic active surfaces in contact between adjacent nano single crystal plates.
図２１は、比較例１のナノ単結晶板材（ナノぺタル）のＮＯの昇温脱離信号強度（Ｓｉｇｎａｌ Ｉｎｔｅｎｓｉｔｙ）と温度の関係を示すグラフである。
得られた昇温脱離信号は、３７９Ｋピークと、３７９Ｋピーク強度より大きなピーク強度を有する４２２Ｋピークの２つのピークが合成されたものであることが分かった。
FIG. 21 is a graph showing the relationship between the temperature rising desorption signal intensity (Signal Intensity) of NO and the temperature of the nano single crystal plate (nanopetal) of Comparative Example 1.
The obtained temperature programmed desorption signal was found to be a combination of two peaks, a 379K peak and a 422K peak having a peak intensity greater than the 379K peak intensity.
図２２は、比較例２のナノ粒子（Ｃｏｍｍｅｒｃｉａｌ ＣｕＯ ＮＰｓ）のＳＥＭ像である。ダマ（塊）になって存在した。 FIG. 22 is an SEM image of nanoparticles (Commercial CuO NPs) of Comparative Example 2. It existed as a lump.
図２３は、比較例２のナノ粒子（Ｃｏｍｍｅｒｃｉａｌ ＣｕＯ ＮＰｓ）におけるＮＯの昇温脱離信号強度（Ｓｉｇｎａｌ Ｉｎｔｅｎｓｉｔｙ）と温度の関係を示すグラフである。
得られたスペクトルは、３７９Ｋピークと、３７９Ｋピーク強度より大きなピーク強度を有する４２２Ｋピークと、３７９Ｋピーク強度と同程度のピーク強度を有する５１０Ｋピークの３つのスペクトルが合成されたものであることが分かった。
FIG. 23 is a graph showing the relationship between the temperature desorption signal intensity (Signal Intensity) of NO and the temperature of nanoparticles (Commercial CuO NPs) of Comparative Example 2.
The obtained spectrum is obtained by synthesizing three spectra of a 379K peak, a 422K peak having a peak intensity greater than the 379K peak intensity, and a 510K peak having a peak intensity comparable to the 379K peak intensity. It was.
図２４は、実施例１のナノ単結晶板材集積触媒と、比較例１のナノ単結晶板材（ナノぺタル）のＣＯ２信号強度（ＣＯ２ ｓｉｇｎａｌ ｉｎｔｅｎｓｉｔｙ）とＤｕｒａｔｉｏｎの関係を示すグラフである。
Ｄｕｒａｔｉｏｎとは、試料表面が反応ガスに曝された時点をゼロとして測った経過時間である。Ｓｉｇｎａｌ ｉｎｔｅｎｓｉｔｙとは、反応ガス組成を分析するガスクロマトグラフからの出力値であり、反応ガス中対象化学種の濃度に比例している。
図２５は、実施例１のナノ単結晶板材集積触媒と、比較例１のナノ単結晶板材（ナノぺタル）のＳｅｌｅｃｔｉｖｉｔｙとＤｕｒａｔｉｏｎの関係を示すグラフである。
Ｓｅｌｅｃｔｉｖｉｔｙとは、先に記載の化学反応式（２）におけるＮ２ＯとＣＯ２のガスクロマトグラフからの出力値の比に比例する値である。
図２６は、比較例１のナノ単結晶板材（ナノぺタル）の触媒反応を説明する図である。
実施例１のナノ単結晶板材集積触媒では、図３に示したように、一面での触媒反応が主体的であるのに対し、比較例１のナノ単結晶板材（ナノぺタル）では、図２６に示すように、側面での触媒反応が一面での触媒反応と同程度となり、図２４、２５に示すような結果をもたらしたと推察した。
FIG. 24 is a graph showing the relationship between the CO 2 signal intensity (CO 2 signal intensity) and Duration of the nano single crystal plate material integrated catalyst of Example 1 and the nano single crystal plate material (nanopetal) of Comparative Example 1.
Duration is the elapsed time measured with the time when the sample surface was exposed to the reaction gas as zero. The signal intensity is an output value from a gas chromatograph that analyzes the reaction gas composition, and is proportional to the concentration of the target chemical species in the reaction gas.
FIG. 25 is a graph showing the relationship between the selectivity and duration of the nano-single crystal plate integrated catalyst of Example 1 and the nano-single crystal plate (nanopetal) of Comparative Example 1.
Selectivity is a value proportional to the ratio of the output values from the gas chromatograph of N 2 O and CO 2 in the chemical reaction formula (2) described above.
FIG. 26 is a diagram illustrating a catalytic reaction of the nano single crystal plate material (nanopetal) of Comparative Example 1.
As shown in FIG. 3, in the nano single crystal plate-integrated catalyst of Example 1, the catalytic reaction on one side is dominant, whereas in the nano single crystal plate (nano-petal) of Comparative Example 1, As shown in FIG. 26, it was guessed that the catalytic reaction on the side surface was the same as the catalytic reaction on the one side, and the results shown in FIGS.
＜結論＞
（１）ボトムアップ−ハイドロサーマル合成により、特異な（００１）面を豊富に有する２Ｄ結晶ＣｕＯ触媒（ナノフラワー）を合成することができた。
（２）２Ｄ結晶ＣｕＯ触媒（ナノフラワー）を構成し、ＣｕＯ（００１）面を有する板状部は互いに、（００１）面に（００１）面とは異なる面が接するように立体的に配置されていて、熱凝集しても、前記（００１）面で重なることがなく、ＮＯ高純度化の触媒としての選択性・効率を低下させることがなかった。
（３）２Ｄ結晶ＣｕＯ触媒（ナノフラワー）は、ＣｕＯのように、貴金属を用いず、安く、豊富な材料を用いることができた。
<Conclusion>
(1) A 2D crystal CuO catalyst (nanoflower) having abundant unique (001) planes could be synthesized by bottom-up hydrothermal synthesis.
(2) The plate-like parts constituting the 2D crystal CuO catalyst (nanoflower) and having the CuO (001) plane are three-dimensionally arranged such that a plane different from the (001) plane is in contact with the (001) plane. Even if the heat aggregation is performed, the (001) plane does not overlap, and the selectivity / efficiency of the NO purification catalyst is not lowered.
(3) The 2D crystal CuO catalyst (nanoflower) can use cheap and abundant materials without using noble metals like CuO.
本発明のナノ単結晶板材集積触媒は、単結晶の触媒活性面を一面とし、触媒不活性面を側面とするナノ単結晶板材が、隣接するナノ単結晶板材間で前記触媒活性面同士を接面させることなく集積されているナノ単結晶板材集積触媒に関するものであり、熱凝集させても、触媒活性面の全面積の大きさを低下させることがなく、触媒活性能を保つことができ、毒性ガスを無毒化する触媒材料を取り扱う産業一般に有用な技術であり、環境産業、触媒産業等において利用可能性がある。 The nano single crystal plate-integrated catalyst of the present invention has a single crystal catalytic active surface as one surface, and a nano single crystal plate material having a catalyst inactive surface as a side surface, and the catalytic active surfaces are in contact with each other between adjacent nano single crystal plate materials. It is related to the nano single crystal plate material accumulation catalyst that is accumulated without facing, and even if heat aggregation, without reducing the size of the total area of the catalyst active surface, it can maintain the catalytic activity ability, This technology is useful in general industries that handle catalyst materials that detoxify toxic gases, and can be used in the environmental industry, the catalyst industry, and the like.
１１…ナノ単結晶板材、１１ａ…一面、１１ｂ…他面、１１ｃ…側面、１２…ナノ単結晶板材、１２ａ…一面、１２ｂ…他面、１２ｃ…側面、１２ｄ…屈曲線、１３…ナノ単結晶板材、１３ａ…一面、１３ｂ…他面、１３ｃ…側面、１３ｄ…屈曲線、２１、２３ａ、２３ｂ、２３ｃ、２３ｄ、２３ｅ…スペース（空隙部）、１０１…ナノ単結晶板材集積触媒。
DESCRIPTION OF SYMBOLS 11 ... Nano single crystal plate material, 11a ... One side, 11b ... Other side, 11c ... Side surface, 12 ... Nano single crystal plate material, 12a ... One side, 12b ... Other side, 12c ... Side surface, 12d ... Bending line, 13 ... Nano single crystal Plate material, 13a ... one surface, 13b ... other surface, 13c ... side surface, 13d ... bending line, 21, 23a, 23b, 23c, 23d, 23e ... space (void part), 101 ... nano single crystal plate material integrated catalyst.
Claims (6)
前記ナノ単結晶板材がＣｕＯであり、前記触媒活性面が（００１）面であることを特徴とするナノ単結晶板材集積触媒。 The single-crystal catalytic active surface is a single surface, and the nano-single crystal plate material having the catalytic inactive surface as a side surface is integrated between adjacent nano-single crystal plate materials without bringing the catalytic active surfaces into contact with each other,
The nano single crystal plate material accumulation catalyst, wherein the nano single crystal plate material is CuO, and the catalytic active surface is a (001) surface.
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