JP2019052116A - Nitrogen-containing polycyclic compound - Google Patents
Nitrogen-containing polycyclic compound Download PDFInfo
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- JP2019052116A JP2019052116A JP2017178162A JP2017178162A JP2019052116A JP 2019052116 A JP2019052116 A JP 2019052116A JP 2017178162 A JP2017178162 A JP 2017178162A JP 2017178162 A JP2017178162 A JP 2017178162A JP 2019052116 A JP2019052116 A JP 2019052116A
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- -1 Nitrogen-containing polycyclic compound Chemical class 0.000 title claims abstract description 52
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 29
- 239000001301 oxygen Substances 0.000 claims abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 19
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 16
- 125000005843 halogen group Chemical group 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 claims description 4
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 39
- 239000002184 metal Substances 0.000 description 29
- 238000006722 reduction reaction Methods 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 23
- 238000000034 method Methods 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000002994 raw material Substances 0.000 description 16
- 238000005259 measurement Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 150000001721 carbon Chemical group 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 12
- 239000000178 monomer Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000010304 firing Methods 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 238000003763 carbonization Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000004993 emission spectroscopy Methods 0.000 description 4
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910002552 Fe K Inorganic materials 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 238000006411 Negishi coupling reaction Methods 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000006619 Stille reaction Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 2
- 238000004998 X ray absorption near edge structure spectroscopy Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002074 nanoribbon Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 238000003696 structure analysis method Methods 0.000 description 2
- 238000001269 time-of-flight mass spectrometry Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- GZUCRSZNKWAPRY-UHFFFAOYSA-N C1(=CC=CC=C1)C1=C(C(=C(C=2C3=CC=CC=C3C3=CC=CC=C3C12)C1=CC=CC=C1)C1OC=CC=C1)C1OC=CC=C1 Chemical group C1(=CC=CC=C1)C1=C(C(=C(C=2C3=CC=CC=C3C3=CC=CC=C3C12)C1=CC=CC=C1)C1OC=CC=C1)C1OC=CC=C1 GZUCRSZNKWAPRY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 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
- 239000011261 inert gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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- Pyridine Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
本発明は、含窒素多環式化合物に関する。より詳しくは、酸素還元触媒として好適に用いることができる含窒素多環式化合物、その焼成体、及び、含窒素多環式化合物又は焼成体を含んで構成される酸素還元触媒に関する。 The present invention relates to a nitrogen-containing polycyclic compound. More specifically, the present invention relates to a nitrogen-containing polycyclic compound that can be suitably used as an oxygen reduction catalyst, a fired body thereof, and an oxygen reduction catalyst that includes the nitrogen-containing polycyclic compound or the fired body.
グラフェンナノリボン（ＧＮＲ）は、ｓｐ２結合で結合した炭素原子が平面上に並んだグラフェン様の構造をもつが、２次元的な平面状ではなく、リボンのような直線型やアームチェア型等の形状を有する。ＧＮＲは、その特異な構造や物性のために数多くの研究がなされ、種々の用途に用いられることが期待されている。例えばＧＮＲには、平面状のグラフェンと異なり、短軸方向が有限であるため、バンドギャップが存在することから、半導体として用いることが期待されている。 Graphene nanoribbon (GNR) has a graphene-like structure in which carbon atoms bonded by sp 2 bonds are arranged on a plane, but it is not a two-dimensional plane, but a linear type such as a ribbon or an armchair type Has a shape. GNR has been researched for its unique structure and physical properties, and is expected to be used in various applications. For example, unlike planar graphene, GNR is expected to be used as a semiconductor because the short axis direction is finite and a band gap exists.
このようなＧＮＲの合成方法は大きく分けて２つある。１つ目がカーボンナノチューブを軸方向に開く方法であり、例えばカーボンナノチューブを酸化剤により開環する方法が開示されている（例えば、非特許文献１参照）。２つ目が有機合成の手法を用いる方法である。有機合成の手法を用いる方法にも、前駆体までは有機合成の手法を用いて得、前駆体のＧＮＲ化は熱的（物理的）作用を利用するものと、ＧＮＲまで全て有機合成の手法を用いて得るものとがある。前者としては、例えば、前駆体となるブロモ体までは有機合成の手法を用いて合成し、ポリマー化及びＧＮＲ化は基板上での加熱で行って直線型ＧＮＲ及びアームチェア型ＧＮＲを得、走査型トンネル顕微鏡を用いて同定したものが開示されている（例えば、非特許文献２参照）。後者としては、例えば、アームチェア型含窒素ＧＮＲを有機合成の手法により得たものが開示されている（例えば、非特許文献３参照）。 There are roughly two methods for synthesizing such GNR. The first is a method of opening a carbon nanotube in the axial direction. For example, a method of opening a carbon nanotube with an oxidizing agent is disclosed (for example, see Non-Patent Document 1). The second is a method using an organic synthesis method. In the method using the organic synthesis method, the precursor is obtained by using the organic synthesis method, and the GNR conversion of the precursor uses the thermal (physical) action, and all the organic synthesis methods up to the GNR are used. There is something to get by using. As the former, for example, a bromo compound as a precursor is synthesized using an organic synthesis method, and polymerization and GNR conversion are performed by heating on a substrate to obtain a linear GNR and an armchair GNR, and scanning. What was identified using the scanning tunnel microscope is disclosed (for example, refer nonpatent literature 2). As the latter, for example, an armchair type nitrogen-containing GNR obtained by an organic synthesis technique is disclosed (for example, see Non-Patent Document 3).
ところで、含窒素ナノカーボン材料と鉄等の金属とを混ぜて、酸素還元触媒として利用する例が開示されている（例えば、非特許文献４参照）。 By the way, an example in which a nitrogen-containing nanocarbon material and a metal such as iron are mixed and used as an oxygen reduction catalyst is disclosed (for example, see Non-Patent Document 4).
上記のとおり、ＧＮＲを種々の用途に用いることが検討されているが、ＧＮＲは幅の長さが異なるもの、直線型のものやアームチェア型のもの、他の元素をドープしたもの等、種々の構造のものが考えられ、まだ充分に検討が進んでいるとはいえず、更なるＧＮＲを開発する余地がある。新たな構造のＧＮＲを開発することは、今後の様々な用途への展開を検討するうえでも好ましい。 As described above, it has been studied to use GNR for various purposes, but GNR has various width lengths, linear type, armchair type, and other elements doped. The structure of this is considered, and it cannot be said that the examination is still sufficiently advanced, and there is room for further GNR development. It is preferable to develop a GNR having a new structure in consideration of future development for various uses.
本発明は、上記現状に鑑みてなされたものであり、新規なＧＮＲを提供することを目的とする。 The present invention has been made in view of the above situation, and an object thereof is to provide a novel GNR.
本発明者らは、新規なＧＮＲについて種々検討し、含窒素ＧＮＲであって、窒素の位置が特定された含窒素多環式化合物を合成した。本発明者らは、この含窒素多環式化合物を焼成・金属担持させたものが酸素還元反応活性に優れ、酸素還元触媒の原料として有用であることを見出し、上記課題をみごとに解決することができることに想到し、本発明に到達したものである。 The present inventors have studied various novel GNRs and synthesized nitrogen-containing polycyclic compounds that are nitrogen-containing GNRs and in which the position of nitrogen is specified. The present inventors have found that this nitrogen-containing polycyclic compound calcined and metal-supported is excellent in oxygen reduction reaction activity and useful as a raw material for an oxygen reduction catalyst, and solves the above-mentioned problems brilliantly. Thus, the present invention has been achieved.
すなわち本発明は、下記一般式（１）で表される構造を含む構成単位を有することを特徴とする含窒素多環式化合物である。 That is, this invention is a nitrogen-containing polycyclic compound characterized by having the structural unit containing the structure represented by following General formula (1).
（式中、Ｘ１及びＸ２は、それぞれ、水素原子、ハロゲン原子、ＯＴｆ基、ＯＴｓ基、又は、該構成単位中の一般式（１）で表される構造以外の別の構造若しくは他の構成単位との結合部位を表し、Ｔｆは、トリフルオロメチルスルホニル基を表し、Ｔｓは、トシル基を表す。Ｙ１、Ｙ２、Ｙ７、及び、Ｙ８は、それぞれ、水素原子と結合した炭素原子、又は、該構成単位中の一般式（１）で表される構造以外の別の構造若しくは他の構成単位と結合した炭素原子を表す。Ｙ３及びＹ４、Ｙ５及びＹ６は、それぞれ、一方が窒素原子を表し、他方が水素原子と結合した炭素原子を表す。点線は、結合が形成されていてもよく、形成されていなくてもよいことを表す。）
以下に本発明を詳述する。
(In the formula, X 1 and X 2 are each a hydrogen atom, a halogen atom, an OTf group, an OTs group, another structure other than the structure represented by the general formula (1) in the structural unit, or other Represents a bonding site with a structural unit, Tf represents a trifluoromethylsulfonyl group, Ts represents a tosyl group, Y 1 , Y 2 , Y 7 , and Y 8 each bonded to a hydrogen atom. A carbon atom or a carbon atom bonded to another structure other than the structure represented by the general formula (1) in the structural unit or another structural unit is represented.Y 3 and Y 4 , Y 5 and Y 6 are And one represents a nitrogen atom and the other represents a carbon atom bonded to a hydrogen atom, and a dotted line represents that a bond may or may not be formed.)
The present invention is described in detail below.
本発明の含窒素多環式化合物は、上述の構成よりなり、本発明の含窒素多環式化合物を用いた高活性の酸素還元触媒を得ることができる。 The nitrogen-containing polycyclic compound of the present invention has the above-described configuration, and a highly active oxygen reduction catalyst using the nitrogen-containing polycyclic compound of the present invention can be obtained.
以下に本発明を詳述する。
なお、以下において記載する本発明の個々の好ましい形態を２つ以上組み合わせたものもまた、本発明の好ましい形態である。
The present invention is described in detail below.
A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.
＜含窒素多環式化合物＞
本発明の含窒素多環式化合物は、上記一般式（１）で表される構造を含む構成単位を有する。本発明の含窒素多環式化合物が上記一般式（１）で表される構造を含む構成単位を有するとは、上記構成単位が、上記一般式（１）で表される構造であってもよく、上記一般式（１）で表される構造に、一般式（１）で表される構造以外の別の構造が付加したものであってもよい。
上記一般式（１）で表される構造以外の別の構造は、上記一般式（１）で表される構造に結合している原子又は原子団であって、上記一般式（１）で表される構造とともに上記構成単位を構成する。上記一般式（１）で表される構造に結合している原子又は原子団としては、平面上に並んだ構造を構成するｓｐ２結合で結合した炭素原子が好ましいが、窒素、酸素、硫黄、ケイ素、リン等の異種元素がドープされていても構わない。
<Nitrogen-containing polycyclic compound>
The nitrogen-containing polycyclic compound of the present invention has a structural unit including the structure represented by the general formula (1). The nitrogen-containing polycyclic compound of the present invention has a structural unit containing the structure represented by the general formula (1), even if the structural unit is a structure represented by the general formula (1). Alternatively, another structure other than the structure represented by the general formula (1) may be added to the structure represented by the general formula (1).
Another structure other than the structure represented by the general formula (1) is an atom or an atomic group bonded to the structure represented by the general formula (1), and is represented by the general formula (1). The structural unit is configured together with the structure to be formed. As the atom or atomic group bonded to the structure represented by the general formula (1), a carbon atom bonded by an sp 2 bond constituting a structure arranged on a plane is preferable, but nitrogen, oxygen, sulfur, Different elements such as silicon and phosphorus may be doped.
本発明の含窒素多環式化合物が有する上記構成単位の数は、１個であってもよく、２個以上が連結したものであってもよい。すなわち、本発明の含窒素多環式化合物は、含窒素ＧＮＲであってもよく、含窒素ＧＮＲの原料であるモノマー又はポリマーであってもよい。
本発明の含窒素多環式化合物は、ＧＮＲ化により共役系を自在に伸ばすことができ、これにより、導電経路を広げることができ、酸素還元反応活性をより優れたものとすることができると考えられる。また、ＧＮＲやその原料であるモノマー又はポリマーは、そのエッジが基本的にいわゆるアームチェアエッジから構成されており、酸素に対して安定である。
The number of the structural units contained in the nitrogen-containing polycyclic compound of the present invention may be one, or two or more may be linked. That is, the nitrogen-containing polycyclic compound of the present invention may be a nitrogen-containing GNR, or a monomer or polymer that is a raw material of the nitrogen-containing GNR.
The nitrogen-containing polycyclic compound of the present invention can freely extend the conjugated system by GNR conversion, thereby expanding the conductive path and improving the oxygen reduction reaction activity. Conceivable. Further, GNR and its raw material monomer or polymer are basically composed of so-called armchair edges, and are stable to oxygen.
上記一般式（１）中、Ｙ３及びＹ４、Ｙ５及びＹ６は、それぞれ、一方が窒素原子を表し、他方が水素原子と結合した炭素原子を表す。なお、言い換えると、Ｙ３及びＹ４の一方が窒素原子を表し、他方が水素原子と結合した炭素原子を表すとともに、Ｙ５及びＹ６の一方が窒素原子を表し、他方が水素原子と結合した炭素原子を表す。
中でも、Ｙ３及びＹ６がそれぞれ水素原子と結合した炭素原子を表し、Ｙ４及びＹ５がそれぞれ窒素原子を表すことが好ましい。これにより、金属元素をキレート化することが可能となり、酸素還元触媒において酸素還元反応活性がより優れたものとなる。
なお、上記一般式（１）中の少なくとも上側３つの点線に結合を形成して本発明の含窒素多環式化合物を得た場合、構成単位間でＹ３及びＹ４、Ｙ５及びＹ６が逆転したモノマーの混合物やポリマー等が得られるときがある。このような形態も、構成単位の一部が、Ｙ３及びＹ６がそれぞれ水素原子と結合した炭素原子を表し、Ｙ４及びＹ５がそれぞれ窒素原子を表す構成単位であるため、本発明における好ましい形態の１つである。
In the general formula (1), Y 3 and Y 4 , Y 5 and Y 6 each represents a carbon atom in which one represents a nitrogen atom and the other is bonded to a hydrogen atom. In other words, one of Y 3 and Y 4 represents a nitrogen atom, the other represents a carbon atom bonded to a hydrogen atom, one of Y 5 and Y 6 represents a nitrogen atom, and the other bonded to a hydrogen atom. Represents a carbon atom.
Among them, it is preferable that Y 3 and Y 6 each represent a carbon atom bonded to a hydrogen atom, and Y 4 and Y 5 each represent a nitrogen atom. Thereby, it becomes possible to chelate the metal element, and the oxygen reduction reaction activity is more excellent in the oxygen reduction catalyst.
When the nitrogen-containing polycyclic compound of the present invention is obtained by forming bonds on at least the upper three dotted lines in the general formula (1), Y 3 and Y 4 , Y 5 and Y 6 are obtained between the structural units. In some cases, a mixture of monomers or a polymer obtained by reversing the above can be obtained. In such a form, part of the structural unit is a structural unit in which Y 3 and Y 6 each represent a carbon atom bonded to a hydrogen atom, and Y 4 and Y 5 each represent a nitrogen atom. This is one of the preferred forms.
上記一般式（１）中、Ｘ１及びＸ２が表すハロゲン原子は、塩素原子又は臭素原子であることが好ましく、臭素原子であることがより好ましい。 In the general formula (1), the halogen atom represented by X 1 and X 2 is preferably a chlorine atom or a bromine atom, and more preferably a bromine atom.
上記一般式（１）中、Ｘ１及びＸ２は、それぞれ、上記構成単位中の一般式（１）で表される構造以外の別の構造若しくは他の構成単位との結合部位を表し、Ｙ１、Ｙ２、Ｙ７、及び、Ｙ８は、それぞれ、上記構成単位中の一般式（１）で表される構造以外の別の構造若しくは他の構成単位と結合した炭素原子を表すことが本発明における好ましい形態の１つである。これにより、含窒素多環式化合物はアームチェア型の含窒素ＧＮＲとなる。 In the general formula (1), X 1 and X 2 each represent a binding site with another structure other than the structure represented by the general formula (1) in the structural unit or another structural unit, and Y 1 , Y 2 , Y 7 , and Y 8 each represent a carbon atom bonded to another structure other than the structure represented by the general formula (1) in the structural unit or another structural unit. This is one of the preferred forms in the present invention. As a result, the nitrogen-containing polycyclic compound becomes an armchair-type nitrogen-containing GNR.
本発明の含窒素多環式化合物が含窒素ＧＮＲの原料であるモノマーである場合、該モノマーとしては、例えば、下記一般式（２）で表されるものが好適なものとして挙げられる。 When the nitrogen-containing polycyclic compound of the present invention is a monomer that is a raw material of nitrogen-containing GNR, examples of the monomer include those represented by the following general formula (2).
上記一般式（２）中、Ｘ１及びＸ２は、それぞれ、水素原子、ハロゲン原子、ＯＴｆ基、ＯＴｓ基、アルキル基、又は、アリール基を表し、Ｔｆは、トリフルオロメチルスルホニル基を表し、Ｔｓは、トシル基を表す。Ｙ３及びＹ４、Ｙ５及びＹ６は、それぞれ、一方が窒素原子を表し、他方が水素原子と結合した炭素原子を表す。点線は、結合が形成されていてもよく、形成されていなくてもよいことを表す。 In the general formula (2), X 1 and X 2 each represent a hydrogen atom, a halogen atom, an OTf group, an OTs group, an alkyl group, or an aryl group, Tf represents a trifluoromethylsulfonyl group, Ts represents a tosyl group. Y 3 and Y 4 , Y 5 and Y 6 each represents a nitrogen atom and the other represents a carbon atom bonded to a hydrogen atom. A dotted line represents that a bond may or may not be formed.
Ｘ１及びＸ２がハロゲン原子、ＯＴｆ基、又は、ＯＴｓ基等の脱離基である場合、これらに対し、鈴木カップリング、根岸カップリング、スティルカップリング等の反応でアルキル基やアリール基を導入することも可能である。これらの形態もまた、本発明の好適な形態である。 When X 1 and X 2 are a leaving group such as a halogen atom, an OTf group, or an OTs group, an alkyl group or an aryl group can be formed by a reaction such as Suzuki coupling, Negishi coupling, or Stille coupling. It is also possible to introduce. These forms are also preferred forms of the present invention.
本発明の含窒素多環式化合物が含窒素ＧＮＲの原料であるポリマーである場合、該ポリマーとしては、例えば、下記一般式（３）で表されるものが好適なものとして挙げられる。 When the nitrogen-containing polycyclic compound of the present invention is a polymer that is a raw material for nitrogen-containing GNR, examples of the polymer include those represented by the following general formula (3).
上記一般式（３）中、Ｘ１及びＸ２は、それぞれ、水素原子、ハロゲン原子、ＯＴｆ基、ＯＴｓ基、アルキル基、又は、アリール基を表し、Ｔｆは、トリフルオロメチルスルホニル基を表し、Ｔｓは、トシル基を表す。Ｙ３及びＹ４、Ｙ５及びＹ６は、それぞれ、一方が窒素原子を表し、他方が水素原子と結合した炭素原子を表す。点線は、結合が形成されていてもよく、形成されていなくてもよいことを表す。ｎは、１以上の数であり、通常は１０００以下である。 In the general formula (3), X 1 and X 2 each represent a hydrogen atom, a halogen atom, an OTf group, an OTs group, an alkyl group, or an aryl group, Tf represents a trifluoromethylsulfonyl group, Ts represents a tosyl group. Y 3 and Y 4 , Y 5 and Y 6 each represents a nitrogen atom and the other represents a carbon atom bonded to a hydrogen atom. A dotted line represents that a bond may or may not be formed. n is a number of 1 or more, and is usually 1000 or less.
Ｘ１及びＸ２がハロゲン原子、ＯＴｆ基、又は、ＯＴｓ基等の脱離基である場合、これらに対し、鈴木カップリング、根岸カップリング、スティルカップリング等の反応でアルキル基やアリール基を導入することも可能である。これらの官能基を導入することで、末端官能基の物性への影響を小さくすることができる。これらの形態もまた、本発明の好適な形態である。 When X 1 and X 2 are a leaving group such as a halogen atom, an OTf group, or an OTs group, an alkyl group or an aryl group can be formed by a reaction such as Suzuki coupling, Negishi coupling, or Stille coupling. It is also possible to introduce. By introducing these functional groups, the influence on the physical properties of the terminal functional group can be reduced. These forms are also preferred forms of the present invention.
本発明の含窒素多環式化合物が含窒素ＧＮＲである場合、含窒素ＧＮＲは、アームチェア型であることが好ましく、例えば、下記一般式（４）で表される骨格を有する含窒素ＧＮＲであることが好ましい。 When the nitrogen-containing polycyclic compound of the present invention is a nitrogen-containing GNR, the nitrogen-containing GNR is preferably an armchair type, for example, a nitrogen-containing GNR having a skeleton represented by the following general formula (4) Preferably there is.
上記一般式（４）中、Ｙ３及びＹ４、Ｙ５及びＹ６は、それぞれ、式（３）において上述したものと同様である。ｎは、１以上の数であり、通常は１０００以下である。
なお、本明細書中、上記一般式（４）で表される骨格を有する含窒素ＧＮＲを、下記一般式（５）で簡略化して表すことがある。
In the general formula (4), Y 3 and Y 4 , Y 5 and Y 6 are the same as those described above in the formula (3). n is a number of 1 or more, and is usually 1000 or less.
In the present specification, the nitrogen-containing GNR having a skeleton represented by the general formula (4) may be simplified and represented by the following general formula (5).
上記一般式（５）中、ｎは、１以上の数であり、通常は１０００以下である。
なお、上述した含窒素ＧＮＲやその原料モノマー、原料ポリマーは、例えば、下記反応式で表される反応を用いて得ることができる。
In the general formula (5), n is a number of 1 or more, and is usually 1000 or less.
In addition, the nitrogen-containing GNR, the raw material monomer, and the raw material polymer described above can be obtained using, for example, a reaction represented by the following reaction formula.
上記反応式中、Ｘは、水素原子又はハロゲン原子を表す。ハロゲン原子は、例えば臭素原子であることが好ましい。得られた生成物は、含窒素ＧＮＲの原料モノマーであり、そのうちＸが水素原子を表すものは、本明細書中、ＰＰｙＴＰ（１，４−ｄｉＰｈｅｎｙｌ−２，３−ｄｉＰｙｒｉｄｙｌＴｒｉＰｈｅｎｙｌｅｎｅ）とも言う。 In the above reaction formula, X represents a hydrogen atom or a halogen atom. The halogen atom is preferably, for example, a bromine atom. The obtained product is a raw material monomer of nitrogen-containing GNR, of which X represents a hydrogen atom, is also referred to as PPyTP (1,4-diphenyl-2,3-diPyrylTriPhenylene) in the present specification.
上記反応式中、Ｘは、ハロゲン原子を表す。ハロゲン原子は、例えば臭素原子であることが好ましい。Ｙ３及びＹ４の一方が窒素原子を表し、他方が水素原子と結合した炭素原子を表す。Ｙ５及びＹ６の一方が窒素原子を表し、他方が水素原子と結合した炭素原子を表す。ｎ及びｐは、それぞれ、１以上の数であり、通常は１０００以下である。［ＰＰｙＴＰ］ｎは、含窒素ＧＮＲの原料ポリマーであり、ＢＰｙ−ＧＮＲは、含窒素ＧＮＲである。
上記反応式で表される反応において、反応温度、反応時間は、適宜設定することができる。
In the above reaction formula, X represents a halogen atom. The halogen atom is preferably, for example, a bromine atom. One of Y 3 and Y 4 represents a nitrogen atom, and the other represents a carbon atom bonded to a hydrogen atom. One of Y 5 and Y 6 represents a nitrogen atom, and the other represents a carbon atom bonded to a hydrogen atom. Each of n and p is a number of 1 or more, and is usually 1000 or less. [PPyTP] n is a raw material polymer of nitrogen-containing GNR, and BPy-GNR is nitrogen-containing GNR.
In the reaction represented by the above reaction formula, the reaction temperature and reaction time can be appropriately set.
本発明の含窒素多環式化合物は、更に、上記構成単位に担持された、周期表の第７〜１１族に属する金属元素から選ばれる少なくとも１種の元素を有することが好ましい。なお、このように金属元素が担持された含窒素多環式化合物を金属複合体と言うこともできる。これにより、酸素還元触媒としての酸素還元反応活性をより優れたものとすることができる。該元素は、原子の状態であってもよく、カチオンであってもよい。また、クラスターや粒子の形態であっても構わない。
周期表の第７〜１１族に属する金属元素の中でも、第８〜１１族に属する金属元素が好ましく、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕがより好ましい。
また上述した一般式（１）で表される構造中の窒素原子に金属元素が配位していることが好ましく、中でも、式（１）中のＹ４及びＹ５がそれぞれ窒素原子を表し、該窒素原子に金属元素が配位していることがより好ましい。これにより、金属元素がキレートされて安定化するとともに、本発明の効果がより顕著なものとなる。
窒素原子に金属元素が配位していることは、Ｘ線光電子分光法、広域Ｘ線吸収微細構造解析法（ＥＸＡＦＳ法）を用いる実施例の方法で測定することができる。
The nitrogen-containing polycyclic compound of the present invention preferably further has at least one element selected from metal elements belonging to Groups 7 to 11 of the periodic table supported on the above structural unit. A nitrogen-containing polycyclic compound in which a metal element is supported in this way can also be called a metal complex. Thereby, the oxygen reduction reaction activity as an oxygen reduction catalyst can be made more excellent. The element may be in an atomic state or a cation. Further, it may be in the form of clusters or particles.
Among metal elements belonging to Groups 7 to 11 of the periodic table, metal elements belonging to Groups 8 to 11 are preferable, and Fe, Co, Ni, and Cu are more preferable.
Moreover, it is preferable that the metal element is coordinated to the nitrogen atom in the structure represented by the general formula (1) described above. Among them, Y 4 and Y 5 in the formula (1) each represent a nitrogen atom, More preferably, a metal element is coordinated to the nitrogen atom. Thereby, the metal element is chelated and stabilized, and the effect of the present invention becomes more remarkable.
The fact that a metal element is coordinated to a nitrogen atom can be measured by the method of an embodiment using X-ray photoelectron spectroscopy or a broad X-ray absorption fine structure analysis method (EXAFS method).
金属元素の含有量は、本発明の含窒素多環式化合物１００質量％中、０．１質量％以上であることが好ましく、０．３質量％以上であることがより好ましく、０．５質量％以上であることが更に好ましい。また、該含有量は、１０質量％以下であることが好ましく、５質量％以下であることがより好ましく、３質量％以下であることが更に好ましい。
金属元素の含有量は、誘導結合プラズマ発光分光分析法（ＩＣＰ−ＡＥＳ法）により実施例の方法で測定することができる。
The content of the metal element is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, in 100% by mass of the nitrogen-containing polycyclic compound of the present invention, and 0.5% by mass. % Or more is more preferable. The content is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less.
The content of the metal element can be measured by the method of the example by inductively coupled plasma emission spectroscopy (ICP-AES method).
上述した含窒素ＧＮＲやその原料モノマー、原料ポリマーと、金属元素を有する化合物とを混合し、加熱等することで、上記構成単位に担持された、上記金属元素を有する本発明の含窒素多環式化合物を得ることができる。金属担持における加熱の温度・時間等の好ましい条件は、後述する焼成における好ましい条件と同様である。また、後述するように、金属担持と焼成とを同時に行っても構わない。
混合に用いる金属元素を有する化合物としては、例えば、金属元素のハロゲン化物等が好ましい。
The nitrogen-containing polycycle of the present invention having the above-mentioned metal element supported on the above-mentioned structural unit by mixing the above-mentioned nitrogen-containing GNR, its raw material monomer, raw material polymer, and a compound having a metal element, and heating. Formula compounds can be obtained. Preferable conditions such as heating temperature and time in the metal loading are the same as the preferable conditions in firing described later. Further, as will be described later, metal loading and firing may be performed simultaneously.
As a compound having a metal element used for mixing, for example, a halide of a metal element is preferable.
（焼成体）
本発明は、本発明の含窒素多環式化合物の焼成体でもある。
本発明の焼成体は、本発明の含窒素多環式化合物である、含窒素ＧＮＲ、その原料モノマー若しくは原料ポリマー、又は、これらの金属担持体（金属複合体）を焼成して得られるものであり、中でも、炭素材料とともに焼成して得られるものであることが好ましい。本明細書中、本発明の含窒素多環式化合物を炭素材料とともに焼成することを炭素化とも言う。
なお、金属元素を担持させ、かつ炭素化した本発明の焼成体を得るうえで、金属元素を担持させることと炭素化とは同時であってもよく、同時でなくてもよい。金属元素を担持させることと炭素化とが同時でない場合、その前後は特に限定されず、金属元素を担持させた後に炭素化を行ってもよく、炭素化の後に金属元素を担持させてもよい。
中でも、簡便性の観点から、金属元素を担持させることと炭素化とは同時であることが特に好ましい。すなわち、上述した含窒素ＧＮＲ、又は、その原料モノマー若しくは原料ポリマーを、炭素材料及び金属元素を有する化合物とともに焼成することが特に好ましい。
本発明の含窒素多環式化合物、焼成体は、上記金属元素を担持させることにより、酸素還元触媒としての活性がより優れたものとなる。
(Fired body)
The present invention is also a fired product of the nitrogen-containing polycyclic compound of the present invention.
The fired body of the present invention is obtained by firing the nitrogen-containing polycyclic compound of the present invention, the nitrogen-containing GNR, its raw material monomer or raw material polymer, or a metal carrier (metal composite) thereof. Among them, it is preferable that the carbon material is obtained by firing together. In the present specification, firing the nitrogen-containing polycyclic compound of the present invention together with a carbon material is also referred to as carbonization.
In addition, in obtaining the fired body of the present invention in which the metal element is supported and carbonized, the support of the metal element and the carbonization may or may not be performed simultaneously. When the loading of the metal element and the carbonization are not simultaneous, there is no particular limitation before and after that, carbonization may be performed after the metal element is loaded, or the metal element may be loaded after the carbonization. .
Among these, from the viewpoint of simplicity, it is particularly preferable that the metal element is supported and the carbonization is performed at the same time. That is, it is particularly preferable that the above-described nitrogen-containing GNR, or its raw material monomer or raw material polymer is baked together with the carbon material and the compound having a metal element.
The nitrogen-containing polycyclic compound and the fired body of the present invention have a more excellent activity as an oxygen reduction catalyst by supporting the metal element.
炭素材料としては、特に限定されないが、活性炭、カーボンブラック等を用いることができ、例えばＶｕｌｃａｎ ＸＣ−７２Ｒ（キャボット社製）等の導電性カーボンブラックを好適に用いることができる。
炭素材料の使用量は、例えば、本発明の含窒素多環式化合物１００質量％に対し、１〜１０００質量％であることが好ましく、５〜５００質量％であることがより好ましく、１０〜３００質量％であることが更に好ましく、３０〜２００質量％であることが特に好ましい。
Although it does not specifically limit as a carbon material, Activated carbon, carbon black, etc. can be used, for example, conductive carbon black, such as Vulcan XC-72R (made by Cabot Corporation), can be used conveniently.
The amount of the carbon material used is, for example, preferably 1 to 1000% by mass, more preferably 5 to 500% by mass, and more preferably 10 to 300% with respect to 100% by mass of the nitrogen-containing polycyclic compound of the present invention. It is more preferable that it is mass%, and it is especially preferable that it is 30-200 mass%.
焼成温度としては、例えば２００〜３０００℃が好ましく、３５０〜２５００℃がより好ましく、５００〜２０００℃が更に好ましい。
焼成時間としては、例えば１０分〜２４時間が好ましく、３０分〜１８時間がより好ましく、２〜１２時間が更に好ましい。
焼成は、例えば空気中、又は、窒素、ヘリウム、アルゴン等の不活性ガス雰囲気中で行うことができる。また、焼成における圧力条件は特に限定されず、加圧条件下、常圧条件下、減圧条件下で行うことができる。
なお、焼成前に、焼成温度以下の温度で適宜予備焼成を行ってもよい。焼成後は、酸洗や水洗、乾燥等を適宜行うことができる。
As a calcination temperature, 200-3000 degreeC is preferable, for example, 350-2500 degreeC is more preferable, and 500-2000 degreeC is still more preferable.
As a baking time, 10 minutes-24 hours are preferable, for example, 30 minutes-18 hours are more preferable, and 2-12 hours are still more preferable.
Firing can be performed, for example, in air or in an inert gas atmosphere such as nitrogen, helium, or argon. Moreover, the pressure conditions in baking are not specifically limited, It can carry out on pressurization conditions, a normal pressure condition, and pressure reduction conditions.
In addition, you may perform preliminary | backup baking suitably at the temperature below baking temperature before baking. After firing, pickling, washing with water, drying and the like can be performed as appropriate.
（酸素還元触媒）
本発明は、本発明の含窒素多環式化合物、又は、本発明の焼成体を含んで構成される酸素還元触媒でもある。
(Oxygen reduction catalyst)
The present invention is also an oxygen reduction catalyst comprising the nitrogen-containing polycyclic compound of the present invention or the fired product of the present invention.
本発明の酸素還元触媒は、本発明の含窒素多環式化合物、又は、本発明の焼成体以外のその他の成分を含んでいてもよい。その他の成分の含有割合は、本発明の酸素還元触媒１００質量％中、３０質量％以下が好ましく、１０質量％以下がより好ましく、１質量％以下が更に好ましい。また、その他の成分を実質的に含有しないことが特に好ましい。 The oxygen reduction catalyst of the present invention may contain other components other than the nitrogen-containing polycyclic compound of the present invention or the fired product of the present invention. The content of other components is preferably 30% by mass or less, more preferably 10% by mass or less, and still more preferably 1% by mass or less in 100% by mass of the oxygen reduction catalyst of the present invention. Further, it is particularly preferable that other components are not substantially contained.
以下に実施例を掲げて本発明を更に詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。なお、特に断りのない限り、「部」は「質量部」を、「％」は「質量％」を意味するものとする。
なお、ＣＯＤは、１，５−シクロオクタジエンを意味する。
The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”.
COD means 1,5-cyclooctadiene.
下記実施例及び比較例においては、次のようにして分析し、評価を行った。
＜ＭＡＬＤＩ−ＴＯＦ ＭＳ（マトリックス支援レーザー脱離イオン化飛行時間型質量分析法）による測定方法＞
サンプルとマトリックス（ジスラノール）をそれぞれＴＨＦ（テトラヒドロフラン）に溶解し、混合した。混合溶液をプレートに滴下し乾燥させ、Ｂｒｕｋｅｒ ａｕｔｏｆｌｅｘ ＩＩＩ（Ｂｒｕｋｅｒ社製）を用いて測定を行った。
In the following Examples and Comparative Examples, analysis and evaluation were performed as follows.
<Measurement Method by MALDI-TOF MS (Matrix Assisted Laser Desorption / Ionization Time-of-Flight Mass Spectrometry)>
The sample and the matrix (disranol) were dissolved in THF (tetrahydrofuran) and mixed. The mixed solution was dropped on a plate and dried, and measurement was performed using a Bruker autoflex III (manufactured by Bruker).
＜誘導結合プラズマ発光分光分析法（ＩＣＰ−ＡＥＳ法）＞
サンプル（約０．５ｍｇ）を、濃硝酸（１ｍｌ）中に分散し、１０５℃で３時間加熱した。加熱終了後、４０℃まで放冷した後、過酸化水素を２滴加えた。超純水（２ｍｌ）を加えたのち、濾過により炭素材料を除去、金属を含む測定試料溶液を得た。Ｓ試料溶液を２５ｍＬにメスアップし、ＳＨＩＭＡＤＺＵ ＩＣＰＳ−８１００（株式会社島津製作所製）を用いて、検量線法により鉄の含有量を評価した。測定は各試料に対して３回行い、平均値を鉄の質量濃度として示した。
<Inductively coupled plasma emission spectroscopy (ICP-AES method)>
A sample (about 0.5 mg) was dispersed in concentrated nitric acid (1 ml) and heated at 105 ° C. for 3 hours. After the completion of heating, the mixture was allowed to cool to 40 ° C., and 2 drops of hydrogen peroxide was added. After adding ultrapure water (2 ml), the carbon material was removed by filtration to obtain a measurement sample solution containing metal. The S sample solution was made up to 25 mL, and the iron content was evaluated by a calibration curve method using SHIMADZU ICPS-8100 (manufactured by Shimadzu Corporation). The measurement was performed three times for each sample, and the average value was shown as the iron mass concentration.
＜元素分析法＞
ｖａｒｉｏ ＥＬ ｃｕｂｅ ＣＨＮＳ（ｅｌｅｍｅｎｔｅｒ社製）を用いてＣＨＮの質量濃度を測定した。
＜熱重量測定＞
ＴｈｅｒｍｏＰｌｕｓＥＶＯＩＩ（株式会社リガク製）を用いて窒素気流下、昇温速度１０℃／ｍｉｎの条件で行った。
＜Ｘ線光電子分光法＞
ＳＨＩＭＡＤＺＵ ＫＲＡＲＯＳＡＸＩＳ−１６５ｘ（株式会社島津製作所製）を用いてＸ線源Ｍｇ−Ｋα、パスエネルギー４０ｋＶの条件下で行った。
<Elemental analysis method>
The mass concentration of CHN was measured using vario EL cube CHNS (manufactured by elementer).
<Thermogravimetry>
ThermoPlus EVO II (manufactured by Rigaku Co., Ltd.) was used under a nitrogen stream under the condition of a heating rate of 10 ° C./min.
<X-ray photoelectron spectroscopy>
This was performed under the conditions of an X-ray source Mg-Kα and a path energy of 40 kV using SHIMADZU KRAROSAXIS-165x (manufactured by Shimadzu Corporation).
＜Ｘ線吸収端近傍構造解析法（ＸＡＮＥＳ法）＞
金属含有量は１−５ｗｔ％程度、また、金属成分以外は全てＣＨＮＯの軽元素であるため全て厚み計算したペレットを作製し、室温大気下の通常の透過法で測定した。測定データは、Ｆｅ−Ｋ吸収端付近のＸＦＳデータ(ｐｒｅ−ｅｄｇｅピーク強度、吸収端の位置、Ｗｈｉｔｅ Ｌｉｎｅ強度、ＥＸＡＦＳ振動,測定範囲：６８００〜８２００ｅＶ。ＳＡＧＡ−ＬＳ ＢＬ１２にて測定を実施した。
<X-ray absorption near edge structure analysis method (XANES method)>
The metal content was about 1-5 wt%, and all the components other than the metal component were light elements of CHNO. Therefore, pellets whose thicknesses were all calculated were prepared and measured by a normal permeation method at room temperature. The measurement data were XFS data in the vicinity of the Fe-K absorption edge (pre-edge peak intensity, absorption edge position, White Line intensity, EXAFS vibration, measurement range: 6800 to 8200 eV. Measurement was performed with SAGA-LS BL12.
＜広域Ｘ線吸収微細構造解析法（ＥＸＡＦＳ法）＞
金属含有量は１−５ｗｔ％程度、また、金属成分以外は全てＣＨＮＯの軽元素であるため全て厚み計算したペレットを作製し、室温大気下の通常の透過法で測定した。測定データは、Ｆｅ−Ｋ吸収端付近のＸＦＳデータ(ＥＸＡＦＳ振動,測定範囲：６８００〜８２００ｅＶ。ＳＡＧＡ−ＬＳ ＢＬ１２にて測定を実施した。
<Wide-area X-ray absorption fine structure analysis method (EXAFS method)>
The metal content was about 1-5 wt%, and all the components other than the metal component were light elements of CHNO. Therefore, pellets whose thicknesses were all calculated were prepared and measured by a normal permeation method at room temperature. The measurement data were XFS data (EXAFS vibration, measurement range: 6800-8200 eV near the Fe-K absorption edge. Measurement was performed with SAGA-LS BL12.
＜酸素還元反応活性の測定＞
カーボン触媒（４ｍｇ）と５ｗｔ％Ｎａｆｉｏｎ（登録商標）溶液（１００μｌ）を撹拌混合した後に、３０分間、氷浴下でソニケーションを行い、カーボン触媒分散液を得た。回転リングディスク電極には、グラッシーカーボン（直径５．０ｍｍ）及び白金リングホルダー（Ｐｔ純度９９．９９％、ＩＤ６．５ｍｍ、ＯＤ７．５ｍｍ）を使用した。研磨したディスク電極上にカーボン触媒分散液（１０μｌ）をゆっくりと滴下し、Ｎａｆｉｏｎ溶液を入れた容器とあわせて、ガラス容器を被せて静置し、乾燥させた。作用極に上述で調製した触媒担持電極、対極に白金メッシュ、参照電極に銀塩化銀電極（＋０．１９９Ｖ ｖｓＮＨＥ)を用いた。回転リングディスク電極（ＲＲＤＥ）を用い、酸素飽和ＨＣｌＯ４溶液（ｐＨ１）、２５℃、電極回転速度２０００ｒｐｍ、回収効率２６％、リング電極の電位Ｅｒｉｎｇ＝１．２Ｖの条件下で測定した。測定は酸素飽和の電解液中、ディスク電極の電位を１．０〜０．０Ｖ（ｖｓ ＲＨＥ）の電位範囲で負から正方向に５ｍＶ／ｓの速度で掃引した。窒素飽和条件における測定結果バックグラウンドとした。
<Measurement of oxygen reduction reaction activity>
A carbon catalyst (4 mg) and a 5 wt% Nafion (registered trademark) solution (100 μl) were mixed with stirring, and then sonicated for 30 minutes in an ice bath to obtain a carbon catalyst dispersion. Glassy carbon (diameter 5.0 mm) and platinum ring holder (Pt purity 99.99%, ID 6.5 mm, OD 7.5 mm) were used for the rotating ring disk electrode. A carbon catalyst dispersion (10 μl) was slowly dropped onto the polished disk electrode, and the glass container was put together with the container containing the Nafion solution, and allowed to stand and dried. The catalyst-supporting electrode prepared above was used as the working electrode, the platinum mesh as the counter electrode, and the silver-silver chloride electrode (+0.199 V vs NHE) as the reference electrode. Using a rotating ring disk electrode (RRDE), measurement was performed under the conditions of an oxygen saturated HClO 4 solution (pH 1), 25 ° C.,
（製造例１〜３）
下記反応式により、実施例１の含窒素多環式化合物（モノマー）であるＰＰｙＴＰ（Ｘ＝Ｈ）、実施例２の含窒素多環式化合物（ポリマー）である［ＰＰｙＴＰ］ｎ、実施例３の含窒素多環式化合物（含窒素ＧＮＲ）であるＢＰｙ−ＧＮＲを合成した。
(Production Examples 1 to 3)
According to the following reaction formula, PPyTP (X = H) which is the nitrogen-containing polycyclic compound (monomer) of Example 1, and [PPyTP] n which is the nitrogen-containing polycyclic compound (polymer) of Example 2 and Example 3 BPy-GNR, which is a nitrogen-containing polycyclic compound (nitrogen-containing GNR), was synthesized.
実施例２の含窒素多環式化合物（ポリマー）である［ＰＰｙＴＰ］ｎを得る反応について、以下に詳しく説明する。 The reaction for obtaining [PPyTP] n which is the nitrogen-containing polycyclic compound (polymer) of Example 2 is described in detail below.
２ツ口フラスコに、Ｎｉ（ＣＯＤ）２（３０４ｍｇ、０．９０ｍｍｏｌ）、２，２’−ビピリジル（１４０ｍｇ、０．９０ｍｍｏｌ）、ＣＯＤ（１６０μＬ、０．９ｍｍｏｌ）、脱気ＤＭＦ（５ｍＬ）を加え、５５℃で３０分間撹拌して反応を行った。
この反応液を、シュレンクフラスコ内の本発明の含窒素多環式化合物のブロモ体（１６０ｍｇ、０．２３ｍｍｏｌ）及び脱気トルエン（５ｍＬ）の混合液に滴下し、２日間８０℃で加熱して撹拌した。
メタノール中で沈殿させ、ろ過し、メタノール、濃塩酸、水、水酸化ナトリウムのメタノール溶液（０．５Ｍ）、メタノール、アセトンで洗浄し、黄色粉末（［ＰＰｙＴＰ］ｎ、１１０ｍｇ）を得た。
To a two-necked flask, Ni (COD) 2 (304 mg, 0.90 mmol), 2,2′-bipyridyl (140 mg, 0.90 mmol), COD (160 μL, 0.9 mmol), and degassed DMF (5 mL) were added. The reaction was carried out with stirring at 55 ° C. for 30 minutes.
This reaction solution was added dropwise to a mixture of the bromo compound (160 mg, 0.23 mmol) of the nitrogen-containing polycyclic compound of the present invention and degassed toluene (5 mL) in a Schlenk flask, and heated at 80 ° C. for 2 days. Stir.
Precipitation in methanol, filtration, and washing with methanol, concentrated hydrochloric acid, water, a methanol solution of sodium hydroxide (0.5 M), methanol, and acetone gave a yellow powder ([PPyTP] n , 110 mg).
実施例３の含窒素多環式化合物（含窒素ＧＮＲ）であるアームチェア型のＢＰｙ−ＧＮＲ（以下、単にＢＰｙ−ＧＮＲとも言う。）を以下の反応式で表される反応により得た。 The armchair type BPy-GNR (hereinafter also simply referred to as BPy-GNR), which is the nitrogen-containing polycyclic compound (nitrogen-containing GNR) of Example 3, was obtained by the reaction represented by the following reaction formula.
シュレンクフラスコ内に、［ＰＰｙＴＰ］ｎ（５００ｍｇ）、ジクロロメタン（２５０ｍＬ）、ニトロメタン中のＦｅＣｌ３（２．５ｇ）を滴下し、窒素バブリングしながら２４時間撹拌した。反応液をろ過し、メタノール、濃塩酸、水、水酸化ナトリウムのメタノール溶液（０．５Ｍ）、メタノール、アセトンで洗浄し、茶色粉末（ＢＰｙ−ＧＮＲ、４００ｍｇ）を得た。 In the Schlenk flask, [PPyTP] n (500 mg), dichloromethane (250 mL), FeCl 3 (2.5 g) in nitromethane were added dropwise and stirred for 24 hours while bubbling nitrogen. The reaction solution was filtered and washed with methanol, concentrated hydrochloric acid, water, a methanol solution of sodium hydroxide (0.5 M), methanol and acetone to obtain a brown powder (BPy-GNR, 400 mg).
（焼成）
酢酸エチル中、ＰＰｙＴＰ、［ＰＰｙＴＰ］ｎ、ＢＰｙ−ＧＮＲ（それぞれ０．１ｍｍｏｌ）と、メタノール中のＦｅＣｌ２・４Ｈ２Ｏ（０．１ｍｍｏｌ）と、炭素材料であるＶｕｌｃａｎ ＸＣ−７２Ｒ（キャボット社製、３３．３ｍｇ）とを、窒素気流下の電気炉中で、１時間で３００℃まで昇温後、２時間３００℃で保持、さらに、１時間で１０００℃まで昇温後、２時間１０００℃で焼成した。その後、８０℃で３時間、０．５Ｍ硫酸を用いて洗浄し、脱イオン水で洗浄し、乾燥した。得られた焼成体をそれぞれＦｅ／ＰＰｙＴＰ＠ＶＣ（実施例４）、Ｆｅ／［ＰＰｙＴＰ］ｎ＠ＶＣ（実施例５）、Ｆｅ／ＢＰｙ−ＧＮＲ＠ＶＣ（実施例６）とも表記する。
(Baking)
PPyTP, [PPyTP] n , BPy-GNR (each 0.1 mmol) in ethyl acetate, FeCl 2 .4H 2 O (0.1 mmol) in methanol, and Vulcan XC-72R (made by Cabot Corporation) as a carbon material. 33.3 mg) in an electric furnace under a nitrogen stream, heated to 300 ° C. in 1 hour, held at 300 ° C. for 2 hours, further heated to 1000 ° C. in 1 hour, then 1000 ° C. for 2 hours. Baked with. Thereafter, it was washed with 0.5 M sulfuric acid at 80 ° C. for 3 hours, washed with deionized water, and dried. The obtained fired bodies are also referred to as Fe / PPyTP @ VC (Example 4), Fe / [PPyTP] n @VC (Example 5), and Fe / BPy-GNR @ VC (Example 6), respectively.
（同定）
図１は、［ＰＰｙＴＰ］ｎ、ＢＰｙ−ＧＮＲについてＭＡＬＤＩ−ＴＯＦＭＳを測定した結果を示す。図２は、［ＰＰｙＴＰ］ｎ、ＢＰｙ−ＧＮＲ、Ｆｅ／ＰＰｙＴＰ＠ＶＣ、Ｆｅ／［ＰＰｙＴＰ］ｎ＠ＶＣ、Ｆｅ／ＢＰｙ−ＧＮＲ＠ＶＣそれぞれについて誘導結合プラズマ発光分光分析法（ＩＣＰ−ＡＥＳ）及び元素分析を測定した結果を示す。図３は、ＰＰｙＴＰ、［ＰＰｙＴＰ］ｎ、ＢＰｙ−ＧＮＲについて熱重量測定を行った結果を示す。この他、１Ｈ−ＮＭＲ、１３Ｃ−ＮＭＲにより各化合物の合成を確認した。
(Identification)
FIG. 1 shows the results of measuring MALDI-TOFMS for [PPyTP] n and BPy-GNR. FIG. 2 shows inductively coupled plasma emission spectroscopy (ICP-AES) and [PPyTP] n , BPy-GNR, Fe / PPyTP @ VC, Fe / [PPyTP] n @ VC, and Fe / BPy-GNR @ VC, respectively. The result of having measured elemental analysis is shown. FIG. 3 shows the results of thermogravimetric measurements on PPyTP, [PPyTP] n and BPy-GNR. In addition, the synthesis of each compound was confirmed by 1 H-NMR and 13 C-NMR.
（ピリジン型窒素と鉄とのＦｅ−Ｎ結合の確認）
図４は、ＢＰｙ−ＧＮＲとＢＰｙ−ＧＮＲに鉄イオンを添加したものについてＸ線光電子分光法を行った結果を示す。鉄イオンを添加したものでは、結合エネルギー４００．２ｅＶにピリジン型窒素と鉄とのＦｅ−Ｎ結合由来のピークを確認した。
図５は、Ｆｅ／ＰＰｙＴＰ＠ＶＣ、Ｆｅ／［ＰＰｙＴＰ］ｎ＠ＶＣ、Ｆｅ／ＢＰｙ−ＧＮＲ＠ＶＣについてＸ線光電子分光法を行った結果を示す。結合エネルギー４００．２ｅＶにおけるＦｅ−Ｎ結合由来のピークが、それぞれ１１．８％、３５．７％、４０．７％確認され、ピリジン型窒素に鉄が配位していることが確認された。
(Confirmation of Fe-N bond between pyridine nitrogen and iron)
FIG. 4 shows the results of X-ray photoelectron spectroscopy performed on BPy-GNR and BPy-GNR added with iron ions. In the case of adding iron ions, a peak derived from the Fe—N bond between pyridine nitrogen and iron was confirmed at a binding energy of 400.2 eV.
FIG. 5 shows the results of X-ray photoelectron spectroscopy for Fe / PPyTP @ VC, Fe / [PPyTP] n @VC, and Fe / BPy-GNR @ VC. Peaks derived from Fe—N bonds at a binding energy of 400.2 eV were confirmed to be 11.8%, 35.7%, and 40.7%, respectively, and it was confirmed that iron was coordinated to pyridine type nitrogen.
図６及び図７は、Ｆｅ／ＰＰｙＴＰ＠ＶＣ、Ｆｅ／［ＰＰｙＴＰ］ｎ＠ＶＣ、Ｆｅ／ＢＰｙ−ＧＮＲ＠ＶＣについてＸ線吸収微細構造を解析した結果を示す。これら焼成体について、Ｆｅ−Ｎ結合由来のピークが観察できた。なお、図６中、ＦｅＴＰＰは、Ｆｅ−Ｎ結合を有するポルフィリン鉄錯体を表す。 6 and 7 show the results of analyzing the X-ray absorption fine structure for Fe / PPyTP @ VC, Fe / [PPyTP] n @VC, and Fe / BPy-GNR @ VC. About these baked bodies, the peak derived from a Fe-N bond has been observed. In FIG. 6, FeTPP represents a porphyrin iron complex having an Fe—N bond.
（酸素還元反応活性）
図８は、Ｆｅ／ＰＰｙＴＰ＠ＶＣ、Ｆｅ／［ＰＰｙＴＰ］ｎ＠ＶＣ、Ｆｅ／ＢＰｙ−ＧＮＲ＠ＶＣについての酸素還元反応活性を示す。それぞれのＥｏｎｓｅｔは０．８７Ｖ、０．８８Ｖ、０．８６Ｖと高い値を示した。このような焼成体は、酸素還元に必要な活性化エネルギーを充分に下げることができると考えられる。なお、図８中、ｎ＝４．０は、還元電子数が４個であることを表す。
(Oxygen reduction reaction activity)
FIG. 8 shows oxygen reduction reaction activity for Fe / PPyTP @ VC, Fe / [PPyTP] n @VC, and Fe / BPy-GNR @ VC. Each E onset showed a high value of 0.87V, 0.88V, and 0.86V. Such a fired body is considered to be able to sufficiently reduce the activation energy required for oxygen reduction. In FIG. 8, n = 4.0 indicates that the number of reduced electrons is four.
図９は、実施例４のＦｅ／ＰＰｙＴＰ＠ＶＣと、比較例であるＦｅ／１＠ＶＣ（比較例１）、Ｆｅ／２＠ＶＣ（比較例２）、Ｆｅ／３＠ＶＣ（比較例３）についての酸素還元反応活性を示す。Ｆｅ／１＠ＶＣ、Ｆｅ／２＠ＶＣ、Ｆｅ／３＠ＶＣは、それぞれ、図９に示す化合物を、本実施例と同じ方法で鉄を担持させ、焼成したものである。実施例の焼成体は、原料であるグラフェンナノリボンを構成する構成単位中の窒素原子の位置及び数が特定されていることにより、非常に優れた酸素還元反応活性を示すことが分かった。 FIG. 9 shows Fe / PPyTP @ VC of Example 4, and Fe / 1 @ VC (Comparative Example 1), Fe / 2 @ VC (Comparative Example 2), and Fe / 3 @ VC (Comparative Example 3) which are comparative examples. ) Shows oxygen reduction reaction activity. Fe / 1 @ VC, Fe / 2 @ VC, and Fe / 3 @ VC are obtained by firing the compound shown in FIG. 9 with iron supported thereon in the same manner as in this example. It was found that the fired bodies of the examples exhibited very excellent oxygen reduction reaction activity by specifying the position and number of nitrogen atoms in the structural unit constituting the graphene nanoribbon as a raw material.
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| CN114181220A (en) * | 2021-12-17 | 2022-03-15 | 中国科学技术大学 | Solenoid-shaped magnetic carbon nano material and preparation method thereof |
| JP7448912B2 (en) | 2020-03-04 | 2024-03-13 | 国立大学法人大阪大学 | Metal composite, nitrogen-containing polycyclic compound, fired body and method for producing the same, oxygen reduction catalyst, oxygen generation catalyst, and hydrogen generation catalyst |
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