JP2018048368A - Production method of amorphous carbon, and amorphous carbon - Google Patents
Production method of amorphous carbon, and amorphous carbon Download PDFInfo
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- JP2018048368A JP2018048368A JP2016183910A JP2016183910A JP2018048368A JP 2018048368 A JP2018048368 A JP 2018048368A JP 2016183910 A JP2016183910 A JP 2016183910A JP 2016183910 A JP2016183910 A JP 2016183910A JP 2018048368 A JP2018048368 A JP 2018048368A
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- 229910003481 amorphous carbon Inorganic materials 0.000 title claims abstract description 103
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 68
- 150000001875 compounds Chemical class 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 43
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000001301 oxygen Substances 0.000 claims abstract description 35
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 35
- 238000006722 reduction reaction Methods 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 239000007789 gas Substances 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 25
- 238000005259 measurement Methods 0.000 claims description 20
- GUOHRXPYGSKUGT-UHFFFAOYSA-N quinolizinium Chemical group C1=CC=CC2=CC=CC=[N+]21 GUOHRXPYGSKUGT-UHFFFAOYSA-N 0.000 claims description 20
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 12
- 238000004832 voltammetry Methods 0.000 claims description 11
- -1 monocyclic aromatic compound Chemical class 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 6
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- 125000002619 bicyclic group Chemical group 0.000 claims description 2
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 4
- 150000001408 amides Chemical class 0.000 abstract description 2
- 150000001412 amines Chemical class 0.000 abstract description 2
- 150000002825 nitriles Chemical class 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 32
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 30
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 25
- 229910052799 carbon Inorganic materials 0.000 description 24
- 229910052697 platinum Inorganic materials 0.000 description 12
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 8
- 239000000446 fuel Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000001237 Raman spectrum Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- XWPCYYOZOJKYKQ-UHFFFAOYSA-N 1-(2-chloroethyl)-3-[2-[2-[[2-chloroethyl(nitroso)carbamoyl]amino]ethyldisulfanyl]ethyl]-1-nitrosourea Chemical compound ClCCN(N=O)C(=O)NCCSSCCNC(=O)N(N=O)CCCl XWPCYYOZOJKYKQ-UHFFFAOYSA-N 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 238000003841 Raman measurement Methods 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001923 cyclic compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- PWICMAZAOPFPOI-UHFFFAOYSA-N CC.[C-]#N Chemical compound CC.[C-]#N PWICMAZAOPFPOI-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- DPOPAJRDYZGTIR-UHFFFAOYSA-N Tetrazine Chemical compound C1=CN=NN=N1 DPOPAJRDYZGTIR-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- WCZVZNOTHYJIEI-UHFFFAOYSA-N cinnoline Chemical compound N1=NC=CC2=CC=CC=C21 WCZVZNOTHYJIEI-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000005087 graphitization Methods 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
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
- Chemical Vapour Deposition (AREA)
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
Description
窒素を含有するアモルファスカーボンの製造方法、該製造方法により得られるアモルファスカーボン、及び該アモルファスカーボンを含む触媒等に関する。 The present invention relates to a method for producing nitrogen-containing amorphous carbon, amorphous carbon obtained by the production method, a catalyst containing the amorphous carbon, and the like.
現在、高活性かつ低コストな光・電気化学触媒材料の開発は、エネルギー問題や環境問題の進展に伴い急務となっている。例えば、酸素と水素を使用し生成物が水だけであるため、クリーンな発電装置として期待されている固体高分子燃料電池（ＰＦＦＣ）では、一般的に白金が触媒として使われている。しかし、白金表面での酸素還元反応速度（Ｏ２＋４Ｈ＋＋４ｅ−→２Ｈ２Ｏ）は比較的低いため、多量の白金触媒が必要となる。燃料電池自動車を例にとると１台あたり１００ｇの白金が必要とされ、これは、コストが高く経済的な面及び資源的な面からみて現実的な値ではなく、固体高分子燃料電池の実用化に向けての大きな障害となっている。また、白金は有機物などによって被毒されてしまい、電極として利用した場合に反応性の低下が起こり長期作動信頼性にも問題がある。そこで、白金を使用しない触媒の開発が望まれている。 Currently, the development of highly active and low-cost photo / electrochemical catalyst materials has become an urgent task with the progress of energy problems and environmental problems. For example, since oxygen and hydrogen are used and the product is only water, platinum is generally used as a catalyst in a solid polymer fuel cell (PFFC) that is expected as a clean power generation device. However, since the oxygen reduction reaction rate (O 2 + 4H + + 4e − → 2H 2 O) on the platinum surface is relatively low, a large amount of platinum catalyst is required. Taking a fuel cell vehicle as an example, 100 g of platinum is required per vehicle, which is not a realistic value in terms of cost and economy and resources, and is practical for a solid polymer fuel cell. It has become a major obstacle to the transformation. In addition, platinum is poisoned by organic matter and the like, and when used as an electrode, the reactivity is lowered and there is a problem in long-term operation reliability. Therefore, development of a catalyst that does not use platinum is desired.
そのため、炭素粒子に白金を担持した触媒が提案されているが、これは白金を使用することにかわりはなく大きなコスト低下は期待できない。また、炭素材料そのものを触媒として使用することも検討され、グラフェンのエッジにキノリジニウム構造を導入した材料が報告されている（非特許文献１）。しかし、グラフェンやグラフェンが積層したグラファイトでは、エッジの数が少なく、酸素還元反応の反応点となるキノリジニウム構造を多く導入することができない。また、グラファイトは層間が酸化され剥離するため、長時間の使用に対する耐久性が低い等の問題がある。一方、ダイヤモンドライクカーボンに窒素を添加して導電性を付与することが提案されているが（非特許文献２、特許文献１）、得られるダイヤモンドライクカーボンの酸素還元反応性は低く、触媒として使用することは難しかった。 For this reason, a catalyst in which platinum is supported on carbon particles has been proposed, but this does not replace the use of platinum, and a large cost reduction cannot be expected. In addition, the use of a carbon material itself as a catalyst has been studied, and a material in which a quinolizinium structure is introduced at the edge of graphene has been reported (Non-Patent Document 1). However, graphene or graphene-laminated graphite has a small number of edges, and cannot introduce a large amount of quinolizinium structure as a reaction point for the oxygen reduction reaction. Moreover, since graphite is oxidized and peeled off, graphite has problems such as low durability for long-term use. On the other hand, it has been proposed to add conductivity to diamond-like carbon by adding nitrogen (Non-patent Document 2, Patent Document 1), but the resulting diamond-like carbon has low oxygen reduction reactivity and is used as a catalyst. It was difficult to do.
本発明の課題は、上記問題を解決し、酸素還元反応の活性が高く、耐久性の高い触媒材料を提供することにある。 An object of the present invention is to solve the above problems and to provide a highly durable catalyst material having high oxygen reduction reaction activity.
本発明者は、従来から炭素材料の研究を行ってきた。そして、アモルファスカーボンに窒素を添加すると導電性を付与できることを見いだした（特許文献１）。そこで、白金を使用しない酸素還元触媒の開発を行うにあたり、アモルファスカーボンに触媒活性を付与できないかと考え様々な検討を行った。その結果、ｓｐ２混成軌道結合からなる相（グラファイト構造相）とｓｐ３混成軌道結合からなる相（ダイヤモンド構造相）とからなるアモルファスカーボンの合成時に、ｓｐ２混成軌道結合からなるクラスター相（以下、ｓｐ２Ｃクラスターともいう。）にキノリジニウム構造を導入できることを見いだした。そして、合成過程の条件を調整することにより、ｓｐ２クラスターの大きさとキノリジニウム構造の導入割合を調整することができ、酸素還元反応の活性が高いアモルファスカーボンが得られることを見いだした。また、こうして得られたアモルファスカーボンは、酸素還元反応の活性が高く、耐久性に優れた触媒として使用できることを見いだした。 The present inventor has conventionally studied carbon materials. And it discovered that electroconductivity could be provided if nitrogen was added to amorphous carbon (patent document 1). Therefore, in developing an oxygen reduction catalyst that does not use platinum, various studies were conducted on the possibility of imparting catalytic activity to amorphous carbon. As a result, when an amorphous carbon composed of a phase composed of sp 2 hybrid orbital bonds (graphite structural phase) and a phase composed of sp 3 hybrid orbital bonds (diamond structural phase) is synthesized, a cluster phase composed of sp 2 hybrid orbital bonds (hereinafter referred to as “cluster phase”). , Also referred to as sp 2 C cluster). The inventors have found that by adjusting the conditions of the synthesis process, the size of the sp 2 cluster and the introduction ratio of the quinolizinium structure can be adjusted, and amorphous carbon having high oxygen reduction reaction activity can be obtained. Further, it has been found that the amorphous carbon thus obtained has a high activity of oxygen reduction reaction and can be used as a catalyst having excellent durability.
すなわち、本発明は以下に示す事項により特定されるものである。
（１）式（Ｉ）、（II）又は（III）で表される第１の化合物と、環内に窒素原子を１個又は２個以上含む複素環式化合物である第２の化合物とを含む原料ガスを反応容器内に導入し、前記原料ガスを前記反応容器内で反応させて、窒素を含有するアモルファスカーボンを反応容器内に設置した基板上に堆積させることを特徴とする窒素を含有するアモルファスカーボンの製造方法。
（２）原料ガスをプラズマ化させることを特徴とする上記（１）記載のアモルファスカーボンの製造方法。
（３）第２の化合物が、六員環からなる単環式芳香族化合物又は２個若しくは３個の六員環の縮合環からなる二環式若しくは三環式芳香族化合物であることを特徴とする上記（１）又は（２）記載のアモルファスカーボンの製造方法。
（４）第２の化合物が、ピリジン、ピラジン及びトリアジンからなる群から選ばれる少なくとも１種であることを特徴とする上記（１）〜（３）のいずれかに記載のアモルファスカーボンの製造方法。
（５）式（Ｉ）、（II）又は（III）で表される第１の化合物と、環内に窒素原子を１個又は２個以上含む複素環式化合物である第２の化合物とを含む原料ガスを反応容器内に導入し、前記原料ガスを反応容器内でプラズマ化して反応させ、反応容器内に設置した基板上に堆積させて得られる窒素を含有するアモルファスカーボン。
（６）キノリジニウム構造を有し、対流ボルタンメトリー測定から算出される酸素還元反応に対する反応電子数が１．５以上であることを特徴とする窒素を含有するアモルファスカーボン。
（７）上記（５）又は（６）記載の窒素を含有するアモルファスカーボンを含む触媒。
（８）キノリジニウム構造を有するアモルファスカーボン酸素還元触媒。
（９）上記（７）又は（８）記載の触媒を備える電極。
That is, the present invention is specified by the following items.
(1) A first compound represented by the formula (I), (II) or (III) and a second compound which is a heterocyclic compound containing one or more nitrogen atoms in the ring. Containing nitrogen, characterized in that a source gas containing is introduced into a reaction vessel, the source gas is reacted in the reaction vessel, and amorphous carbon containing nitrogen is deposited on a substrate placed in the reaction vessel A method for producing amorphous carbon.
(2) The method for producing amorphous carbon as described in (1) above, wherein the source gas is turned into plasma.
(3) The second compound is a monocyclic aromatic compound composed of a six-membered ring or a bicyclic or tricyclic aromatic compound composed of a condensed ring of two or three six-membered rings. The method for producing amorphous carbon according to (1) or (2) above.
(4) The method for producing amorphous carbon as described in any one of (1) to (3) above, wherein the second compound is at least one selected from the group consisting of pyridine, pyrazine and triazine.
(5) A first compound represented by formula (I), (II) or (III) and a second compound which is a heterocyclic compound containing one or more nitrogen atoms in the ring. Amorphous carbon containing nitrogen obtained by introducing a raw material gas into a reaction vessel, converting the raw material gas into plasma in the reaction vessel, reacting it, and depositing it on a substrate placed in the reaction vessel.
(6) A nitrogen-containing amorphous carbon having a quinolizinium structure and having a reaction electron number for an oxygen reduction reaction calculated from convective voltammetry measurement of 1.5 or more.
(7) The catalyst containing the amorphous carbon containing nitrogen as described in said (5) or (6).
(8) An amorphous carbon oxygen reduction catalyst having a quinolizinium structure.
(9) An electrode comprising the catalyst according to (7) or (8) above.
本発明のアモルファスカーボンの製造方法は、アモルファスカーボンにキノリジニウム構造を効果的に導入することができ、酸素還元反応の活性が高いアモルファスカーボンを製造することができる。また、本発明のアモルファスカーボンは、酸素還元反応の活性が高く、耐久性が高い。そのため酸素還元反応の活性が高く、耐久性に優れた触媒として使用できる。 The method for producing amorphous carbon of the present invention can effectively introduce a quinolizinium structure into amorphous carbon, and can produce amorphous carbon having high oxygen reduction reaction activity. In addition, the amorphous carbon of the present invention has high oxygen reduction reaction activity and high durability. Therefore, it can be used as a catalyst having high activity of oxygen reduction reaction and excellent durability.
本発明の窒素を含有するアモルファスカーボンの製造方法は、式（Ｉ）、（II）又は（III）で表される第１の化合物と、環内に窒素原子を１個又は２個以上含む複素環式化合物である第２の化合物とを含む原料ガスを反応容器内に導入し、前記原料ガスを反応容器内で反応させて、窒素を含有するアモルファスカーボンを反応容器内に設置した基板上に堆積させることを特徴とする。 The method for producing nitrogen-containing amorphous carbon of the present invention includes a first compound represented by the formula (I), (II) or (III) and a complex containing one or more nitrogen atoms in the ring. A raw material gas containing a second compound, which is a cyclic compound, is introduced into a reaction vessel, the raw material gas is reacted in the reaction vessel, and amorphous carbon containing nitrogen is placed on the substrate placed in the reaction vessel. It is characterized by depositing.
式（Ｉ）〜（III）中、Ｒ、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５及びＲ６は、Ｈ又は置換基を有してもよいアルキル基を表し、それぞれの式中で同一でも異なっていてもよい。前記アルキル基は、特に限定されるものではないが、例えば、炭素数が１〜６のアルキル基を挙げることができる。炭素数が１〜６のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、ネオペンチル基、ｔ−ペンチル基、ｎ−へキシル基、イソへキシル基等を挙げることができる。前記置換基としては、特に限定されるものではないが、例えば、カルボキシル基、アミド基、イミド基、エステル基、水酸基等を挙げることができる。本発明では、第１の化合物は、アモルファスカーボンを合成しやすくするだけでなく、アモルファスカーボン中に３つのｓｐ３混成炭素と結合する窒素を導入し、前記窒素上に余る電子によるホッピング伝導を利用してアモルファスカーボンに導電性を付与する働きをする。触媒として固体高分子燃料電池等の電極に使用する場合、導電性が高い方が電極としての性能が向上すると考えられる。そのため、第１の化合物としては、窒素原子を含みｓｐ３混成炭素からなる化合物が好ましく、ニトリル、アミド及びアミンにおいて、有機基をアルキル基とした式（Ｉ）〜（III）で表される化合物を使用している。また、炭素数が小さい方が窒素を導入しやすい傾向があるため、式（Ｉ）で表される化合物におけるＲ、式（II）で表される化合物におけるＲ１〜Ｒ３の少なくとも一つ、及び式（III）で表される化合物におけるＲ４〜Ｒ６の少なくとも一つは、メチル基、エチル基、又はプロピル基であることが好ましい。 In formulas (I) to (III), R, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 represent H or an optionally substituted alkyl group, May be the same or different. Although the said alkyl group is not specifically limited, For example, a C1-C6 alkyl group can be mentioned. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, and isopentyl group. Group, neopentyl group, t-pentyl group, n-hexyl group, isohexyl group and the like. Although it does not specifically limit as said substituent, For example, a carboxyl group, an amide group, an imide group, an ester group, a hydroxyl group etc. can be mentioned. In the present invention, the first compound not only facilitates the synthesis of amorphous carbon, but also introduces hopping conduction by electrons remaining on the nitrogen by introducing nitrogen bonded to three sp 3 hybrid carbons into the amorphous carbon. Thus, it serves to impart conductivity to the amorphous carbon. When used for an electrode of a polymer electrolyte fuel cell or the like as a catalyst, it is considered that the higher the conductivity, the better the performance as an electrode. Therefore, as the first compound, a compound containing a nitrogen atom and comprising sp 3 hybrid carbon is preferable, and compounds represented by formulas (I) to (III) in which an organic group is an alkyl group in nitrile, amide and amine Is used. Moreover, since the one where carbon number is smaller tends to introduce nitrogen, at least one of R 1 to R 3 in the compound represented by R, R in the compound represented by the formula (II), And at least one of R 4 to R 6 in the compound represented by Formula (III) is preferably a methyl group, an ethyl group, or a propyl group.
第１の化合物である式（Ｉ）〜（III）で表される化合物は、特に限定されるものではないが、例えば、式（Ｉ）で表される化合物としては、シアン化水素、アセトニトリル、エタンシアニド、プロパンシアニド等を挙げることができ、式（II）で表される化合物としては、ホルムアミド、アセトアミド等を挙げることができ、式（III）で表される化合物としては、メチルアミン、エチルアミン等を挙げることができる。なかでも、アセトニトリル、メチルアミンが好ましい。 The compounds represented by the formulas (I) to (III) as the first compound are not particularly limited, but examples of the compound represented by the formula (I) include hydrogen cyanide, acetonitrile, ethanecyanide, Examples of the compound represented by the formula (II) include formamide and acetamide. Examples of the compound represented by the formula (III) include methylamine and ethylamine. Can be mentioned. Of these, acetonitrile and methylamine are preferred.
第２の化合物としては、環内に窒素原子を１個又は２個以上含む複素環式化合物であれば、特に限定されるものではなく、窒素原子を１個含んでいてもよく、２個以上含んでいてもよい。また、単環式化合物及び多環式化合物のいずれでもよく、多環式化合物は縮合環式化合物であってもよい。また、置換基を有していてもよい。本発明では、第２の化合物は、アモルファスカーボン中のｓｐ２Ｃクラスターにキノリジニウム構造を形成する働きをする。ｓｐ２Ｃクラスターを形成し、キノリジニウム構造を形成しやすくする観点から、不飽和結合を有する複素環式芳香族化合物が好ましく、六員環を有する化合物が好ましい。六員環中で炭素と窒素がｓｐ２結合で結合しつつ、分子サイズが小さいものの方が窒素原子をｓｐ２Ｃクラスター中に導入しやすいとの観点から、六員環からなる化合物又は２個若しくは３個の六員環の縮合環からなる化合物が好ましい。一個の六員環からなる、環内に窒素原子を１個又は２個以上含む単環式の複素環式芳香族化合物としては、例えば、ピリジン、ピラジン、ピリミジン、ピリダジン、トリアジン、テトラジン等を挙げることができる。また、二個の六員環の縮合環からなる、環内に窒素原子を１個又は２個以上含む二環式の複素環式芳香族化合物としては、キノリン、イソキノリン、キノキサリン、キナゾリン、シンノリン等を挙げることができ、三個の六員環の縮合環からなる、環内に窒素原子を１個又は２個以上含む三環式の複素環式芳香族化合物としては、フェナントロリン、アクリジン等を挙げることができる。なかでも、ピリジン、ピラジン及びトリアジンが好ましい。 The second compound is not particularly limited as long as it is a heterocyclic compound containing one or two or more nitrogen atoms in the ring, and may contain one or more nitrogen atoms. May be included. Moreover, any of a monocyclic compound and a polycyclic compound may be sufficient, and a polycyclic compound may be a condensed cyclic compound. Moreover, you may have a substituent. In the present invention, the second compound functions to form a quinolizinium structure in sp 2 C clusters in amorphous carbon. From the viewpoint of forming an sp 2 C cluster and easily forming a quinolizinium structure, a heterocyclic aromatic compound having an unsaturated bond is preferable, and a compound having a six-membered ring is preferable. A compound consisting of a six-membered ring or two compounds, in which carbon and nitrogen are bonded by an sp 2 bond in a six-membered ring and a molecule having a smaller molecular size is easier to introduce a nitrogen atom into the sp 2 C cluster. Or the compound which consists of a condensed ring of three 6-membered rings is preferable. Examples of monocyclic heteroaromatic compounds composed of one 6-membered ring and containing one or more nitrogen atoms in the ring include pyridine, pyrazine, pyrimidine, pyridazine, triazine, tetrazine and the like. be able to. In addition, bicyclic heterocyclic aromatic compounds composed of two 6-membered condensed rings and containing one or more nitrogen atoms in the ring include quinoline, isoquinoline, quinoxaline, quinazoline, cinnoline, etc. Examples of the tricyclic heterocyclic aromatic compound composed of three six-membered condensed rings and containing one or more nitrogen atoms in the ring include phenanthroline and acridine. be able to. Of these, pyridine, pyrazine and triazine are preferable.
本発明の製造方法では、式（Ｉ）、（II）又は（III）で表される第１の化合物と、環内に窒素原子を１個又は２個以上含む複素環式化合物である第２の化合物とを含む原料ガスを反応容器内に導入し、前記原料ガスを反応容器内で反応させて、窒素を含有するアモルファスカーボンを反応容器内に設置した基板上に堆積させる。この方法は、ＣＶＤ法といわれる方法であり、反応容器内への原料ガスの導入量、反応容器内の温度、圧力、基板の温度等は適宜選択できるが、プラズマを利用したプラズマＣＶＤ法が好ましい。本発明において原料ガスを反応容器内に導入するとは、第１の化合物と第２の化合物の両方を含む原料ガスを調製して反応容器内に導入すること、及び第１の化合物を含む原料ガスと、第２の化合物を含む原料ガスを別々に反応容器内に導入することにより、両者を含む原料ガスを反応容器内に導入することの両方を意味する。また、式（Ｉ）、（II）又は（III）で表される第１の化合物は、これらを単独で原料として用いてもよく、２種以上を原料として用いてもよい。第２の化合物も、１種のみを用いてもよく、２種以上を用いてもよい。第１の化合物と第２の化合物との混合比率は、特に限定されるものではないが、［第１の化合物］：［第２の化合物］が８：２〜２：８が好ましく、６：４〜３：７がより好ましい。また、プラズマＣＶＤ法の場合、添加ガスとして、アルゴン、ヘリウム等の不活性ガスや水素などを原料ガスと共に反応容器内へ導入することが好ましい。電極に印加する電力（プラズマ出力）を低くするとアモルファス構造を維持できるが、キノリジニウム構造の導入割合を高くし難く、プラズマ出力を高くするとｓｐ２Ｃクラスターを細分化できるが、高くしすぎるとｓｐ２混成結合炭素化が進行し剥離しやすくなる。また、反応容器内の温度を高くするほど、ｓｐ２混成結合炭素比率が上昇しｓｐ２Ｃクラスターが拡大してグラファイト化が進む。プラズマ出力及び反応容器内の温度は、これらを考慮して適宜選択することができる。アモルファス構造を維持したままｓｐ２Ｃクラスターを細分化し、キノリジニウム構造の導入比率を高める観点から、プラズマ出力は、１５０〜５００Ｗが好ましく、成膜中の基板温度は、２００〜３００℃が好ましい。 In the production method of the present invention, the first compound represented by the formula (I), (II) or (III) and the second compound which is a heterocyclic compound containing one or more nitrogen atoms in the ring. A raw material gas containing the above compound is introduced into a reaction vessel, the raw material gas is reacted in the reaction vessel, and amorphous carbon containing nitrogen is deposited on a substrate installed in the reaction vessel. This method is called a CVD method, and the amount of source gas introduced into the reaction vessel, the temperature in the reaction vessel, the pressure, the temperature of the substrate, etc. can be selected as appropriate, but the plasma CVD method using plasma is preferred. . In the present invention, the introduction of the raw material gas into the reaction vessel means that a raw material gas containing both the first compound and the second compound is prepared and introduced into the reaction vessel, and the raw material gas containing the first compound And by introducing the source gas containing the second compound separately into the reaction vessel, the source gas containing both is introduced into the reaction vessel. Moreover, the 1st compound represented by Formula (I), (II) or (III) may be used individually as a raw material, and may use 2 or more types as a raw material. The second compound may also be used alone or in combination of two or more. The mixing ratio of the first compound and the second compound is not particularly limited, but [first compound]: [second compound] is preferably 8: 2 to 2: 8, and 6: 4-3: 7 is more preferable. In the case of the plasma CVD method, it is preferable to introduce an inert gas such as argon or helium, hydrogen, or the like as an additive gas into the reaction vessel together with the source gas. Although A lower power (plasma power) applied to the electrodes an amorphous structure can be maintained, it is difficult to increase the introduction rate of quinolizinium structure, the higher the plasma output sp 2 C clusters can be subdivided, too high sp 2 Hybrid bond carbonization proceeds and becomes easy to peel off. Moreover, the higher the temperature in the reaction vessel, the higher the sp 2 hybrid bonded carbon ratio, the larger the sp 2 C cluster, and the graphitization proceeds. The plasma output and the temperature in the reaction vessel can be appropriately selected in consideration of these. From the viewpoint of subdividing the sp 2 C clusters while maintaining the amorphous structure and increasing the introduction ratio of the quinolizinium structure, the plasma output is preferably 150 to 500 W, and the substrate temperature during film formation is preferably 200 to 300 ° C.
本発明の窒素を含有するアモルファスカーボンは、本発明の製造方法により製造することができる。本発明の製造方法により得られる窒素を含有するアモルファスカーボンは、キノリジニウム構造を有し、優れた酸素還元反応活性を示す。これは、本発明の製造方法によると、窒素を含有させたアモルファスカーボンを合成する際に、サイズの小さなｓｐ２Ｃクラスターを多数形成することができ、ｓｐ２Ｃクラスターのエッジ部に形成されるキノリジニウム構造の割合を多くできるためと考えられる。このため、本発明の窒素を含有するアモルファスカーボンは、酸素４電子還元の活性サイト数が増加するので、優れた酸素還元反応活性を示す。図１に、本発明のアモルファスカーボンにおけるキノリジニウム構造と酸素の吸着に関する模式図を示す。本発明の窒素を含有するアモルファスカーボンは、対流ボルタンメトリー測定の結果から算出される酸素還元反応に対する反応電子数が１．５以上が好ましく、１．８以上が更に好ましく、２．０以上がより好ましい。本発明の窒素を含有するアモルファスカーボンにおけるｓｐ２Ｃクラスターサイズは、キノリジニウム構造の割合を多くする観点及びアモルファス構造を維持する観点から、２〜５ｎｍが好ましく、３〜４ｎｍがより好ましい。また、本発明の窒素を含有するアモルファスカーボンにおける三つのｓｐ２混成結合炭素と結合した窒素（Ｃ−Ｎ（＝Ｃ）−Ｃ；第４級窒素）の割合は、キノリジニウム構造の割合を多くする観点から０．４〜４．０原子％が好ましく、０．６〜３．０原子％がより好ましい。本発明のアモルファスカーボンにおけるｓｐ２混成結合炭素（ｓｐ２Ｃ）とｓｐ３混成結合炭素（ｓｐ３Ｃ）の比率（ｓｐ２Ｃ：ｓｐ３Ｃ）は６０：４０〜８０：２０が好ましく、７０：３０〜８０：２０がより好ましい。前記反応電子数、ｓｐ２Ｃクラスターサイズ、三つのｓｐ２混成結合炭素と結合した窒素の割合、及びｓｐ２Ｃとｓｐ３Ｃの比率は、実施例に記載した方法で測定及び算出することができる。また、本発明の窒素を含有するアモルファスカーボンは、グラファイトのように剥離することなく耐久性に優れる。そのため、本発明の窒素を含有するアモルファスカーボンは、酸素還元反応の活性が高く、長期間安定して使用できる触媒として用いることができる。本発明の触媒は、本発明の窒素を含有するアモルファスカーボンを含み、該アモルファスカーボンのみからなってもよく、触媒活性に影響のない範囲で他の成分を含んでもよい。本発明の触媒は、固体高分子燃料電池等の電極に使用することができ、本発明の触媒を備えた電極は、酸素還元反応の活性が高く、長期間安定して使用できる。 The nitrogen-containing amorphous carbon of the present invention can be produced by the production method of the present invention. The nitrogen-containing amorphous carbon obtained by the production method of the present invention has a quinolizinium structure and exhibits excellent oxygen reduction reaction activity. This is because according to the production method of the present invention, when synthesizing amorphous carbon containing nitrogen, a large number of sp 2 C clusters having a small size can be formed and formed at the edge of the sp 2 C cluster. This is thought to be because the proportion of the quinolizinium structure can be increased. For this reason, the nitrogen-containing amorphous carbon of the present invention exhibits an excellent oxygen reduction reaction activity because the number of active sites for oxygen 4-electron reduction increases. FIG. 1 is a schematic diagram relating to the adsorption of quinolizinium structure and oxygen in the amorphous carbon of the present invention. In the nitrogen-containing amorphous carbon of the present invention, the number of reaction electrons for the oxygen reduction reaction calculated from the result of convective voltammetry measurement is preferably 1.5 or more, more preferably 1.8 or more, and more preferably 2.0 or more. . The sp 2 C cluster size in the nitrogen-containing amorphous carbon of the present invention is preferably 2 to 5 nm and more preferably 3 to 4 nm from the viewpoint of increasing the proportion of the quinolizinium structure and maintaining the amorphous structure. The ratio of nitrogen (CN (= C) -C; quaternary nitrogen) bonded to three sp 2 hybrid bonded carbons in the nitrogen-containing amorphous carbon of the present invention increases the ratio of the quinolizinium structure. From a viewpoint, 0.4-4.0 atomic% is preferable and 0.6-3.0 atomic% is more preferable. The ratio (sp 2 C: sp 3 C) of sp 2 hybrid bonded carbon (sp 2 C) to sp 3 hybrid bonded carbon (sp 3 C) in the amorphous carbon of the present invention is preferably 60:40 to 80:20, 70 : 30 to 80:20 is more preferable. The number of reaction electrons, sp 2 C cluster size, the ratio of nitrogen bonded to three sp 2 hybrid bonded carbons, and the ratio of sp 2 C and sp 3 C can be measured and calculated by the method described in the examples. it can. Moreover, the amorphous carbon containing nitrogen of this invention is excellent in durability, without peeling like graphite. Therefore, the nitrogen-containing amorphous carbon of the present invention has a high oxygen reduction reaction activity and can be used as a catalyst that can be used stably for a long period of time. The catalyst of the present invention contains the amorphous carbon containing nitrogen of the present invention, may consist of the amorphous carbon alone, or may contain other components within a range that does not affect the catalytic activity. The catalyst of the present invention can be used for an electrode of a solid polymer fuel cell or the like, and an electrode equipped with the catalyst of the present invention has a high oxygen reduction reaction activity and can be used stably for a long period of time.
実施例で得られたアモルファスカーボンは、以下の測定方法で評価した。
（ＸＰＳ測定）
実施例で得られたアモルファスカーボンの元素組成をＸＰＳ測定装置（Thermo Scientific, Model. K-AlphaTM+ X-ray Photoelectron Spectrometer System）を使用してＸＰＳ法により調べた。Ｘ線源は単色化されたＡｌＫα線（１４６８．６ｅＶ）とし、測定角は９０°とした。結合エネルギー分解能は、０．５ｅＶであった。０〜１１００ｅＶの範囲を、１０ｅＶ／ｍｉｎ（０．１ｅＶ／ｓｔｅｐ）の掃引速度で測定した。測定した結果、２８５ｅＶ、３９８ｅＶ及び５３１ｅＶの位置に、それぞれＣ １ｓ、Ｎ １ｓ及びＯ １ｓのピークが確認された。各ピーク強度から元素組成比を算出した。また、測定範囲を３９１〜４０８ｅＶの範囲とし、掃引速度を１ｅＶ／ｍｉｎとして測定し、測定されたデータのピーク分離を行い、ｓｐ３混成結合炭素と結合した窒素（Ｎ−Ｃ；ピロール型窒素）、ｓｐ混成結合炭素と結合した窒素（Ｎ−Ｃ）、二つのｓｐ２混成結合炭素と結合した窒素（Ｃ−Ｎ−Ｃ；ピリジン型窒素）及び三つのｓｐ２混成結合炭素と結合した窒素（Ｃ−Ｎ（＝Ｃ）−Ｃ；第４級窒素）の各ピークに分離し、アモルファスカーボンに含まれる窒素における第４級窒素の割合を算出した。各ピークのピーク位置は、それぞれ３９８．３ｅＶ、３９８．９ｅＶ、３９９．９ｅＶ、４０１．８ｅＶであり、実施例で得られたアモルファスカーボンの全てで４０１．８ｅＶにキノリジニウム構造由来の成分が観測された。アモルファスカーボン中の窒素元素比（原子％）に第４級窒素の割合を乗じてアモルファスカーボン中の第４級窒素元素比（原子％）を算出した。
The amorphous carbon obtained in the examples was evaluated by the following measuring method.
(XPS measurement)
The elemental composition of the amorphous carbon obtained in the examples was examined by the XPS method using an XPS measuring apparatus (Thermo Scientific, Model. K-Alpha ™ + X-ray Photoelectron Spectrometer System). The X-ray source was a monochromatic AlKα ray (1468.6 eV), and the measurement angle was 90 °. The binding energy resolution was 0.5 eV. A range of 0 to 1100 eV was measured at a sweep rate of 10 eV / min (0.1 eV / step). As a result of the measurement, peaks of C 1s, N 1s and O 1s were confirmed at positions of 285 eV, 398 eV and 531 eV, respectively. The elemental composition ratio was calculated from each peak intensity. In addition, the measurement range is 391 to 408 eV, the sweep rate is 1 eV / min, the measured data is separated, and nitrogen is bonded to sp 3 hybrid bonded carbon (N—C: pyrrole nitrogen) , Nitrogen bonded to sp hybrid bonded carbon (N—C), nitrogen bonded to two sp 2 hybrid bonded carbon (C—N—C; pyridine type nitrogen) and nitrogen bonded to three sp 2 hybrid bonded carbon ( C—N (═C) —C; quaternary nitrogen) was separated, and the ratio of quaternary nitrogen in nitrogen contained in amorphous carbon was calculated. The peak positions of each peak were 398.3 eV, 398.9 eV, 399.9 eV, and 401.8 eV, respectively, and a component derived from a quinolizinium structure was observed at 401.8 eV in all of the amorphous carbons obtained in the examples. . The ratio of quaternary nitrogen in the amorphous carbon (atomic%) was calculated by multiplying the ratio of nitrogen in the amorphous carbon (atomic%) by the ratio of quaternary nitrogen.
（ラマンスペクトル測定）
励起源としてＡｒ＋レーザー（波長５１４．５ｎｍ）を用いるラマン顕微鏡システム（Jasco Cop. RPM-500）を使用して、実施例で得られたアモルファスカーボンのラマンスペクトルを得た。観察されたラマンスペクトルは、アモルファスカーボンで典型的に観察されるＧピーク及びＤピークから構成されていた。これは、得られたアモルファスカーボンにおけるｓｐ２混成結合炭素は、クラスターを形成していることを示す。ｓｐ２／ｓｐ３混成結合炭素の元素比率は、次式（ａ）により求め、ｓｐ２混成結合炭素のクラスター（以下、ｓｐ２Ｃクラスターともいう。）の直径は、次式（ｂ）により求めた。
式（ａ）：ｓｐ３content ＝ ０．２４−４８．９(ωＧ−０．１５８０)
ここで、ωＧは、ラマン散乱測定において観測されたＧピークのピーク位置を周波数に換算したものである。アモルファスカーボンでは、アモルファスカーボンを構成するｓｐ２／ｓｐ３炭素比とラマン散乱測定におけるＧピーク位置に相関性があり、式（ａ）は様々なｓｐ２／ｓｐ３炭素比をもつアモルファスカーボンのラマン散乱測定におけるＧピーク位置のプロットから求められた経験的な等式として、当該技術分野で通常用いられている。ラマン測定で得られたスペクトルを、ＧピークとＤピークにピーク分離し分離したＧピークのピーク位置を式（ａ）に代入してｓｐ３成分量を算出した。
式（ｂ）：Ｌａ ＝ Ｃ（ＩＤ／ＩＧ）−１
ここで、スケーリング係数Ｃは、４４Åである。アモルファスカーボン中のｓｐ２炭素凝集部分（ｓｐ２Ｃクラスター）の結晶化度が高いほど、Ｇピーク強度ＩＧは高くなり、これに反してｓｐ２カーボン部位の欠陥に比例するＤピークのピーク強度ＩＤは低くなる。したがって結晶化度はＩＤ／ＩＧに反比例する。式（ｂ）は、様々なｓｐ２Ｃクラスターサイズをもつアモルファスカーボンのラマン散乱測定より算出したＩＤ／ＩＧのプロットから求められた経験的な等式として、当該技術分野で通常用いられている。ラマン測定で得られたスペクトルを、ＧピークとＤピークにピーク分離し、ＧピークとＤピークのピーク強度を式（ｂ）に代入してｓｐ２Ｃクラスターサイズを算出した。
(Raman spectrum measurement)
Using a Raman microscope system (Jasco Cop. RPM-500) using an Ar + laser (wavelength 514.5 nm) as an excitation source, a Raman spectrum of the amorphous carbon obtained in the example was obtained. The observed Raman spectrum consisted of G and D peaks typically observed with amorphous carbon. This indicates that the sp 2 hybrid bonded carbon in the obtained amorphous carbon forms a cluster. The element ratio of sp 2 / sp 3 hybrid bonded carbon is obtained from the following formula (a), and the diameter of the sp 2 hybrid bonded carbon cluster (hereinafter also referred to as sp 2 C cluster) is obtained from the following formula (b). It was.
Formula (a): sp 3 content = 0.24-48.9 (ω G -0.1580)
Here, ω G is obtained by converting the peak position of the G peak observed in the Raman scattering measurement into a frequency. In the case of amorphous carbon, there is a correlation between the sp 2 / sp 3 carbon ratio constituting the amorphous carbon and the G peak position in the Raman scattering measurement, and the formula (a) shows the Raman of amorphous carbon having various sp 2 / sp 3 carbon ratios. It is commonly used in the art as an empirical equation determined from a plot of G peak position in a scatter measurement. The spectrum obtained by Raman measurement was separated into a G peak and a D peak and the peak position of the separated G peak was substituted into formula (a) to calculate the amount of sp 3 components.
Formula (b): La = C ( ID / IG ) -1
Here, the scaling coefficient C is 44Å. The higher the crystallinity of the sp 2 carbon aggregate portions in the amorphous carbon (sp 2 C clusters), G peak intensity I G is high, the peak intensity of D peak is proportional to the defect of the sp 2 carbon site on the contrary ID is low. Therefore crystallinity is inversely proportional to I D / I G. Formula (b), as the empirical equations determined from a plot of I D / I G calculated from Raman scattering measurement of amorphous carbon with various sp 2 C cluster size, commonly used in the art Yes. The spectrum obtained by Raman measurement was peak-separated into G peak and D peak, and the peak intensity of G peak and D peak was substituted into formula (b) to calculate sp 2 C cluster size.
（対流ボルタンメトリー測定）
不導体被覆金属棒の先端に、中心に直径1ｃｍの円形の穴のあいたポリプロピレンキャップにより実施例で得られたアモルファスカーボンを装着し、金属棒の導体部分とアモルファスカーボンの導通をとって回転電極を作製した。アモルファスカーボンは直径１ｃｍの円形の穴部分で溶液と接し、アモルファスカーボン層の厚みは１μｍであった。作製した電極を回転ディスク電極測定ユニット（Hokuto, Dynamic electrode system; HR-201 and 202, Potentio/Galvanostat; HSV-100）に装着して、酸素で過飽和された０．１ＭＫＯＨ溶液中に室温で浸漬し、対極に白金線を用いて、回転速度５００ｒｐｍで回転させながら、掃引レート５ｍＶｓ−１で電極電位０．５Ｖ ｖｓ．Ａｇ|ＡｇＣｌから３．０Ｖ ｖｓ．Ａｇ|ＡｇＣｌまで掃引しボルタモグラムを得た。同じ実験を１０回繰り返し、−１．７ ｖｓ．Ａｇ|ＡｇＣｌにおける電流値の１０回の平均値を試料のｉＬとして式（ｃ）に代入し、酸素の還元に対する電子数ｎを算出した。
式（ｃ）： ｉＬ ＝ ０．６２ｎＦＡＤ２／３ω１／２ｖ−１．５Ｃ＊
ここで、ｉＬは観測される電流値、Ａは電極面積、Ｄは電解液中の酸素分子の拡散係数、ｖは電解液の粘度、Ｃ＊は電解液中の酸素飽和濃度、ωは回転電極の回転周波数、Ｆはファラデー定数（９．６４８５×１０４Ｃ／ｍｏｌ）であり、式（ｃ）はこれらの関係を表す式として当該技術分野で通常用いられる式である。電極面積Ａは０．７８５ｃｍ２、電解液中の酸素分子の拡散係数Ｄは１．９×１０−５ｃｍ２ｓ−１、電解液の粘度ｖは０．０１ｃｍ２／ｓ、電解液中の酸素飽和濃度Ｃ＊は１．２×１０−６ｍｏｌ／ｃｍ２であった。
(Convection voltammetry measurement)
Attach the amorphous carbon obtained in the example with a polypropylene cap with a circular hole with a diameter of 1 cm in the center to the tip of the non-conductive coated metal rod, and connect the conductive portion of the metal rod to the amorphous carbon to connect the rotating electrode. Produced. The amorphous carbon was in contact with the solution at a circular hole having a diameter of 1 cm, and the thickness of the amorphous carbon layer was 1 μm. The prepared electrode is attached to a rotating disk electrode measurement unit (Hokuto, Dynamic electrode system; HR-201 and 202, Potentio / Galvanostat; HSV-100) and immersed in a 0.1 M KOH solution supersaturated with oxygen at room temperature. Using a platinum wire as the counter electrode, while rotating at a rotation speed of 500 rpm, the electrode potential was 0.5 V vs. at a sweep rate of 5 mVs −1. 3.0V vs. Ag | AgCl. A voltammogram was obtained by sweeping to Ag | AgCl. The same experiment was repeated 10 times, and -1.7 vs. Ag | 10 times of the average value of the current value in AgCl into Equation (c) as i L of the sample was calculated electron number n for the reduction of oxygen.
Formula (c): i L = 0.62 nFAD 2/3 ω 1/2 v −1.5 C *
Here, i L is the observed current value, A is the electrode area, D is the diffusion coefficient of oxygen molecules in the electrolyte, v is the viscosity of the electrolyte, C * is the oxygen saturation concentration in the electrolyte, and ω is the rotation The rotational frequency of the electrode, F, is a Faraday constant (9.6485 × 10 4 C / mol), and the formula (c) is a formula that is usually used in the art as a formula representing these relationships. The electrode area A is 0.785 cm 2 , the diffusion coefficient D of oxygen molecules in the electrolyte is 1.9 × 10 −5 cm 2 s −1 , the viscosity v of the electrolyte is 0.01 cm 2 / s, The oxygen saturation concentration C * was 1.2 × 10 −6 mol / cm 2 .
［実施例１］
窒素を含有するアモルファスカーボンを、カソードカップリング型高周波プラズマ励起化学蒸着（ＲＦ−ＰｅＣＶＤ）装置（１３．５６ＭＨｚ，ＳＡＭＣＯ Ｃｏ．，Ｌｔｄ．Ｍｏｄｅｌ ＢＰ−１）により調製した。アセトニトリルとピリジンをモル比で８：２に混合した混合物を原料として用い、アルゴンガスを添加ガスとして用いて、温度５０℃、原料ガスの流量１ｓｃｃｍ、アルゴンガスの流量２０ｓｃｃｍで反応容器内に導入した。高周波出力を１７５Ｗとして、原料ガスをプラズマ化し反応させて、基板上にアモルファスカーボンを堆積させた。反応容器内の圧力は２０Ｐａであり、反応中の基板温度は２５０℃であった。堆積時間は４０分とした。堆積された薄膜の厚みは２．７０μｍであった。
[Example 1]
Amorphous carbon containing nitrogen was prepared by a cathode coupling type high frequency plasma enhanced chemical vapor deposition (RF-PeCVD) apparatus (13.56 MHz, SAMCO Co., Ltd. Model BP-1). A mixture of acetonitrile and pyridine in a molar ratio of 8: 2 was used as a raw material, and argon gas was used as an additive gas. The mixture was introduced into the reaction vessel at a temperature of 50 ° C., a raw material gas flow rate of 1 sccm, and an argon gas flow rate of 20 sccm. . The high frequency output was set to 175 W, and the raw material gas was converted into plasma and reacted to deposit amorphous carbon on the substrate. The pressure in the reaction vessel was 20 Pa, and the substrate temperature during the reaction was 250 ° C. The deposition time was 40 minutes. The thickness of the deposited thin film was 2.70 μm.
［実施例２〜４］
原料として用いるアセトニトリルとピリジンの混合比を、それぞれモル比で６：４、４：６及び２：８とした以外は実施例１と同じ条件でアモルファスカーボンを堆積させて、実施例２〜４の窒素ドープアモルファスカーボンを調製した。実施例１〜４で得られたアモルファスカーボンのｓｐ２混成結合炭素（ｓｐ２Ｃ）及びｓｐ３混成結合炭素（ｓｐ３Ｃ）の元素比率（％）、ｓｐ２Ｃクラスターサイズ（ｎｍ）、第４級窒素（ｓｐ２ＣＮＣＣ）の元素比率（％）及び反応電子数を表１に示す。
[Examples 2 to 4]
Amorphous carbon was deposited under the same conditions as in Example 1 except that the mixing ratio of acetonitrile and pyridine used as raw materials was 6: 4, 4: 6, and 2: 8 in molar ratios, respectively. Nitrogen doped amorphous carbon was prepared. Element ratio (%) of sp 2 hybrid bond carbon (sp 2 C) and sp 3 hybrid bond carbon (sp 3 C) of the amorphous carbon obtained in Examples 1 to 4, sp 2 C cluster size (nm), first Table 1 shows the element ratio (%) of quaternary nitrogen (sp 2 CNCC) and the number of reaction electrons.
［実施例５〜８］
アセトニトリルとピリジンの混合比をモル比で４：６とし、高周波出力をそれぞれ１５０Ｗ、２００Ｗ、２５０Ｗ及び３００Ｗとした以外は実施例１と同じ条件でアモルファスカーボンを堆積させて、実施例５〜８の窒素ドープアモルファスカーボンを調製した。実施例５〜８で得られたアモルファスカーボンのｓｐ２Ｃ（％）、ｓｐ３Ｃ（％）、ｓｐ２Ｃクラスターサイズ（ｎｍ）、ｓｐ２ＣＮＣＣ（％）及び反応電子数を表２に示す。表３に、実施例５〜８で得られたアモルファスカーボンにおけるＣ、Ｎ、Ｏの元素組成比（原子％）及び前記Ｎ中の第４級Ｎ（ｓｐ２ＣＮＣＣ）の元素組成比（アモルファスカーボンにおける原子％）を示し、表４に、対流ボルタンメトリー試験の結果を示す。また、０〜１１００ｅＶの範囲を、１０ｅＶ／ｍｉｎ（０．１ｅＶ／ｓｔｅｐ）の掃引速度でＸＰＳ測定した結果、３９１〜４０８ｅＶの範囲を、１ｅＶ／ｍｉｎの掃引速度でＸＰＳ測定した結果とピーク分離した結果、及びラマンスペクトルを実施例８で得られたアモルファスカーボンについて、図２〜図４にそれぞれ示す。
[Examples 5 to 8]
Amorphous carbon was deposited under the same conditions as in Example 1 except that the mixing ratio of acetonitrile and pyridine was 4: 6 in molar ratio, and the high frequency output was 150 W, 200 W, 250 W, and 300 W, respectively. Nitrogen doped amorphous carbon was prepared. Table 2 shows sp 2 C (%), sp 3 C (%), sp 2 C cluster size (nm), sp 2 CNCC (%) and the number of reaction electrons of the amorphous carbon obtained in Examples 5 to 8. . Table 3 shows the elemental composition ratio (atomic%) of C, N, and O in the amorphous carbon obtained in Examples 5 to 8 and the elemental composition ratio of quaternary N (sp 2 CNCC) in the N (amorphous carbon). Table 4 shows the results of the convective voltammetry test. In addition, as a result of XPS measurement in the range of 0 to 1100 eV at a sweep speed of 10 eV / min (0.1 eV / step), the range of 391 to 408 eV was peak-separated from the result of XPS measurement at a sweep speed of 1 eV / min. The results and Raman spectrum of the amorphous carbon obtained in Example 8 are shown in FIGS.
［実施例９、１０］
アセトニトリルとピラジンを原料として用い、アセトニトリルとピラジンの混合比をモル比で８：２とし、高周波出力を１７５Ｗとした以外は実施例１と同じ条件でアモルファスカーボンを堆積させて、実施例９の窒素ドープアモルファスカーボンを調製した。また、アセトニトリルとトリアジンを原料として用い、アセトニトリルとトリアジンの混合比をモル比で８：２とし、高周波出力を１５０Ｗとした以外は実施例１と同じ条件でアモルファスカーボンを堆積させて、実施例１０の窒素ドープアモルファスカーボンを調製した。実施例９及び１０で得られたアモルファスカーボンのｓｐ２Ｃ（％）、ｓｐ３Ｃ（％）、ｓｐ２Ｃクラスターサイズ（ｎｍ）、ｓｐ２ＣＮＣＣ（％）及び反応電子数を表５に示す。
[Examples 9 and 10]
Amorphous carbon was deposited under the same conditions as in Example 1 except that acetonitrile and pyrazine were used as raw materials, the mixing ratio of acetonitrile and pyrazine was 8: 2, and the high frequency output was 175 W. Doped amorphous carbon was prepared. Amorphous carbon was deposited under the same conditions as in Example 1 except that acetonitrile and triazine were used as raw materials, the mixing ratio of acetonitrile and triazine was 8: 2 in molar ratio, and the high frequency output was 150 W. Example 10 A nitrogen-doped amorphous carbon was prepared. Table 5 shows sp 2 C (%), sp 3 C (%), sp 2 C cluster size (nm), sp 2 CNCC (%) and the number of reaction electrons of the amorphous carbon obtained in Examples 9 and 10. .
実施例１〜１０で得られたアモルファスカーボンは、いずれも反応電子数が１．５以上であり少なくとも２電子還元反応活性を示し、さらに実施例３、７、８及び９で得られたアモルファスカーボンは、反応電子数が２．０以上であり４電子還元反応活性を示した。また、実施例７で得られたアモルファスカーボンについて、対流ボルタンメトリー測定を１セットを５０回サイクルとして、３セット行った。その結果を図５に示す。対流ボルタンメトリー測定を１５０サイクル行っても酸素還元反応の活性が失われず、電気化学反応に対する安定性を有していた。 All of the amorphous carbons obtained in Examples 1 to 10 have a reaction electron number of 1.5 or more and show at least two-electron reduction reaction activity. Further, the amorphous carbons obtained in Examples 3, 7, 8 and 9 Had a reaction electron number of 2.0 or more and exhibited a 4-electron reduction reaction activity. Moreover, about the amorphous carbon obtained in Example 7, three sets of convective voltammetry measurements were performed with one set as 50 cycles. The result is shown in FIG. Even after 150 cycles of convective voltammetry measurement, the activity of the oxygen reduction reaction was not lost, and it had stability to the electrochemical reaction.
［比較例１］
原料をアセトニトリルとした以外は、実施例１と同じ条件でアモルファスカーボンを堆積させて、比較例１の窒素ドープアモルファスカーボンを調製した。比較例１で得られたアモルファスカーボンについても、実施例と同様にＸＰＳ測定、ラマンスペクトル測定及び対流ボルタンメトリー測定を行い、ｓｐ２Ｃ（％）、ｓｐ３Ｃ（％）、ｓｐ２Ｃクラスターサイズ（ｎｍ）、ｓｐ２ＣＮＣＣ（％）及び反応電子数を求めた。その結果を表６に示す。比較例１で得られたアモルファスカーボンでは、ｓｐ２ＣＮＣＣ結合はみられるものの、極めて少ない反応電子数しか観察されなかった。これは、窒素がｓｐ２Ｃクラスターのエッジ部ではなく、内部の炭素と置換しているため酸素還元反応の反応点となるキノリジニウム構造が形成できなかったためとみられる。
[Comparative Example 1]
Amorphous carbon was deposited under the same conditions as in Example 1 except that the raw material was acetonitrile, to prepare nitrogen-doped amorphous carbon of Comparative Example 1. The amorphous carbon obtained in Comparative Example 1 was subjected to XPS measurement, Raman spectrum measurement, and convective voltammetry measurement in the same manner as in Example, and sp 2 C (%), sp 3 C (%), sp 2 C cluster size ( nm), sp 2 CNCC (%) and the number of reaction electrons. The results are shown in Table 6. In the amorphous carbon obtained in Comparative Example 1, sp 2 CNCC bonds were observed, but only a very small number of reaction electrons were observed. This seems to be because the quinolizinium structure that becomes the reaction point of the oxygen reduction reaction could not be formed because nitrogen was substituted for the carbon inside rather than the edge of the sp 2 C cluster.
図６に、実施例８で得られたアモルファスカーボン、比較例１で得られたアモルファスカーボン、グラッシーカーボン及びプラチナを用いて対流ボルタンメトリー測定を行った結果を示す。実施例８で得られた本発明のアモルファスカーボンは、プラチナとほぼ同様の酸素還元反応活性を有していた。 FIG. 6 shows the results of convective voltammetry measurement using the amorphous carbon obtained in Example 8, the amorphous carbon obtained in Comparative Example 1, the glassy carbon, and platinum. The amorphous carbon of the present invention obtained in Example 8 had almost the same oxygen reduction reaction activity as platinum.
本発明の窒素を含有するアモルファスカーボンの製造方法は、窒素を含有し、酸素還元反応の活性が高く、耐久性の高いアモルファスカーボンを製造することができる。そのため、酸素還元触媒等の触媒として好適に用いることのできるアモルファスカーボンを製造できる。本発明の窒素を含有するアモルファスカーボンは、酸素還元反応の活性が高く、耐久性が高く長期安定性に優れるため、触媒、特に酸素還元反応活性が求められる用途の触媒として好適に用いることができる。特に、固体高分子燃料電池等の燃料電池の電極用の触媒として好適に用いることができる。 The method for producing nitrogen-containing amorphous carbon according to the present invention can produce amorphous carbon containing nitrogen, having high oxygen reduction reaction activity, and high durability. Therefore, amorphous carbon that can be suitably used as a catalyst such as an oxygen reduction catalyst can be produced. The nitrogen-containing amorphous carbon of the present invention has high oxygen reduction reaction activity, high durability, and excellent long-term stability. Therefore, it can be suitably used as a catalyst, particularly a catalyst for applications requiring oxygen reduction reaction activity. . In particular, it can be suitably used as a catalyst for electrodes of fuel cells such as solid polymer fuel cells.
Claims (9)
An electrode comprising the catalyst according to claim 7 or 8.
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| JPS63221840A (en) * | 1987-03-09 | 1988-09-14 | Minolta Camera Co Ltd | Manufacture of amorphous hydrogenated carbon membranes |
| JP2013155406A (en) * | 2012-01-30 | 2013-08-15 | Toyota Central R&D Labs Inc | Amorphous carbon film, method for manufacturing amorphous carbon film, and conductive member provided with amorphous carbon film, and fuel cell separator |
| JP2014201463A (en) * | 2013-04-02 | 2014-10-27 | 旭化成ケミカルズ株式会社 | Nitrogen-containing carbon material and method for producing the same, and electrode for fuel cell |
| WO2015005309A1 (en) * | 2013-07-12 | 2015-01-15 | 昭和電工株式会社 | Oxygen reduction catalyst and use therefor |
| JP2016166102A (en) * | 2015-03-09 | 2016-09-15 | 国立大学法人山口大学 | Production method of amorphous carbon nanoparticle and amorphous carbon nanoparticle |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS63221840A (en) * | 1987-03-09 | 1988-09-14 | Minolta Camera Co Ltd | Manufacture of amorphous hydrogenated carbon membranes |
| JP2013155406A (en) * | 2012-01-30 | 2013-08-15 | Toyota Central R&D Labs Inc | Amorphous carbon film, method for manufacturing amorphous carbon film, and conductive member provided with amorphous carbon film, and fuel cell separator |
| JP2014201463A (en) * | 2013-04-02 | 2014-10-27 | 旭化成ケミカルズ株式会社 | Nitrogen-containing carbon material and method for producing the same, and electrode for fuel cell |
| WO2015005309A1 (en) * | 2013-07-12 | 2015-01-15 | 昭和電工株式会社 | Oxygen reduction catalyst and use therefor |
| JP2016166102A (en) * | 2015-03-09 | 2016-09-15 | 国立大学法人山口大学 | Production method of amorphous carbon nanoparticle and amorphous carbon nanoparticle |
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