JP2003200057A - High efficiency atmospheric nitrogen fixation compounded photocatalytic material composed of visible ray responsible titanium oxide/conductive polymer compounded material - Google Patents
High efficiency atmospheric nitrogen fixation compounded photocatalytic material composed of visible ray responsible titanium oxide/conductive polymer compounded materialInfo
- Publication number
- JP2003200057A JP2003200057A JP2002004161A JP2002004161A JP2003200057A JP 2003200057 A JP2003200057 A JP 2003200057A JP 2002004161 A JP2002004161 A JP 2002004161A JP 2002004161 A JP2002004161 A JP 2002004161A JP 2003200057 A JP2003200057 A JP 2003200057A
- Authority
- JP
- Japan
- Prior art keywords
- ammonium salt
- titanium oxide
- conductive polymer
- nitrogen gas
- ammonia
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000000463 material Substances 0.000 title claims abstract description 42
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 27
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 19
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 title abstract description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 50
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 37
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 24
- 150000001450 anions Chemical class 0.000 claims abstract description 21
- 238000006552 photochemical reaction Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 38
- 239000002131 composite material Substances 0.000 claims description 34
- 239000011941 photocatalyst Substances 0.000 claims description 31
- 230000003100 immobilizing effect Effects 0.000 claims description 15
- 238000005868 electrolysis reaction Methods 0.000 claims description 11
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 4
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 238000013032 photocatalytic reaction Methods 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 18
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 14
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000013078 crystal Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910017464 nitrogen compound Inorganic materials 0.000 description 3
- 150000002830 nitrogen compounds Chemical class 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- HHEFNVCDPLQQTP-UHFFFAOYSA-N ammonium perchlorate Chemical compound [NH4+].[O-]Cl(=O)(=O)=O HHEFNVCDPLQQTP-UHFFFAOYSA-N 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- KBLZDCFTQSIIOH-UHFFFAOYSA-N perchloric acid;tetrabutylazanium Chemical compound OCl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- ZCWKIFAQRXNZCH-UHFFFAOYSA-M tetramethylazanium;perchlorate Chemical compound C[N+](C)(C)C.[O-]Cl(=O)(=O)=O ZCWKIFAQRXNZCH-UHFFFAOYSA-M 0.000 description 1
- -1 was used as an anode Chemical compound 0.000 description 1
Landscapes
- Treatments Of Macromolecular Shaped Articles (AREA)
- Catalysts (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、光活性能を改善し
た水分を含む窒素ガスから光化学反応によりアンモニア
を生成させる光触媒機能を持つ酸化チタンおよび該酸化
チタンの表面に該光化学反応により生成するアンモニア
とアンモニウム塩を形成する陰イオンとを存在させた導
電性ポリマーを形成し光活性的に接触複合化した窒素ガ
スをアンモニウム塩として固定化する複合化光触媒材料
に関する。TECHNICAL FIELD The present invention relates to titanium oxide having a photocatalytic function for producing ammonia by photochemical reaction from nitrogen gas containing water having improved photoactivity and ammonia produced by the photochemical reaction on the surface of the titanium oxide. The present invention relates to a composite photocatalyst material for immobilizing, as an ammonium salt, nitrogen gas that is photoactively contact-complexed by forming a conductive polymer in the presence of an anion that forms an ammonium salt.
【０００２】[0002]
【従来の技術】地球上の人口が爆発的に増大している現
在、生物体内にある１／３の窒素は合成アンモニアから
生産される窒素化合物に支えられている。しかしなが
ら、空中窒素から合成アンモニアを生産するハーバー・
ボッシュ法は高温高圧を必要とするエネルギー消費型の
アンモニア生産プロセスであり、さら、液体窒素と反応
させる水素ガスは石油の分解で得られるものを利用して
いる。従って、石油が枯渇する将来において前記生物体
内で要求される窒素化合物を支えるためには、ハーバー
法などの代替プロセスの開発が急務であり、国際的な課
題となっている。2. Description of the Related Art With the explosive increase in population on earth, 1/3 of the nitrogen in living organisms is supported by nitrogen compounds produced from synthetic ammonia. However, harbors that produce synthetic ammonia from airborne nitrogen
The Bosch method is an energy-consuming ammonia production process that requires high temperature and high pressure, and the hydrogen gas that reacts with liquid nitrogen uses that obtained from the decomposition of petroleum. Therefore, in order to support the nitrogen compounds required in the living body in the future when petroleum is depleted, it is an urgent task to develop an alternative process such as the harbor method, which has become an international issue.
【０００３】しかるに、Ｎ2の結合エネルギーは９４２
ｋＪ／ｍｏｌであり、イオン化ポテンシャルは１５．６
ｅＶ（因みに、Ａｒは１５．８ｅＶ）と窒素ガスから前
記従来技術の問題点をなくした窒素を固定するプロセス
の開発は非常に困難な課題である。このような中で、代
替プロセスとしては、空中窒素を有機金属錯体に固定化
し、ついで化学還元を行ってアンモニアガスを合成する
常温、常圧の方法（Ｇ．Ｌ．Ｌｅｉｇｈ，科学（Ｓｃｉ
ｅｎｃｅ）誌，第２７９巻，５０６−５０７頁，１９９
８年参照）と、酸化チタンに光を照射し、その表面で空
中窒素をアンモニアガスに変換する方法（文献１：Ｉｎ
ｄｉａｎ Ｊｏｕｒｎａｌ ｏｆ Ｃｈｅｍｉｓｔｒｙ、
Ｖｏｌ．３５Ａ、Ｊｕｎｅ １９９６，ｐｐ４４３−４
５３、文献２：Ｇ．Ｎ．Ｓｃｈｒａｕｚｅｒ ａｎｄ
Ｔ．Ｄ．Ｇｕｔｈ，アメリカ化学会（Ｊｏｕｒｎａｌ
ｏｆ ｔｈｅ Ａｍｅｒｉｃａｎ Ｃｈｅｍｉｃａｌ Ｓｏ
ｃｉｅｔｙ）誌，第９９巻２２号，７１８９−７１９３
頁，１９７７年）などが提案されている。However, the binding energy of N 2 is 942.
kJ / mol, with an ionization potential of 15.6
It is a very difficult task to develop a process for fixing nitrogen, which eliminates the problems of the conventional technique from eV (Ar is 15.8 eV) and nitrogen gas. In such a situation, as an alternative process, a method of immobilizing air nitrogen to an organometallic complex and then chemically reducing it to synthesize ammonia gas at room temperature and atmospheric pressure (GL Leigh, Science (Sci.
ence), vol. 279, pp. 506-507, 199.
8 years) and a method of irradiating titanium oxide with light and converting atmospheric nitrogen into ammonia gas on the surface (Reference 1: In
dian Journal of Chemistry,
Vol. 35A, June 1996, pp443-3.
53, Reference 2: G.I. N. Schrauser and
T. D. Guth, American Chemical Society (Journal
of the American Chemical So
city) magazine, Vol. 99, No. 22, 7189-7193.
Page, 1977) and the like have been proposed.
【０００４】また、本発明者らは、光触媒機能を持つ酸
化チタンと窒素ガスから光化学反応により生成するアン
モニアとアンモニウム塩を形成する陰イオンを存在させ
た導電性ポリマーとを光活性的に接触複合化た複合化光
触媒材料を、水分を含む窒素ガス雰囲気と光化学反応可
能に接触する条件下で、該複合化光触媒材料に光照射し
て該窒素ガスを光化学反応によりアンモニアに変換し、
変換されたアンモニアを該陰イオンのアンモニウム塩と
して固定化する光化学反応に使用する複合化光触媒材料
を用いた光化学反応を利用した窒素ガスをアンモニウム
塩として固定化する方法を提案している（特開２００１
−７２９８５、２００１年３月２１日公開）。しかしな
がら、上記提案では窒素固定化効率が非常に低く、より
効率的な複合化光触媒材料が望まれる。The inventors of the present invention also photoactively contact-composite titanium oxide having a photocatalytic function with ammonia produced by a photochemical reaction from nitrogen gas and a conductive polymer containing an anion forming an ammonium salt. The compounded photocatalytic material is converted into ammonia by photoirradiating the compounded photocatalytic material with light by irradiating the compounded photocatalytic material with light under a condition that the compounded photocatalytic material is in contact with a nitrogen gas atmosphere containing water in a photochemically reactable manner,
A method of immobilizing nitrogen gas as an ammonium salt by using a photochemical reaction using a composite photocatalyst material for use in a photochemical reaction of immobilizing the converted ammonia as an ammonium salt of the anion has been proposed (Japanese Patent Application Laid-Open No. 2000-242242). 2001
-72985, published March 21, 2001). However, in the above proposal, the nitrogen fixing efficiency is very low, and a more efficient composite photocatalytic material is desired.
【０００５】[0005]
【発明が解決しようとする課題】本発明の課題は、光活
性能を改善した窒素ガスをアンモニウム塩として固定化
する複合化光触媒材料を提供することにある。前記課題
を解決するために、高光活性の光触媒材料を検討する中
で、チタン金属を酸化する電解電圧の条件およびモノマ
ーを酸化重合する電解電圧条件として特定の条件を選択
することにより、窒素ガスをアンモニウム塩として固定
化する効率的な複合化光触媒材料が得られることを見出
し、前記課題を解決することができた。SUMMARY OF THE INVENTION An object of the present invention is to provide a composite photocatalyst material for immobilizing nitrogen gas having an improved photoactivity as an ammonium salt. In order to solve the above problems, in studying a photocatalytic material having high photoactivity, nitrogen gas is selected by selecting specific conditions as conditions of electrolysis voltage for oxidizing titanium metal and electrolysis voltage conditions for oxidative polymerization of monomers. It has been found that an efficient composite photocatalyst material that is immobilized as an ammonium salt can be obtained, and the above-mentioned problems can be solved.
【０００６】[0006]
【課題を解決するための手段】本発明は、光触媒機能を
持つ酸化チタンと水分を含む窒素ガスから光化学反応に
より生成するアンモニアとアンモニウム塩を形成する陰
イオンを存在させた導電性ポリマーとを光活性的に接触
複合化た複合化光触媒材料を、水分を含む窒素ガス雰囲
気と光化学反応可能に接触する条件下で、該複合化光触
媒材料に光照射して該窒素ガスを光化学反応によりアン
モニアに変換し、変換されたアンモニアを該陰イオンの
アンモニウム塩として固定化する光化学反応に使用する
複合化光触媒材料において、該複合化光触媒材料がチタ
ン金属を０Ｖより大きく１５Ｖ以下の電解電圧において
酸化して生成させた光触媒機能を持つ酸化チタンおよび
該酸化チタンの表面に少なくとも該カチオンおよびアニ
オンからなる塩、および該導電性ポリマーを形成するモ
ノマーが存在する電解液中で７０Ｖ±３０Ｖの定電解電
圧を印加して該モノマーを電解酸化重合して該陰イオン
が存在する導電性ポリマーの層を形成することにより得
られたものであることを特徴とする窒素ガスをアンモニ
ウム塩として固定化する複合化光触媒材料である。SUMMARY OF THE INVENTION The present invention provides a photopolymerization of titanium oxide having a photocatalytic function, ammonia produced by a photochemical reaction from nitrogen gas containing water, and a conductive polymer in the presence of an anion forming an ammonium salt. The composite photocatalyst material, which has been actively contact-composited, is irradiated with light to the nitrogen gas atmosphere containing water so as to allow photochemical reaction, and the nitrogen gas is converted into ammonia by photochemical reaction. In the composite photocatalyst material used in the photochemical reaction of immobilizing the converted ammonia as the ammonium salt of the anion, the composite photocatalyst material is produced by oxidizing titanium metal at an electrolysis voltage of more than 0 V and 15 V or less. Titanium oxide having a photocatalytic function and a salt comprising at least the cation and anion on the surface of the titanium oxide, And applying a constant electrolysis voltage of 70 V ± 30 V in an electrolytic solution in which the monomer forming the conductive polymer is present to electrolytically oxidatively polymerize the monomer to form a layer of the conductive polymer in which the anion is present. A composite photocatalyst material for immobilizing nitrogen gas as an ammonium salt, which is obtained by
【０００７】好ましくは、生成アンモニアとアンモニウ
ム塩を形成する陰イオンの存在する導電性ポリマーの膜
厚が１μｍ±０．５μｍの範囲であることを特徴とする
前記窒素ガスをアンモニウム塩として固定化する複合化
光触媒材料であり、より好ましくは、生成アンモニアと
アンモニウム塩を形成する陰イオンが過塩素酸イオンＣ
ｌＯ4 -であることを特徴とする前記各窒素ガスをアンモ
ニウム塩として固定化する複合化光触媒材料である。前
記アンモニウム塩として固定することにより、窒素ガス
を取り扱いやすい固体燃料もしくは固体窒素化合物とし
て固定化することが可能になった。Preferably, the nitrogen gas is immobilized as an ammonium salt, characterized in that the film thickness of the conductive polymer in the presence of anions forming an ammonium salt with the produced ammonia is in the range of 1 μm ± 0.5 μm. It is a composite photocatalyst material, and more preferably, the anion forming ammonium salt with the produced ammonia is perchlorate ion C.
lO 4 - is a composite photocatalyst material, wherein the immobilizing each nitrogen gas as ammonium salt, which is a. By fixing as the ammonium salt, it became possible to fix nitrogen gas as a solid fuel or solid nitrogen compound that is easy to handle.
【０００８】[0008]
【本発明の実施の態様】本発明をより詳細に説明する。
Ａ．本発明の特徴の第１は、図１から理解されるよう
に、金属チタンを０Ｖより大きく１５Ｖ以下の、特に１
０Ｖ以下の電解電圧下において酸化することにより固定
化効率を格段に改善した酸化チタン膜を見出したことに
ある。図１は、陽極酸化電位を変えて酸化チタン膜を作
製し、その上に定電解電圧の７０Ｖで３−メチルチオフ
ェンを過塩素酸テトラブチルアンモニウム（ＴＢＡＰ）
の存在下で酸化重合して過塩素酸イオンＣｌＯ4 -を内包
したポリ（３−メチルチオフェン）を導電性ポリマーと
する導電性膜を形成して複合化した、窒素ガスをアンモ
ニウム塩として固定化する複合化光触媒材料の窒素固定
効率を測定した結果を示している。上記実験において、
窒素ガス源としては、室温の湿度４０％の空気を用い
た。また、光源としては、１２００ルックスの疑似太陽
光を用いた。生成した塩、ここでは過塩素酸アンモニウ
ムの収量は、得られた針状過塩素酸アンモニウム結晶を
水に溶解し、インドナフトール法を用いて定量測定した
結果から算出した。以下の実験では、特にことわらない
限りこの実験条件で測定した結果を示す。カチオンのテ
トラブチルアンモニウムイオンに代えて、アルカリ金
属、例えばＬｉのイオンを用いても同様の結果が得られ
る。窒素ガス中に水分を存在させることは必須である。
水分量は光化学反応によるアンモニアの生成量に関連
し、化学量論量的には、窒素ガスの３倍モルの水分であ
る。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail. A. The first feature of the present invention is, as can be understood from FIG.
It is the discovery of a titanium oxide film having markedly improved immobilization efficiency by being oxidized under an electrolysis voltage of 0 V or less. FIG. 1 shows a titanium oxide film prepared by changing the anodic oxidation potential, and tetramethylammonium perchlorate (TBAP) on which 3-methylthiophene is added at a constant electrolysis voltage of 70V.
Oxidative polymerization to perchlorate ion ClO in the presence of 4 - immobilization containing poly (3-methylthiophene) forming a conductive film to the conductive polymer complexed, the nitrogen gas as an ammonium salt The result of having measured the nitrogen fixation efficiency of the composite photocatalyst material which shows is shown. In the above experiment,
Air having a room temperature and a humidity of 40% was used as the nitrogen gas source. Also, as the light source, pseudo sunlight of 1200 lux was used. The yield of the produced salt, here ammonium perchlorate, was calculated from the result of quantitative measurement of the obtained needle-like ammonium perchlorate crystal in water and the indonaphthol method. In the following experiments, unless otherwise stated, the results measured under these experimental conditions are shown. Similar results can be obtained by using an alkali metal ion such as Li in place of the cation tetrabutylammonium ion. The presence of water in nitrogen gas is essential.
The amount of water is related to the amount of ammonia produced by the photochemical reaction, and stoichiometrically, the amount of water is 3 times the molar amount of nitrogen gas.
【０００９】Ｂ．本発明の特徴の第２は、導電性ポリマ
ー膜の厚さを１μｍ±０．５μｍにすることにより固定
化の効率が顕著に改善されることを見出したことであ
る。図２は陽極酸化電位５Ｖで作製した酸化チタン膜の
表面に定電解電圧の７０Ｖで３−メチルチオフェンを過
塩素酸テトラブチルアンモニウム（ＴＢＡＰ）の存在下
で酸化重合して過塩素酸イオンＣｌＯ4 -を内包したポリ
（３−メチルチオフェン）を導電性ポリマーとする種々
の膜厚の導電性膜を光触媒機能を持つ酸化チタン層表面
に形成した窒素ガスをアンモニウム塩として固定化する
複合化光触媒材料について、窒素固定効率を測定した結
果を示す。窒素固定効率の最大値は３．６ｍｍｏｌ／ｍ
2であり、その時の窒素固定化速度は２１μｍｏｌｍ-2
ｈ-1である。膜厚の制御は、通電電気量と膜厚は比例す
るから、通電電気量を制御することにより実施し得る。B. The second feature of the present invention is that the immobilization efficiency is remarkably improved by setting the thickness of the conductive polymer film to 1 μm ± 0.5 μm. FIG. 2 shows that 3-methylthiophene was oxidatively polymerized at a constant electrolysis voltage of 70 V in the presence of tetrabutylammonium perchlorate (TBAP) on the surface of a titanium oxide film prepared with an anodic oxidation potential of 5 V to generate perchlorate ion ClO 4 - composite photocatalyst material for immobilizing nitrogen gas formed in the titanium oxide layer surface as the ammonium salt having a photocatalytic function of various thicknesses of the conductive film to encapsulated poly (3-methylthiophene) was the electrically conductive polymer The results of measuring the nitrogen fixation efficiency of the are shown below. The maximum value of nitrogen fixation efficiency is 3.6 mmol / m
2 and the nitrogen fixation rate at that time was 21 μmolm −2
h -1 . The film thickness can be controlled by controlling the amount of electricity supplied, because the amount of electricity supplied is proportional to the amount of electricity supplied.
【００１０】Ｃ．本発明の特徴の第３は、本発明の窒素
ガスをアンモニウム塩として固定化する複合化光触媒材
料は、酸化チタン膜の光吸収特性が紫外光領域の光（４
００ｎｍ以下）を吸収するだけなのに対し、可視光領域
の光により窒素ガスをアンモニウム塩としての固定化す
ることができることである。本発明の窒素固定複合化光
触媒材料が光活性を示す波長特性を調べるために、光フ
ィルターを用いて、疑似太陽光を単色光とし、かつ、各
波長の光量を３０μＷ／ｃｍ2とし、露光時間５日での
過塩素酸アンモニウム収量を測定した。本発明の複合化
光触媒材料を用いると、図３に示される結果から、可視
光により窒素ガスをアンモニウム塩として固定できるこ
とが理解され、太陽光の利用率が高いことが判る。C. The third feature of the present invention is that the composite photocatalyst material of the present invention for immobilizing nitrogen gas as an ammonium salt has a light absorption property of the titanium oxide film in the ultraviolet region (4
It is possible to immobilize nitrogen gas as an ammonium salt by the light in the visible light region, while only absorbing (00 nm or less). In order to investigate the wavelength characteristic in which the nitrogen-fixing composite photocatalyst material of the present invention exhibits photoactivity, pseudo-sunlight is converted into monochromatic light with an optical filter, and the light amount of each wavelength is set to 30 μW / cm 2 , and the exposure time is set. The ammonium perchlorate yield at 5 days was measured. When the composite photocatalyst material of the present invention is used, it is understood from the results shown in FIG. 3 that nitrogen gas can be fixed as an ammonium salt by visible light, and the utilization rate of sunlight is high.
【００１１】Ｄ．本発明の導電性ポリマー層を形成する
際に電解液中に添加して、電解中にアンモニアをアンモ
ニウム塩として固定する陰イオンを該ポリマー層中に封
入できる該陰イオンを含む電解質としては、本発明者ら
が提案した、前記先願の発明（特開２００１−７２９８
５、２００１年３月２１日公開）で使用したものを利用
できる。
Ｅ．図４は、本発明の窒素ガスを光化学反応にによりア
ンモニウム塩として固定する原理を示すものである。D. The electrolyte containing the anion that can be added to the electrolytic solution when forming the conductive polymer layer of the present invention and encapsulate the anion that fixes ammonia as an ammonium salt during electrolysis in the polymer layer is The invention of the previous application proposed by the inventors (Japanese Patent Application Laid-Open No. 2001-7298)
5, published on March 21, 2001). E. FIG. 4 shows the principle of fixing nitrogen gas of the present invention as an ammonium salt by a photochemical reaction.
【００１２】[0012]
【実施例】ここでは、更に具体的な例を実施例として示
すが、これは本発明をより理解し易くするためのもので
あり、本発明を限定するものではない。EXAMPLES Here, more specific examples will be shown as examples, but this is for the purpose of making the present invention more easily understandable, and does not limit the present invention.
【００１３】実施例１
脱脂、フツ酸による酸化物除去を行ったチタン板を陽極
とし、過塩素酸テトラブチルアンモニウムを０．１モル
溶解したジクロロメタン電解液中で白金板を陰極とし
て、白金板に対して＋５Ｖの電解電圧をかけて酸化し
て、チタン板上に酸化チタン薄膜を形成した。Example 1 A titanium plate, which had been degreased and whose oxide had been removed with hydrofluoric acid, was used as an anode, and a platinum plate was used as a cathode in a dichloromethane electrolyte solution in which 0.1 mol of tetrabutylammonium perchlorate was dissolved. On the other hand, an electrolytic voltage of +5 V was applied for oxidation to form a titanium oxide thin film on the titanium plate.
【００１４】前記酸化チタン薄膜を陽極とし、過塩素酸
テトラブチルアンモニウムを０．１モルと３−メチルチ
オフェンを０．０８モルを溶解したジクロロメタン溶液
を電解液とし、白金板を陰極として白金板に対して＋７
０Ｖの定電解電圧をかけて３−メチルチオフェンを酸化
重合し前記酸化チタン薄膜上に過塩素酸イオンＣｌＯ 4 -
を封入したポリ（３−メチルチオフェン）膜を形成し
た。この時の通電電気量は２００ミリクーロン／ｃｍ2
（ｍＣ／ｃｍ2）とした。Using the titanium oxide thin film as an anode, perchloric acid
Tetrabutylammonium 0.1 mol and 3-methylthio
Dichloromethane solution containing 0.08 mol of offene
+7 against the platinum plate with the platinum plate as the cathode
Oxidize 3-methylthiophene by applying a constant electrolysis voltage of 0V
Polymerized to form a perchlorate ion ClO on the titanium oxide thin film. Four -
To form a poly (3-methylthiophene) film encapsulating
It was The amount of electricity supplied at this time is 200 millicoulombs / cm.2
(MC / cm2).
【００１５】酸化チタン膜／過塩素酸イオンを内包する
ポリ（３−メチルチオフェン）膜からなる複合化光触媒
材料が光化学的に窒素ガスを過塩素酸アンモニウム塩と
して固定化する効果を以下の方法により確認した。
（１） 前記作製した複合化光触媒材料を、外部から光
照射可能で、窒素ガスの水分を制御できるシールドボッ
クス装置内に配置し、該シールドボックス内の相対湿度
を４０％に制御し、該水分を含む窒素ガスと該複合化光
触媒材料とを光化学反応可能に接触させ、外部から１２
００ルックスの疑似太陽光を照射した。
（２） 一定時間露光後、前記複合化光触媒材料上に過
塩素酸アンモニウム針状結晶が形成された。該針状結晶
を水に溶解し、前記インドナフトール法で前記過塩素酸
アンモニウムの収量を測定した。The effect of the composite photocatalyst material comprising a titanium oxide film / a poly (3-methylthiophene) film encapsulating perchlorate ions to photochemically immobilize nitrogen gas as ammonium perchlorate salt by the following method. confirmed. (1) The composite photocatalyst material prepared above is placed in a shield box device that can be irradiated with light from the outside and can control the moisture content of nitrogen gas, and the relative humidity in the shield box is controlled to 40% to obtain the moisture content. The nitrogen gas containing nitrogen and the composite photocatalyst material are brought into contact with each other so as to allow photochemical reaction, and
It was irradiated with pseudo sunlight of 00 lux. (2) After exposure for a certain period of time, needle crystals of ammonium perchlorate were formed on the composite photocatalyst material. The needle crystals were dissolved in water, and the yield of the ammonium perchlorate was measured by the indonaphthol method.
【００１６】一週間照射後の過塩素酸アンモニウム生成
量の測定結果を、酸化チタン形成の陽極酸化電位と過塩
素酸アンモニウム針状結晶の収量の関係を示す図１中に
示す。この図１から、１５Ｖ以下、特に１０Ｖ以下で作
製した酸化チタンを用いた場合に窒素固定反応の活性が
高いことが判る。陽極酸化電位を低くして作製した酸化
チタンほど酸素欠陥（化学量論量に対して酸素原子が欠
損している部位）が多く観察されることから、その部位
が窒素固定反応の活性を高めているものと推測される。The results of measuring the amount of ammonium perchlorate produced after irradiation for one week are shown in FIG. 1, which shows the relationship between the anodic oxidation potential of titanium oxide formation and the yield of ammonium perchlorate needle crystals. From this FIG. 1, it can be seen that the activity of the nitrogen fixing reaction is high when titanium oxide produced at 15 V or less, particularly 10 V or less is used. Titanium oxide produced with a lower anodizing potential has more oxygen defects (sites where oxygen atoms are deficient with respect to the stoichiometric amount), so these sites should enhance the activity of the nitrogen fixation reaction. Presumed to be present.
【００１７】通電量を変えて作製した、換言すれば、膜
厚を変えて作成した複合化光触媒材料の、膜厚と過塩素
酸アンモニウム針状結晶の収量の関係を図２に示す。図
２の膜厚と収量の関係において、特定の膜厚において収
率のピークが存在することが判る。これは、薄すぎると
光活性に機能する空乏層の形成が充分でなく、厚すぎる
と空乏層まで光が到達しないことによるものと推測され
る。膜厚１μｍにおいて最大の過塩素酸アンモニウム針
状結晶の収量が達成でき、その時の窒素固定化速度は２
１μｍｏｌ・ｍ-2・ｈ-1であった。FIG. 2 shows the relationship between the film thickness and the yield of acicular ammonium perchlorate crystals of the composite photocatalyst material prepared by changing the amount of electricity applied, in other words, by changing the film thickness. From the relationship between the film thickness and the yield in FIG. 2, it can be seen that there is a yield peak at a specific film thickness. It is presumed that this is because when the thickness is too thin, the formation of the depletion layer that functions photoactively is not sufficient, and when it is too thick, the light does not reach the depletion layer. The maximum yield of needle crystals of ammonium perchlorate can be achieved at a film thickness of 1 μm, and the nitrogen immobilization rate at that time is 2
It was 1 μmol · m −2 · h −1 .
【００１８】実施例２
実施例１のＴＢＡＰに代えて過塩素酸リチウムを用いて
実施した場合においても、ほぼ同様の結果が得られた。Example 2 Almost the same result was obtained when lithium perchlorate was used instead of TBAP in Example 1.
【００１９】[0019]
【発明の効果】以上述べたように、本発明で確立した窒
素ガスをアンモニウム塩として固定化する複合化光触媒
材料を作成する方法を採用することにより、可視光応答
性、固定化効率を顕著に向上させた、常温常圧において
窒素ガスをアンモニウム塩として固定化できる複合化光
触媒材料を提供することができた、という優れた作用・
効果がもたらされた。As described above, by adopting the method for producing a composite photocatalyst material for immobilizing nitrogen gas as an ammonium salt, which is established in the present invention, visible light responsiveness and immobilization efficiency are remarkably improved. The excellent action of being able to provide an improved composite photocatalyst material capable of immobilizing nitrogen gas as an ammonium salt at normal temperature and pressure.
The effect was brought.
【図１】 酸化チタン形成の陽極酸化電位と過塩素酸ア
ンモニウム針状結晶の収量の相関FIG. 1 Correlation between the anodic oxidation potential of titanium oxide formation and the yield of needle crystals of ammonium perchlorate.
【図２】 窒素ガスから光化学反応により生成するアン
モニアとアンモニウム塩を形成する陰イオンを存在させ
た導電性ポリマーの膜厚と過塩素酸アンモニウム針状結
晶の収量の相関FIG. 2 Correlation between film thickness of conductive polymer in the presence of anion forming ammonium salt and ammonia formed by photochemical reaction from nitrogen gas and yield of ammonium perchlorate needle crystals.
【図３】 本発明の窒素ガスをアンモニウム塩として固
定化する複合化光触媒材料の波長特性FIG. 3 is a wavelength characteristic of a composite photocatalyst material of the present invention in which nitrogen gas is immobilized as an ammonium salt.
【図４】 本発明の窒素ガスをアンモニウム塩として固
定化する複合化光触媒材料による光窒素固定の原理FIG. 4 Principle of photonitrogen fixation by a composite photocatalyst material of the present invention in which nitrogen gas is immobilized as ammonium salt.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4G069 AA03 BA04A BA04B BA17 BA18 BA22A BA22B BA36A BA48A BB01A BB01B BD02A BD02B BD12A BD12B BE21A BE21B CB81 EA11 EB15X EB15Y ─────────────────────────────────────────────────── ─── Continued front page F-term (reference) 4G069 AA03 BA04A BA04B BA17 BA18 BA22A BA22B BA36A BA48A BB01A BB01B BD02A BD02B BD12A BD12B BE21A BE21B CB81 EA11 EB15X EB15Y
Claims (3)
む窒素ガスから光化学反応により生成するアンモニアと
アンモニウム塩を形成する陰イオンを存在させた導電性
ポリマーとを光活性的に接触複合化した複合化光触媒材
料を、水分を含む窒素ガス雰囲気と光化学反応可能に接
触する条件下で、該複合化光触媒材料に光照射して該窒
素ガスを光化学反応によりアンモニアに変換し、変換さ
れたアンモニアを該陰イオンのアンモニウム塩として固
定化する光化学反応に使用する複合化光触媒材料におい
て、該複合化光触媒材料がチタン金属を０Ｖより大きく
１５Ｖ以下の電解電圧において酸化して生成させた光触
媒機能を持つ酸化チタンおよび該酸化チタンの表面に少
なくとも該陰イオン、および該導電性ポリマーを形成す
るモノマーが存在する電解液中で７０Ｖ±３０Ｖの定電
解電圧を印加して該モノマーを電解酸化重合して該陰イ
オンが存在する導電性ポリマーの層を形成することによ
り得られたものであることを特徴とする窒素ガスをアン
モニウム塩として固定化する複合化光触媒材料。1. A composite obtained by photoactively contact-compositing titanium oxide having a photocatalytic function, ammonia produced by a photochemical reaction from nitrogen gas containing water, and a conductive polymer in which an anion forming an ammonium salt is present. The composite photocatalyst material is irradiated with light under a condition of contacting with a nitrogen gas atmosphere containing water so as to allow photochemical reaction to convert the nitrogen gas into ammonia by a photochemical reaction, and the converted ammonia is converted into ammonia. A composite photocatalyst material for use in a photochemical reaction that is immobilized as an ammonium salt of an anion, wherein the composite photocatalyst material is a titanium oxide having a photocatalytic function produced by oxidizing titanium metal at an electrolysis voltage of more than 0 V and 15 V or less. And at least the anion and the monomer forming the conductive polymer are present on the surface of the titanium oxide. And a constant electrolysis voltage of 70 V ± 30 V in an electrolytic solution to electrolytically oxidatively polymerize the monomer to form a layer of a conductive polymer in which the anion is present. A composite photocatalyst material for immobilizing nitrogen gas as an ammonium salt.
する陰イオンが存在する導電性ポリマーの層の膜厚が１
μｍ±０．５μｍの範囲であることを特徴とする請求項
１に記載の窒素ガスをアンモニウム塩として固定化する
複合化光触媒材料。2. The film thickness of the conductive polymer layer in which anions that form ammonium salts with the produced ammonia are present is 1.
The composite photocatalyst material for immobilizing nitrogen gas as an ammonium salt according to claim 1, wherein the composite photocatalyst material has a range of μm ± 0.5 μm.
する陰イオンが過塩素酸イオンＣｌＯ4 -であることを特
徴とする請求項１または２に記載の窒素ガスをアンモニ
ウム塩として固定化する複合化光触媒材料。3. The composite photocatalyst for immobilizing nitrogen gas as an ammonium salt according to claim 1, wherein the anion forming the ammonium salt with the produced ammonia is a perchlorate ion ClO 4 −. material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002004161A JP4098527B2 (en) | 2002-01-11 | 2002-01-11 | Highly efficient air-nitrogen-fixed composite photocatalyst material composed of titanium oxide / conductive polymer composite with visible light response |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002004161A JP4098527B2 (en) | 2002-01-11 | 2002-01-11 | Highly efficient air-nitrogen-fixed composite photocatalyst material composed of titanium oxide / conductive polymer composite with visible light response |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003200057A true JP2003200057A (en) | 2003-07-15 |
| JP4098527B2 JP4098527B2 (en) | 2008-06-11 |
Family
ID=27643563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002004161A Expired - Fee Related JP4098527B2 (en) | 2002-01-11 | 2002-01-11 | Highly efficient air-nitrogen-fixed composite photocatalyst material composed of titanium oxide / conductive polymer composite with visible light response |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4098527B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006021112A (en) * | 2004-07-07 | 2006-01-26 | Kyoto Univ | Ultraviolet and visible ray responsive titania based photocatalyst |
| WO2007097220A1 (en) * | 2006-02-21 | 2007-08-30 | Kyoto University | Visible light-responsive photocatalyst |
| WO2008108016A1 (en) * | 2007-03-08 | 2008-09-12 | National University Corporation Chiba University | Nitrogen-fixing material, process for producing the same, and method of fixing nitrogen |
| WO2012011324A1 (en) * | 2010-07-21 | 2012-01-26 | 日立造船株式会社 | Method for synthesizing ammonia |
| JP2012055786A (en) * | 2010-09-03 | 2012-03-22 | Chiba Univ | Nitrogen fixation material and nitrogen fixation method using the same |
| JP2014151291A (en) * | 2013-02-12 | 2014-08-25 | Denso Corp | Ammonia-producing catalyst |
| US9592495B2 (en) | 2013-12-24 | 2017-03-14 | Denso Corporation | Ammonia synthesis catalyst |
| CN114749115A (en) * | 2022-03-24 | 2022-07-15 | 福州大学 | Gas-phase photocatalytic nitrogen fixation reaction method |
| CN114849726A (en) * | 2022-06-23 | 2022-08-05 | 杭州师范大学 | Iron-tungsten oxide photocatalyst with rich oxygen vacancies, preparation and nitrogen fixation application |
-
2002
- 2002-01-11 JP JP2002004161A patent/JP4098527B2/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006021112A (en) * | 2004-07-07 | 2006-01-26 | Kyoto Univ | Ultraviolet and visible ray responsive titania based photocatalyst |
| US7153808B2 (en) | 2004-07-07 | 2006-12-26 | Kyoto University | Ultraviolet and visible-light-sensitive titania-based photocatalyst |
| JP4576526B2 (en) * | 2004-07-07 | 2010-11-10 | 国立大学法人京都大学 | Ultraviolet and visible light responsive titania photocatalyst |
| WO2007097220A1 (en) * | 2006-02-21 | 2007-08-30 | Kyoto University | Visible light-responsive photocatalyst |
| WO2008108016A1 (en) * | 2007-03-08 | 2008-09-12 | National University Corporation Chiba University | Nitrogen-fixing material, process for producing the same, and method of fixing nitrogen |
| JP2008221037A (en) * | 2007-03-08 | 2008-09-25 | Chiba Univ | Nitrogen-fixing material, manufacturing method thereof, and nitrogen-fixing method |
| CN103108994B (en) * | 2010-07-21 | 2016-01-20 | 日立造船株式会社 | The synthetic method of ammonia |
| JP2012025985A (en) * | 2010-07-21 | 2012-02-09 | Hitachi Zosen Corp | Method for synthesizing ammonia |
| CN103108994A (en) * | 2010-07-21 | 2013-05-15 | 日立造船株式会社 | Method for synthesizing ammonia |
| US8801915B2 (en) | 2010-07-21 | 2014-08-12 | Hitachi Zosen Corporation | Method for synthesizing ammonia |
| WO2012011324A1 (en) * | 2010-07-21 | 2012-01-26 | 日立造船株式会社 | Method for synthesizing ammonia |
| JP2012055786A (en) * | 2010-09-03 | 2012-03-22 | Chiba Univ | Nitrogen fixation material and nitrogen fixation method using the same |
| JP2014151291A (en) * | 2013-02-12 | 2014-08-25 | Denso Corp | Ammonia-producing catalyst |
| US9592495B2 (en) | 2013-12-24 | 2017-03-14 | Denso Corporation | Ammonia synthesis catalyst |
| CN114749115A (en) * | 2022-03-24 | 2022-07-15 | 福州大学 | Gas-phase photocatalytic nitrogen fixation reaction method |
| CN114849726A (en) * | 2022-06-23 | 2022-08-05 | 杭州师范大学 | Iron-tungsten oxide photocatalyst with rich oxygen vacancies, preparation and nitrogen fixation application |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4098527B2 (en) | 2008-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Velichenko et al. | Electrodeposition of lead dioxide from methanesulfonate solutions | |
| Zhang et al. | Eiectrogenerated Chemiluminescent Emission from an Organized (LB) Monolayer of a Ru (bpy) t+-Based Surfactant on Semiconductor and Metal Electrodes | |
| Melendres et al. | On the composition of the passive film on nickel: a surface-enhanced Raman spectroelectrochemical study | |
| JP2003200057A (en) | High efficiency atmospheric nitrogen fixation compounded photocatalytic material composed of visible ray responsible titanium oxide/conductive polymer compounded material | |
| Ferro et al. | Physicochemical properties of fluorinated diamond electrodes | |
| Suhadolnik et al. | Influence of anodization-electrolyte aging on the photocatalytic activity of TiO2 nanotube arrays | |
| Andrieux et al. | Catalysis of electrochemical reactions at derivatized electrodes: Kinetic model for stationary voltammetric techniques and preparative scale electrolysis | |
| Kim et al. | Direct and indirect effects in pulse irradiated concentrated aqueous solutions of chloride and sulfate ions | |
| Erwin et al. | The crystallization and dissolution of sodium urate | |
| Sandifer | Theory of interfacial potential differences: effects of adsorption onto hydrated (gel) and nonhydrated surfaces | |
| Tasaka et al. | Anodic oxidation mechanism of hypochlorite ion on platinum electrode in alkaline solution | |
| Sobkowski et al. | The influence of halide ions on methanol adsorption and oxidation on a platinized electrode | |
| Sato et al. | Anodic oxide on silver in alkaline solution | |
| JPS6256588A (en) | Method for decomposing water by visible radiation | |
| Kolthoff et al. | Halide films at the convection mercury electrode | |
| Ivanov et al. | Octadecylamine-based Langmuir-Blodgett films containing iron and copper hexacyanoferrates | |
| Weber et al. | The Radiation Decolorization of Dilute Dye Solutions; Chlor Phenol Red1, 2 | |
| JPS6236008A (en) | Polytungstic acid having peroxo structure and method for synthesizing said acid | |
| Miyoshi et al. | Photochemical property and surface characterization of silver-loaded zirconium phosphate | |
| Ogawa et al. | Characterization and material conditions of conducting polymer/titanium oxide hybrid systems used for dinitrogen fixation under ordinary pressure and temperature | |
| Harada et al. | Study of photocatalytic reaction of TiO2 using TiO2/Au mosaic electrode arrays | |
| Lu et al. | Room temperature electrodeposition of Ag3PO4 films | |
| Endo et al. | Hydrogenation of CO2 on the cathodized tungsten trioxide/polyaniline/polyvinylsulfate-modified electrode in aqueous solution | |
| RU2695352C1 (en) | Method of producing nanosized calcium particles in an aqueous medium | |
| Dorain | The observation with surface-enhanced Raman scattering of the sequential electrochemical formation of adsorbed oxide, hydroxide, and water on a silver electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20031031 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20040123 |
|
| RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20040129 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20060706 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20060801 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060920 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20080304 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20080313 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110321 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120321 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130321 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130321 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140321 Year of fee payment: 6 |
|
| LAPS | Cancellation because of no payment of annual fees |