JP4962958B2 - 可視光応答型光触媒 - Google Patents
可視光応答型光触媒 Download PDFInfo
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- JP4962958B2 JP4962958B2 JP2007196654A JP2007196654A JP4962958B2 JP 4962958 B2 JP4962958 B2 JP 4962958B2 JP 2007196654 A JP2007196654 A JP 2007196654A JP 2007196654 A JP2007196654 A JP 2007196654A JP 4962958 B2 JP4962958 B2 JP 4962958B2
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- Prior art keywords
- organic semiconductor
- type organic
- group
- photocatalyst
- adsorbent
- 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.)
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- 239000000463 material Substances 0.000 claims description 17
- LKKPNUDVOYAOBB-UHFFFAOYSA-N naphthalocyanine Chemical class N1C(N=C2C3=CC4=CC=CC=C4C=C3C(N=C3C4=CC5=CC=CC=C5C=C4C(=N4)N3)=N2)=C(C=C2C(C=CC=C2)=C2)C2=C1N=C1C2=CC3=CC=CC=C3C=C2C4=N1 LKKPNUDVOYAOBB-UHFFFAOYSA-N 0.000 claims description 13
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 13
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- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 208000008842 sick building syndrome Diseases 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 125000003375 sulfoxide group Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XXWSZMQKQLNDLC-UHFFFAOYSA-N tetraaminoethylene Chemical group NC(N)=C(N)N XXWSZMQKQLNDLC-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Water Treatment By Sorption (AREA)
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Catalysts (AREA)
Description
p型有機半導体としては、大環状の配位子化合物又はその金属錯体が挙げられる。大環状の配位子化合物とは、不対電子を有する原子を環上に含み、金属の配位子となり得る環状化合物の意であり、また、その金属錯体とは、該大環状配位子と金属原子からなる金属化合物の意味である。不対電子を有する原子としては、例えば、窒素原子、酸素原子が挙げられ、窒素原子が好ましい。金属原子としては、周期律表1〜15族の各金属元素が挙げられ、好ましくは4〜14族の金属元素である。また、金属錯体は、例えば、該金属原子と大環状の配位子化合物とが1:1、1:2又は2:1(モル比)からなり、平面4配位の錯体を形成するものであればよい。
で表されるフタロシアニン誘導体が挙げられる。
で表されるナフタロシアニン誘導体が挙げられる。
で表されるポルフィリン誘導体が挙げられる。
また、n型有機半導体としては、多環式芳香族化合物が挙げられる。該多環式芳香族化合物は、一部が飽和していても良い。多環式芳香族化合物とは、少なくとも2個以上の芳香環が縮環した構造を有する化合物、或いは複数の芳香環が不飽和結合(二重結合、三重結合等)を介して結合した構造を有する化合物等を意味する。芳香環としては、ベンゼン環等のほかに、ピロール環、イミダゾール環、ピリジン環、キノキサリン環等の複素芳香環も含まれる(いずれの環も一部が飽和していても良い)。
で表されるペリレン誘導体が挙げられる。
で表されるナフタレン誘導体が挙げられる。
本発明の可視光応答型光触媒で用いる吸着材としては特に限定はなく、例えば、活性炭、活性アルミナ、モレキュラーシーブ、シリカゲル、粘土などの吸着能が高い材料や、イオン交換樹脂、キトサン、ポリプロピレン、有機ゲルなどの薄膜化できる高分子材料等が挙げられる。このうち、被処理物がアミン類やカルボン酸類の吸着には、特にイオン交換樹脂が好適である。被処理物がアミン類の場合には陽イオン交換樹脂が好ましく、具体的には、パーフルオロスルホン酸又はその塩/PTFE(ポリテトラフルオロエチレン)の共重合体(例えばナフィオン(登録商標))や、パーフルオロカルボン酸又はその塩/PTFEの共重合体(例えばフレミオン(登録商標))等が挙げられる。被処理物がカルボン酸類の場合には陰イオン交換樹脂が好ましい。
本発明の可視光応答型光触媒は、p−n接合したp型有機半導体とn型有機半導体のうちのp型有機半導体の表面の全部もしくは一部に吸着材が接触した形態を有しており、かかる接合形態であれば特に限定はない。なお、n型有機半導体及びp型有機半導体は前記したものを用いることができる。
本発明の可視光応答型光触媒は、光照射下、気相又は水相中に含まれる有機物或いは窒素、硫黄又はリンを含む無機物等の分解対象物と接触することにより、分解することができる。
(1)光触媒材料として、n型半導体である3,4,9,10−ペリレンテトラカルボキシル−ビスベンズイミダゾール(以下「PTCBI」と表記する)及びp型半導体である無金属フタロシアニン(以下「H2Pc」と表記する)を用いた。本発明においては、それぞれ昇華精製したものを用いた。
(2)光触媒として用いる三重層フィルムの作製は、市販のNafion膜(Nafion 117, 50 μm厚)に二種類の有機半導体を真空蒸着することにより行った。まず、3つのNafion膜上に、それぞれH2Pcを50nmの厚さで積層して二層フィルムを形成し、次いで、それぞれのH2Pc層上に厚さ50nm、100nm、及び200nmのPTCBI層を有する三層からなる光触媒吸着材複合体(a)、(b)及び(c)を得た。各光触媒吸着材複合体を必要な大きさ(例えば1cm2)に切断した。
(3)実験装置及び方法を図1に示した。円筒状の密閉可能なガラス瓶(容積542 mL)を反応容器とした。気体の漏洩及び混入の無いようにゴム製Oリングでフタを挟み、更にそのOリングにシリコーングリースを塗布した。有機物を容器内に投入するためにガスクロマトグラフィーインジェクション部用セプタムゴムで塞いだ注射針(内径1 mm)をフタに挟んだ。反応容器内に三重層フィルム片1cm2と、理研計器社製アミンセンサー(型番ES−23RV)を静置した。
(4)反応容器内を20.0±0.1oCに保つことにより蒸気圧を制御したトリメチルアミン(N(CH3)3)を0.1mL、上記セプタムゴム部より容器内に注入した。
(5)光触媒反応はハロゲンランプを光源として行った。この時、反応容器内の光触媒表面の照射強度は100 mWcm-2であった。上記ガスセンサーでトリメチルアミン濃度を測定し、その分解量を定量した。
(6)上記(4)の結果、図2の(a)、(b)及び(c)に示すように、投入直後にトリメチルアミンの濃度の増加が起こった。それと平行して(5)の結果、トリメチルアミンのNafion膜への吸着および光触媒膜による分解反応の進行により、トリメチルアミン濃度の減少が観察された。500-700秒後には投入量の10%にまで減少した。
(b) Nafion(50 μm)/H2Pc(50 nm)/PTCBI (100 nm)
(c) Nafion(50 μm)/H2Pc(50 nm)/PTCBI (200 nm)
なお、図2及び図3の(c)は同じサンプルである。
(1)実施例1と同じ実験装置をもちいた。
(2)まず、実施例1のサンプル(a)を用いて、実施例1と同様にトリメチルアミンを投入した。トリメチルアミンの濃度が十分減少した20分後に、実施例1の(4)と全く同様の操作を行った。図4(B)のように再投入直後にトリメチルアミンの濃度の増加が起こった。それと平行して、トリメチルアミンのNafion膜への吸着および有機光触媒膜による分解反応の進行により、トリメチルアミン濃度の減少が観察された。再投入の1800秒後には投入量の10%にまで減少した。この操作を複数回繰り返した。毎回同様の結果が繰り返し観測された。図4(B)を参照。
(3)さらに、この操作を繰り返した結果を図5に示す。これによれば、長期に繰り返しトリメチルアミンを導入してもその蓄積はなく低濃度に維持されていることがわかる。
(1)光触媒吸着材複合体に代えて、Nafion膜(1cm2、厚さ50μm)を試験片としてサンプル(d)を作成し、実施例1と同様の操作を行った。その結果を図2及び3の(d)に示す。
(2)上記(1)で得られたサンプル(d)を用いて、実施例2(1)〜(2)と同様の操作を行った。その結果を図4(C)に示す。トリメチルアミンの再投入直後にトリメチルアミンの濃度の増加が起こった。再投入を繰り返すごとに減少しなくなった。
光触媒吸着材複合体に代えて、ガラス片(1cm2)にPTCBIを200nmの厚さで、次いで、PTCBI上にH2Pcを50nmの厚さで積層してサンプル(e)を作成し、実施例1と同様の操作を行った。その結果を図2の(e)に示す。
た。
比較例3(可視光照射時におけるブランク実験評価1)
光触媒吸着材複合体に代えて、1cm2のガラス片を加え、実施例1と同様の操作を行った。その結果を図2の(f)に示す。
比較例4(可視光照射時におけるブランク実験評価2)
光触媒吸着材複合体を加えずに、実施例1と同様の操作を行った。その結果を図2の(g)に示す。
図2より、Nafionを用いる(a)〜(d)では、トリメチルアミンの減少量は著しく大きくなる。その中でも光触媒吸着材複合体のある(a)〜(c)は減少量が大きく、特にPTCBIの厚い方でトリメチルアミンの減少量が大きいことが確認された。これに対し(e)〜(g)では、トリメチルアミンの減少はほとんど見られない。
光触媒吸着材複合体に代えて、Nafion膜(1cm2)にH2Pcを50nmの厚さで積層してサンプル(h)を作成し、実施例1と同様の操作を行った。その結果を図3の(h)に示す。
光触媒吸着材複合体に代えて、Nafion膜(1cm2)にH2Pcを50nmの厚さで積層した。引き続きH 2 Pcの蒸着されていない裏面にH2Pcを50nmの厚さで積層してサンプル(i)を作成し、実施例1と同様の操作を行った。その結果を図3の(i)に示す。
可視光照射しないこと以外は、実施例2と同様の操作を行った。その結果を図4の(A)に示す。トリメチルアミンの再投入直後にトリメチルアミンの濃度の増加が起こった。再投入を繰り返すごとに減少しなくなった。
Claims (1)
- p型有機半導体とn型有機半導体と吸着材とを含有する可視光応答型光触媒であって、
該吸着材層上に、該p型有機半導体層及び該n型有機半導体層がこの順に積層した三層構造を有し、
該p型有機半導体の表面の全部又は一部に該吸着材が接触し、
該p型有機半導体層の厚さが5〜500nm程度であり、
該p型有機半導体の材料が、フタロシアニン誘導体、ナフタロシアニン誘導体、及びポルフィリン誘導体からなる群から選ばれる少なくとも1種であり、
該n型有機半導体の材料が、フラーレン類、カーボンナノチューブ類、電子供与体をドープした導電性高分子、ペリレン誘導体、及びナフタレン誘導体からなる群から選ばれる少なくとも1種であり、
該吸着材がイオン交換樹脂である
可視光応答型光触媒。
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