JP2005213123A - 炭素ドープ酸化チタンとその製造法、光触媒、及び該触媒を用いた有機化合物の酸化方法 - Google Patents
炭素ドープ酸化チタンとその製造法、光触媒、及び該触媒を用いた有機化合物の酸化方法 Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 132
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 24
- 150000002894 organic compounds Chemical class 0.000 title claims abstract description 22
- 230000001590 oxidative effect Effects 0.000 title claims description 8
- 239000003054 catalyst Substances 0.000 title description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 12
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000002978 peroxides Chemical class 0.000 claims abstract description 11
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- 238000010304 firing Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- -1 carbon ion Chemical class 0.000 abstract description 8
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- XQAXGZLFSSPBMK-UHFFFAOYSA-M [7-(dimethylamino)phenothiazin-3-ylidene]-dimethylazanium;chloride;trihydrate Chemical compound O.O.O.[Cl-].C1=CC(=[N+](C)C)C=C2SC3=CC(N(C)C)=CC=C3N=C21 XQAXGZLFSSPBMK-UHFFFAOYSA-M 0.000 description 6
- 125000005842 heteroatom Chemical group 0.000 description 6
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
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- 150000001491 aromatic compounds Chemical class 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
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- 239000000758 substrate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
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Images
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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
【解決手段】 本発明の炭素ドープ酸化チタンは、酸化チタンに炭素原子がドープされている。前記炭素原子は炭酸イオンとしてドープされていていることが好ましい。本発明の炭素ドープ酸化チタンは、酸素原子を有するチタン化合物と炭素源との混合物を焼成処理することにより製造できる。本発明の有機化合物の酸化方法は、酸化チタンに炭素原子がドープされた炭素ドープ酸化チタンからなる光触媒の存在下、被酸化部位を有する有機化合物を光照射下に分子状酸素又は過酸化物により酸化することを特徴とする。
【選択図】 なし
Description
本発明の他の目的は、有機化合物を光照射下で効率よく酸化する方法を提供することにある。
で表される単位を有している。X,Y,Zにおけるヘテロ原子としては、窒素原子、酸素原子、硫黄原子などが挙げられる。
チオウレア5.2gとチタンテトライソプロポキシド4.8gを500mlのエタノールに加え、十分に撹拌して得た混合液を、白色スラリー状になるまで減圧下で濃縮した。濃縮物を室温で36時間風乾することにより白色の粉末を得た。得られた粉末を素焼きの蓋付き容器に入れ、蓋を封じた状態の容器を、電気炉で400〜700℃の温度で加熱することにより焼成処理を行った。この条件では、容器内へ混入する酸素の量が制限されるため、貧酸素存在下で焼成が行われている。得られた焼成物をイオン交換水で十分に洗浄することにより黄色の炭素ドープ酸化チタン触媒を粉末で得た。
得られた炭素ドープ酸化チタン触媒のXPS(X-rey Photoemission Spectroscopy)による炭素1s殻のスペクトルを測定した。その結果を図1に示す。図1中、ドーピングされた炭素原子に起因するピークを矢印で示す。
アナターゼ型二酸化チタン粉末[商品名「ST−01」、アナターゼ型含量100%、石原産業(株)製、平均粒子径7nm、比表面積236m2/g]3gとチオウレア11gを乳鉢に入れ、十分に混合して得られた混合物を素焼きの蓋付き容器に入れ、蓋を封じた状態の容器を、電気炉で400〜700℃の温度で加熱することにより焼成処理を行った。この条件では、容器内へ混入する酸素の量が制限されるため、貧酸素存在下で焼成が行われている。得られた焼成物をイオン交換水で十分に洗浄することにより黄色の炭素ドープ酸化チタン触媒を粉末で得た。
得られた炭素ドープ酸化チタン触媒の結晶相のスペクトルを測定した。その結果を図2における「Cドープ」に示す。
さらに、アナターゼ型二酸化チタン粉末(商品名「ST−01」)のスペクトルを測定した。その結果を図2における「ST−01」に示す。
実施例1において、混合物を入れた容器の蓋をあけた状態で焼成処理を行った点以外は、実施例1と同様の操作を行って窒素ドープ酸化チタン触媒を粉末で得た。なお、この条件では、容器内へ酸素が十分に供給された状態で焼成処理が行われている。
得られた酸化チタン触媒の結晶相のスペクトルを測定した。その結果を図2における「Nドープ」に示す。
チオウレア10gとチタンテトライソプロポキシド15gを500mlのエタノールに加え、十分に撹拌して得た混合液を、白色スラリー状になるまで減圧下で濃縮した。濃縮物を室温で36時間風乾することにより粉末を得た。得られた粉末を素焼きの蓋付き容器に入れ、容器の蓋をあけた状態で、電気炉で500〜700℃の温度で加熱することにより焼成処理を行った。なお、この条件では、容器内へ酸素が十分に供給された状態で焼成処理が行われている。得られた焼成物をイオン交換水で十分に洗浄することにより黄色の硫黄ドープ酸化チタン触媒を粉末で得た。
得られた酸化チタン触媒の結晶相のスペクトルを測定した。その結果を図2における「Sドープ」に示す。
メチレンブルーの分解性能(酸化的分解)
実施例1で得た炭素ドープ酸化チタン触媒、比較例2で得た硫黄ドープ酸化チタン触媒、及びアナターゼ型二酸化チタン粉末[商品名「ST−01」、アナターゼ型含量100%、石原産業(株)製、平均粒子径7nm、比表面積236m2/g]について、各酸化チタン触媒100mgを、0.05mMのメチレンブルー溶液(pH=3)50mlに加え、超音波照射により分散させ、得られた分散液を遮光して吸着平衡に達するまで半日程度磁気撹拌した。この母液から3gをサンプリングして試験管に移し、サンプルが空気と接触する状態(試験管を開放した状態)で、Xeランプ(500W)を光源に用い、UVカットフィルタ[東芝社製の色ガラスフィルター(商品名「UV−35」、「L−40」、「Y−44」、「Y−52」)]により照射波長を制限して各サンプルごとに10分間光照射した。
得られた懸濁液を遠心分離し、酸化チタン触媒を分離した後の液体について、メチレンブルーの残量をXPSスペクトル測定装置(吸収波長664nm)で測定した。得られた測定値より単位時間当たりのメチレンブルー量[mM/min]を算出し、メチレンブルーの分解性能を評価した。その結果を図3に示す。
Claims (5)
- 酸化チタンに炭素原子がドープされた炭素ドープ酸化チタン。
- 炭素原子が炭酸イオンとしてドープされている請求項1記載の炭素ドープ酸化チタン。
- 酸素原子を有するチタン化合物と炭素源との混合物を焼成処理することにより、酸化チタンに炭素原子がドープされた炭素ドープ酸化チタンを得ることを特徴とする炭素ドープ酸化チタンの製造法。
- 酸化チタンに炭素原子がドープされた炭素ドープ酸化チタンからなる光触媒。
- 請求項4記載の光触媒の存在下、被酸化部位を有する有機化合物を光照射下に分子状酸素又は過酸化物により酸化することを特徴とする有機化合物の酸化方法。
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