JP4421219B2 - Sulfur-containing metal oxide - Google Patents
Sulfur-containing metal oxide Download PDFInfo
- Publication number
- JP4421219B2 JP4421219B2 JP2003143980A JP2003143980A JP4421219B2 JP 4421219 B2 JP4421219 B2 JP 4421219B2 JP 2003143980 A JP2003143980 A JP 2003143980A JP 2003143980 A JP2003143980 A JP 2003143980A JP 4421219 B2 JP4421219 B2 JP 4421219B2
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- Prior art keywords
- sulfur
- metal oxide
- titanium
- containing metal
- atom
- 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.)
- Expired - Lifetime
Links
- 229910052717 sulfur Inorganic materials 0.000 title claims description 140
- 239000011593 sulfur Substances 0.000 title claims description 119
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 113
- 229910044991 metal oxide Inorganic materials 0.000 title claims description 57
- 150000004706 metal oxides Chemical class 0.000 title claims description 54
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 70
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 45
- 238000010304 firing Methods 0.000 claims description 36
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 33
- 125000004434 sulfur atom Chemical group 0.000 claims description 33
- 229910052719 titanium Inorganic materials 0.000 claims description 32
- 239000010936 titanium Substances 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 28
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- -1 alicyclic hydrocarbon Chemical class 0.000 claims description 16
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 16
- 238000007539 photo-oxidation reaction Methods 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 13
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 12
- 150000004703 alkoxides Chemical class 0.000 claims description 12
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 12
- 229910052726 zirconium Inorganic materials 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 229910052715 tantalum Inorganic materials 0.000 claims description 11
- 125000002015 acyclic group Chemical group 0.000 claims description 7
- 125000004429 atom Chemical group 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- VULAXXNFNMUCIP-UHFFFAOYSA-M [NH4+].[O-]S(=O)(=O)O[Ti] Chemical compound [NH4+].[O-]S(=O)(=O)O[Ti] VULAXXNFNMUCIP-UHFFFAOYSA-M 0.000 claims description 2
- 230000002950 deficient Effects 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000000843 powder Substances 0.000 description 46
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 17
- 239000004408 titanium dioxide Substances 0.000 description 16
- 238000000862 absorption spectrum Methods 0.000 description 15
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 14
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 13
- 150000003585 thioureas Chemical class 0.000 description 13
- 229910001936 tantalum oxide Inorganic materials 0.000 description 12
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 11
- 229960000907 methylthioninium chloride Drugs 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 9
- 229910001928 zirconium oxide Inorganic materials 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 229910002367 SrTiO Inorganic materials 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000003463 sulfur Chemical class 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 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 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N Oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- VLLNJDMHDJRNFK-UHFFFAOYSA-N adamantan-1-ol Chemical compound C1C(C2)CC3CC2CC1(O)C3 VLLNJDMHDJRNFK-UHFFFAOYSA-N 0.000 description 1
- IYKFYARMMIESOX-SPJNRGJMSA-N adamantanone Chemical compound C([C@H](C1)C2)[C@H]3C[C@@H]1C(=O)[C@@H]2C3 IYKFYARMMIESOX-SPJNRGJMSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002831 nitrogen free-radicals Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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
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- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、光酸化触媒として有用な新規な含硫黄金属酸化物およびその製造方法、並びに該含硫黄金属酸化物を用いて有機化合物を酸化して酸化誘導体を製造する方法に関する。
【０００２】
【従来の技術】
二酸化チタンは光酸化触媒として良く知られているが、従来、その活性は紫外線領域でのみ発現するものであった。近年、可視光領域でその活性を発現させようとする試みが多くなされている。その代表的手法としては、金属イオンを高エネルギービームによって導入した二酸化チタン（特許文献１参照。）、金属イオンを含む層状チタン酸化合物（特許文献２参照。）及び金属または金属化合物のクラスターを分散させた二酸化チタン（特許文献３参照。）等に見られるように、チタンと他の金属を共存させる手法が挙げられる。
【０００３】
また、最近では安定した酸素欠陥をもつ二酸化チタン（特許文献４参照。）、窒素ラジカルがトラップされた二酸化チタン（特許文献５参照。）、窒素をドープした窒酸化チタン（特許文献６参照。）等のように、金属を使用しない手法が注目されている。また、硫黄をドープした二酸化チタン（特許文献７参照。）も報告されており、スパッタリングによって酸素を硫黄アニオンで置換することにより可視光領域で活性を発現できるとされている。このような硫黄をドープした二酸化チタンに関しては、旭良司、森川健志らによって計算がなされており、可視光に活性を持つことが示唆されるが、酸素を硫黄に置き換えるには窒素に置き換えることに比べて非常に高いエネルギーが必要であり、硫黄のドープは困難であるとされている（非特許文献１参照。）。さらに、他の金属酸化物の硫黄ドープについても同様に、酸素を硫黄アニオンで置換した例が知られている（特許文献６及び８参照。）。
【０００４】
【特許文献１】
特開平９−２６２４８２号公報
【特許文献２】
特許第３０４６５８１号明細書
【特許文献３】
特開平１１−１０４５００号公報
【特許文献４】
特開２０００−１５７８４１号公報
【特許文献５】
特開２００１−１９０９５３号公報
【特許文献６】
特開２００１−２０５０９４号公報
【特許文献７】
特開２００１−２０５１０３号公報
【特許文献８】
特開２００１−２０５１０４号公報
【非特許文献１】
サイエンス，２００１年，第２９３巻，ｐ．２６９
【０００５】
【発明が解決しようとする課題】
本発明は、可視光領域でその活性を発現する新規な光酸化触媒及びその簡便なな製造方法を提供することを課題とする。
【０００６】
【課題を解決するための手段】
本発明者は上記課題を解決すべく、新しい概念として、チタン原子を非金属原子で置換することにより可視光領域で活性が発現させることができるのではないかと考え、鋭意検討を行った。その結果、チタンのアルコキシドとチオ尿素類との混合物を焼成して得た含硫黄チタン酸化物は、可視光領域の光照射で酸化触媒としての触媒能を発揮するという新たな知見を得た。そして、このようにして得られた含硫黄チタン酸化物について種々分析したところ、該含硫黄チタン酸化物において硫黄原子は陽イオン性を示すことが明らかとなった。このことは、上記含硫黄チタン酸化物に含まれる硫黄原子はチタン原子を置換する形で導入されていることを意味し、該含硫黄チタン酸化物は、酸素原子に置換する形で硫黄原子が導入されている従来の含硫黄チタン酸化物とは全く別の新規な化合物であることを意味する。
【０００７】
さらに、発明者は他の金属酸化物についても同様に、金属の代わりに陽イオンとして硫黄原子を導入することを着想し、検討を行ったところ、そのような硫黄原子の導入が比較的容易に実現できること、硫黄原子が陽イオンとして導入された金属酸化物は光酸化触媒として機能することを確認し、本発明を完成するに至った。
【０００８】
即ち、第一の本発明は、硫黄原子を陽イオンとして含有する、別言すれば、金属原子の一部が硫黄原子で置換されていることを特徴とする含硫黄金属酸化物であって、該含硫黄金属酸化物の主成分となる金属酸化物がチタン、ジルコニウム及びタンタルからなる群より選ばれる少なくとも１種の金属を含む金属酸化物である含硫黄金属酸化物である。該本発明の含硫黄チタン酸化物は、その一部の酸素原子が欠損しているかまたは窒素原子に置換されていてもよい。
【０００９】
また、第二の本発明は、チタン、ジルコニウム及びタンタルからなる群より選ばれる少なくとも１種の金属アルコキシドを含む金属アルコシドと環状又は非環状のチオ尿素（以下、チオ尿素類ともいう。）との混合物を、酸素を含む雰囲気中５００℃〜９００℃の温度範囲で焼成することを特徴とする本発明の含硫黄金属酸化物の製造方法である。
【００１０】
また、第三の本発明は、含硫黄金属酸化物の酸素原子が窒素原子に置換されていない本発明の含硫黄金属酸化物を製造する方法であって、チタン、ジルコニウム及びタンタルからなる群より選ばれる少なくとも１種の金属を含む金属酸化物と環状又は非環状のチオ尿素との混合物を、酸素を含む雰囲気中３００℃〜５００℃の温度範囲で焼成することを特徴とする方法である。
【００１１】
さらに、第四の発明は、硫酸チタンアンモニウムを５００℃〜９００℃の温度範囲で焼成することにより、一部の酸素原子が欠損しているかまたは窒素原子に置換された本発明の含硫黄チタン酸化物を製造する方法である。
【００１２】
更に、第五の本発明は、本発明の含硫黄金属酸化物からなる光酸化触媒である。また、第六の本発明は、該光酸化触媒を用いて脂環式炭化水素化合物を酸化することを特徴とする脂環式炭化水素誘導体の製造方法である。
【００１３】
【発明の実施の形態】
本発明の含硫黄金属酸化物は、チタン、ジルコニウム及びタンタルからなる群より選ばれる少なくとも１種の金属を含む金属酸化物であって、該金属原子の一部が硫黄原子で置換されている（別言すると、硫黄原子を陽性イオン性元素として含有する）。硫黄原子を陽イオン性元素として、即ち＋（正）の電荷を有する状態で含有することにより、このような形で硫黄原子を含有しない金属酸化物と比べて、光酸化触媒として機能させるための作動光の波長範囲が広がり、可視光域の光も作動光とすることが可能となる。例えば、硫黄の含量によっては６００ｎｍ以下の波長にも吸収を持たせることができる。
【００１４】
本発明の含硫黄金属酸化物は、硫黄原子を＋（正）の電荷を有する状態で含有する、チタン、ジルコニウム及びタンタルからなる群より選ばれる少なくとも１種の金属を含む金属酸化物であれば、硫黄原子の含有量は特に限定されないが、可視光での吸光度（光触媒として作用するときの可視光の有効利用率）と安定性のバランス上、硫黄の含有量は、金属原子と硫黄原子の合計モル数に対して０．１モル％〜１０モル％であるのが好適である。また、硫黄原子の電荷状態も陽イオン性であれば特に限定されないが、Ｘ線光電子分光法で測定したときの硫黄２ｐ電子に帰属されるピークが結合エネルギーで表して、１６７〜１７２ｅＶであるのが好適である。通常、このような結合エネルギーの範囲に２ｐ電子のピークを有する硫黄原子は６価のカチオンとして存在することが知られている。因みに、本発明の含硫黄酸化物の一つである含硫黄チタン酸化物をＸ線光電子分光法で測定した場合、上記硫黄に基づくピークの他に、酸素１ｓ電子に帰属されるピークが５２９〜５３５ｅＶに認められ、チタン２ｐ電子に帰属されるピークが４５８〜４６３ｅＶに認められる。
【００１５】
本発明の含硫黄金属酸化物の主成分となる金属酸化物は、光酸化触媒として作用するという点で、チタン、ジルコニウム及びタンタルからなる群より選ばれる少なくとも１種を含む金属酸化物、特に酸化チタン、酸化ジルコニウム、酸化タンタルまたはチタン酸ストロンチウムであるのが好適である。
【００１６】
また、本発明の含硫黄金属酸化物の結晶系は特に限定されず、結晶性であっても非晶質であってもよい。また、本発明の含硫黄金属酸化物、特に含硫黄チタン酸化物においては、一部の酸素原子が欠損してもよく、または一部の酸素原子が窒素原子に置換されていてもよい。例えば、好適な本発明の含硫黄チタン酸化物の組成を具体的に示せば以下のとおりである。
【００１７】
Ｔｉ０．９９９〜０．９Ｓ０．００１〜０．１Ｏ２．０〜１．９Ｎ０〜０．１
なお、酸素原子の一部が窒素原子で置換されている本発明の含硫黄チタン酸化物をＸ線光電子分光法で測定した場合、窒素１ｓ電子に帰属されるピークが３９６〜３９８ｅＶに認められる。
【００１８】
本発明の含硫黄酸化物は（１）チタン、ジルコニウム及びタンタルからなる群より選ばれる少なくとも１種の金属アルコキシドを含む金属アルコシドと環状又は非環状のチオ尿素との混合物を、酸素を含む雰囲気中５００℃〜９００℃の温度範囲で焼成することによって好適に製造することができる。また、含硫黄金属酸化物の酸素原子が窒素原子に置換されていない本発明の含硫黄金属酸化物については、（２）チタン、ジルコニウム及びタンタルからなる群より選ばれる少なくとも１種の金属を含む金属酸化物と環状又は非環状のチオ尿素との混合物を、酸素を含む雰囲気中３００℃〜５００℃の温度範囲で焼成することにより好適に製造することができる。また、本発明の含硫黄チタン酸化物については、（３）硫酸チタンアンモニウムを５００℃〜９００℃の温度範囲で焼成することによっても製造することができる。
【００１９】
上記（１）の方法は、簡便であるばかりでなく、硫黄の含量の調節が容易であるという特徴を有する。該方法においては、得られる目的物が均質となるという理由から、金属のアルコキシドとチオ尿素類を有機溶媒に溶解させて均一溶液とした後、有機溶媒を減圧留去して粉末を得、これを上記温度範囲で焼成するのが好適である。ここで用いる金属のアルコキシドは、チタン、ジルコニウム及びタンタルからなる群より選ばれる少なくとも１種の金属アルコキシドを含む金属アルコシドであれば特に限定されないが、溶解性の観点から炭素数５以下の低級アルコールのアルコキシドが好ましく、入手の面からテトライソプロポキシドが特に好ましい。また、環状、非環状のチオ尿素（チオ尿素類）としては、入手の面からは無置換のチオ尿素｛Ｓ＝Ｃ（ＮＨ２）２｝が特に好ましい。
【００２０】
金属アルコシドとチオ尿素類との量比は特に限定されないが、この量比によって最終的に得られる含硫黄酸化物の組成が概略決定されるので、最終的に得ようとする化合物の組成に基づいて適宜決定すればよい。但し、後述するように焼成中に硫黄原子が焼失するので、チオ尿素類の量は計算値よりも若干多めにしておくのが好適である。なお、チオ尿素由来の窒素はほとんど認められない。
【００２１】
溶媒としては金属のアルコキシドやチオ尿素類と反応しない溶媒であれば特に限定されず、ヘキサン、ヘプタン等の脂肪族炭化水素、トルエン、キシレン等の芳香族の炭化水素、塩化メチレン、クロロホルム等の塩素化炭化水素、酢酸エチル、酢酸イソブチル等のエステル類、アセトニトリル、ブチロニトリル等のニトリル類、アセトン、メチルエチルケトン等のケトン類、メタノール、エタノール、イソプロパノール等のアルコール類等が使用できる。チオ尿素類にチオ尿素を用いる場合はその溶解性からアルコール類が特に好ましい。
【００２２】
焼成方法は、５００℃〜９００℃の間で焼成する方法であれば特に限定されないが、焼成温度が高いほど、また焼成時間が長いほど硫黄の含量は少なくなっていく傾向があるので、焼成時間は３時間〜１０時間の間とするのが好適である。また、焼成は、酸素を含む雰囲気で行われるが、特別な装置を要しないという観点から大気中で焼成するのが最も好適である。
【００２３】
前記（２）の方法は、金属アルコキシドに代えて金属酸化物を使用し、さらに焼成温度を３００〜５００℃とする以外は上記（１）の方法とほぼ同様にして行なうことができる。該方法では、チオ尿素類を有機溶媒に溶解させた溶液と原料金属酸化物粉末とを良く混合してスラリーを得た後に有機溶媒を減圧留去して粉末を得た後に、或いは原料金属酸化物粉末にチオ尿素類を有機溶媒に溶解させた溶液をスプレーする等により均一にふりかけてから溶媒を除去した後に、これを上記温度範囲で焼成すればよい。また、有機溶媒を使用しないで金属酸化物粉末とチオ尿素類とを直接混合して焼成することもできる。後者の方法は、溶剤を用いず、物理的な混合と焼成だけで含硫黄金属酸化物が得られるため操作が簡便であり、工業的製法として有用である。用いるチオ尿素類も（１）の場合と同様に環状、非環状のチオ尿素が利用できるが、入手の面からは無置換のチオ尿素｛Ｓ＝Ｃ（ＮＨ２）２｝が特に好ましい。焼成条件に関しても（１）の場合と同様に前記焼成温度にあわせて焼成時間を適宜調節すればよい。
【００２４】
また、前記（３）の方法によれば、本発明のチタン原子の一部が硫黄原子で置換され、さらに酸素原子の一部が窒素原子で置換されている含硫黄二酸化チタンを簡便に製造することができる。例えば、硫酸チタンの水溶液をアンモニア水又はアンモニアガスで中和して硫酸チタンアンモニウムを沈殿させ、ろ過、乾燥して粉末を得、これを６００℃で３時間、大気圧下で焼成することにより上記のような含硫黄二酸化チタンを容易に製造することができる。なお、焼成に際して焼成温度が高いほど、また、焼成時間が長いほど硫黄および窒素の含量は少なくなっていくので、所望の含量になるように焼成温度と焼成時間を調節すればよい。
【００２５】
このようにして製造された本発明の含硫黄金属酸化物は、光触媒として機能するばかりでなく、硫黄を含まない金属酸化物が活性を示さないような可視光領域にも活性を有するという特徴を有する。このため、アダマンタン等の脂環式炭化水素化合物を酸素酸化してアルコールやケトンに転化させる際の光酸化触媒として好適に使用することができる。なお、このような特徴は、金属原子を非金属元素によって置換することによって発現したものであり、該非金属元素は硫黄に限定されるものではない。例えばチタン原子をリン等のＳ以外の元素で置換する場合には、焼成前の前駆体としてリン等の非金属元素を含有するものを用いればよい。
上記の光酸化反応で原料として使用できる脂環式炭化水素化合物は特に限定されないが、生成物の有用性の観点からアダマンタンを用いるのが好適である。
【００２６】
また、反応方法は特に限定されないが、溶媒中、本発明の含硫黄金属酸化物の存在下、光照射しながら脂環式炭化水素化合物を酸素と接触されるのが好適である。このとき溶媒としては、酸化すべき脂環式炭化水素化合物より酸化されにくいものであれば特に限定されないが、アセトニトリル、ブチロニトリル等のニトリル類が好適に使用できる。また、反応方式は特に限定されず、回分式でも流通式でも行なうことができる。触媒量は特に限定されず、脂環式炭化水素１００重量部に対して０．０１重量部から５０００重量部の広い範囲が適用可能であり、流通式の場合はより少ない触媒量で行なうこともできる。照射する光の強度や波長についても特に限定されず、触媒量に合わせた（即ち、全ての光を触媒が吸収するような）強度がエネルギー効率の面から推奨され、波長についても触媒が吸収できる波長（紫外線を含む）であれば特に限定されないが、本触媒の特徴を最大限に発揮するためには可視光領域の波長を選択することが望ましい。反応時間や反応温度についても特に限定されず、反応の進行状態によって適宜決定すればよい。
【００２７】
【実施例】
以下に実施例をあげて本発明をさらに詳細に述べるが、本発明はこれらの実施例によって何ら制限されるものではない。
【００２８】
実施例１
５００ｍｌのエタノール中でチタンテトライソプロポキシド１５ｇ（５３ｍｍｏｌ）とチオ尿素１０ｇ（１３２ｍｍｏｌ，２．５ｅｑ．ｔｏＴｉ）を混合し、均一に溶解するまで１時間以上攪拌した。この溶液をエバポレーターで減圧留去し、完全に乾固する前に取り出して大気圧下、風乾した。この粉末を大気中で５００℃、３時間焼成して黄色から白色の粉末を得た。得られた粉末についてＸ線光電子分光スペクトル測定を行ったところ、４５９．７ｅＶ、１６９．０ｅＶおよび５３１．３ｅＶにそれぞれＴｉ２ｐ、Ｓ２ｐおよびＯ１ｓに相当するピークが観測されたことから、該粉末はチタン原子が硫黄原子で置換された含硫黄チタン酸化物であることが確認された。また、これらピークの強度比に基づいて組成を決定したところ、その組成はＴｉ０．８７Ｓ０．１３Ｏ２．００であった。なお、本実施例で得られた含硫黄チタン酸化物をＳ−ＴｉＯ２（５００℃３ｈ）と略記する。
【００２９】
図１に実施例１で得られた各粉末の拡散反射吸収スペクトルを、後述する実施例２〜３で得られた粉末の拡散反射吸収スペクトルおよび市販の二酸化チタンであるＰＴ−１０１の拡散反射吸収スペクトルと共に示した。また、実施例１で得られた粉末Ｓ−ＴｉＯ２（５００℃３ｈ）のＸ線光電子分光スペクトルを図２〜図４に示した。図１に示されるように、これら粉末は何れも可視光域に吸収を持つことが分かる。
【００３０】
実施例２
焼成条件を６００℃、３時間にした他は、実施例１と同様にして粉末を得た。Ｘ線光電子分光スペクトル測定から、得られた粉末は組成Ｔｉ０．９０Ｓ０．１０Ｏ２．００のチタン原子が硫黄原子で置換された含硫黄チタン酸化物であることが確認された。なお、本実施例で得られた含硫黄チタン酸化物をＳ−ＴｉＯ２（６００℃３ｈ）と略記する。
【００３１】
実施例３
焼成条件を７００℃、３時間にした他は、実施例１と同様にして粉末を得た。Ｘ線光電子分光スペクトル測定から、得られた粉末は組成Ｔｉ０．９１Ｓ０．０９Ｏ２．００のチタン原子が硫黄原子で置換された含硫黄チタン酸化物であることが確認された。なお、本実施例で得られた含硫黄チタン酸化物をＳ−ＴｉＯ２（７００℃３ｈ）と略記する。
【００３２】
実施例４
焼成条件を５００℃、１０時間にした他は、実施例１と同様にして粉末を得た。Ｘ線光電子分光スペクトル測定から、得られた粉末は組成Ｔｉ０．８８Ｓ０． １２Ｏ２．００のチタン原子が硫黄原子で置換された含硫黄チタン酸化物であることが確認された。なお、本実施例で得られた含硫黄チタン酸化物をＳ−ＴｉＯ２（５００℃１０ｈ）と略記する。
【００３３】
実施例５
焼成条件を６００℃、１０時間にした他は、実施例１と同様にして粉末を得た。Ｘ線光電子分光スペクトル測定から、得られた粉末は組成Ｔｉ０．９０Ｓ０．１０Ｏ２．００のチタン原子が硫黄原子で置換された含硫黄チタン酸化物であることが確認された。なお、本実施例で得られた含硫黄チタン酸化物をＳ−ＴｉＯ２（６００℃１０ｈ）と略記する。
【００３４】
実施例６
３０％Ｔｉ（ＳＯ４）２溶液を純水で３倍程度に希釈後、２５％ＮＨ３水溶液を滴下し、ｐＨ７付近になるように調整し、白色の懸濁液を得た。減圧濾過後、ヌッチェ上、純水で１０回洗浄し白色のケーキを１０７℃で一晩乾燥した。やや黄色がかった凝集した固体を乳鉢で砕き、アンモニア気流（１ｍｌ／ｍｉｎ．）下、６００℃−３ｈｒ焼成して黄色の粉末を得た。Ｘ線光電子分光スペクトル測定から、得られた粉末は組成Ｔｉ０．９９Ｓ０．０１Ｏ１．９９Ｎ０．０１のチタン原子が硫黄原子で置換され、更に酸素原子の一部が窒素原子で置換された含硫黄チタン酸化物であることが確認された。なお、本実施例で得られた含硫黄チタン酸化物をＴｉＮＳＯ（１）と略記する。
【００３５】
実施例７
３０％Ｔｉ（ＳＯ４）２溶液を純水で３倍程度に希釈後、２５％ＮＨ３水溶液を滴下し、ｐＨ７付近になるように調整し、白色の懸濁液を得た。これに再びＴｉ（ＳＯ４）２溶液を加えpH 1とした。減圧濾過後、得られた白色のケーキを１０７℃で一晩乾燥した。やや黄色がかった非常に凝集した固体を乳鉢で砕き、アンモニア気流（１ｍｌ／ｍｉｎ．）下、６００℃−３ｈｒ焼成して黄色の粉末を得た。Ｘ線光電子分光スペクトル測定から、得られた粉末は組成Ｔｉ０．９８５Ｓ０．０１５Ｏ１．９９Ｎ０．０１のチタン原子が硫黄原子で置換され、更に酸素原子の一部が窒素原子で置換された含硫黄チタン酸化物であることが確認された。なお、本実施例で得られた含硫黄チタン酸化物をＴｉＮＳＯ（２）と略記する。
【００３６】
参考例
ＴｉＣｌ４（９９．０％）に２５％ＮＨ３水溶液を滴下し、ｐＨ７付近になるように調整して白色の懸濁液を得た。減圧濾過後、ヌッチェ上、純水で１０回洗浄した。白色のケーキを１０７℃で一晩乾燥した。やや黄色がかった凝集した固体を乳鉢で砕き、アンモニア気流（１ｍｌ／ｍｉｎ．）下、６００℃−３ｈｒ焼成して黄色の粉末を得た。Ｘ線光電子分光スペクトル測定から、得られた粉末は組成Ｔｉ１．００Ｏ１．９９Ｎ０．０１の酸素原子の一部が窒素原子で置換されたチタン酸化物であることが確認された。なお、本実施例で得られた含硫黄チタン酸化物をＴｉＮＯと略記する。
【００３７】
実施例８〜１１および比較例１〜２
６本の試験管にそれぞれアダマンタン０．０４ｇ、ブチロニトリル１．９６ｇ及びアセトニトリル２．００ｇを加え均一溶液を得た。各試験管にそれぞれ実施例１、４、２、５で得た本発明の含硫黄チタン酸化物及び市販のチタニア（Ｓｔ−４１比較例１，Ｐ−２５比較例２）を添加し、更にスラーラーピースを入れ、懸濁させた。なお、添加量は予備実験により、量子収率が比較できるよう、それぞれの粉末について加える触媒量を調べて、照射光の光をすべて吸収できる条件を探して決定した。また、溶解、懸濁には超音波処理を用いた。試験管はシリコーン栓とフローシールで密閉した。酸素（気体）を、注射針を用いて２ｍｌ／ｍｉｎ．で１５分バブリングさせた。（このとき圧抜きのための針も刺した。）
光照射は１０００Ｗキセノンランプを用いて各試験管に光照射を行った。このとき、波長制御のために短波長カットフィルター（４４０ｎｍ以下カット）を用いた。反応中はマグネティクスターラーで攪拌した。
【００３８】
反応後、遠心分離により触媒と溶液を分離し、溶液について生成物を評価した。分析はガスクロマトグラフおよびＧＣＭＡＳＳで行った。
【００３９】
結果を図５に示す。ここでＳｔ−４１、Ｐ−２５は市販の二酸化チタンであり、Ｓ−ＴｉＯ２は本発明のチタン原子の一部が硫黄原子で置換されている含硫黄二酸化チタンである。また、括弧内は焼成条件を示す。
【００４０】
図５に示されるように、本発明のＳ−ＴｉＯ２は市販の二酸化チタンに比べ、４４０ｎｍ以下の可視光を照射した場合、明らかに活性が高いことが判る。
【００４１】
実施例１２〜１３および比較例３〜５
実施例６と７で得られた粉末について実施例８と同様に、アダマンタンの酸化を行なった。結果を図６に示す。ここでＳｔ−４１、Ｐ−２５は市販の二酸化チタンであり、ＴｉＮＯは参考例で調製した粉末である。図６に示されるように、本発明のチタン原子の一部が硫黄原子で置換されており、かつ、一部の酸素原子が窒素原子で置換されている含硫黄チタン酸化物は４４０ｎｍ以下の可視光を照射した場合、市販の二酸化チタンあるいはチタン原子の一部が硫黄原子で置換していないが、一部の酸素原子が窒素原子で置換されているチタン酸化物に比べて、明らかに活性が高いことが判る。
【００４２】
実施例１４
チタン酸ストロンチウム（富士チタン工業製、ＨＰＳＴ−１）２．００１１ｇとチオ尿素（ＷＡＫＯ製、ｍｉｎ．９８．０％）８．００２４ｇを１：４の比で混合した。その混合物を乳鉢に入れ、粒径が同じになるように擦り合わせながら均一になるまで攪拌した。その混合物を焼成用のボートに移し電気炉（伸化電機製作所、型式：ＳＴ−０５）で焼成を行った。焼成は３００℃で３ｈｒ行った。焼成後、固まった黄色の物質を粉末状態になるまで粉砕した。この含硫黄チタン酸ストロンチウムの硫黄含量をＸ線光電子分光スペクトルから算出したところ、１．５％であった。本実施例で得られた含硫黄チタン酸ストロンチウムをＳ−ＳｒＴｉＯ３（３００℃）と略記する。図７に本実施例で得られた粉末の拡散反射吸収スペクトルを、後述する実施例１５〜１６で得られた粉末の拡散反射吸収スペクトルおよび市販のチタン酸ストロンチウム（ＳｒＴｉＯ３）の拡散反射吸収スペクトルと共に示した。図７に示されるように、これら粉末は何れも可視光域に吸収を持つことが分かる。
【００４３】
実施例１５
焼成条件を４００℃で３ｈｒにした他は実施例８と同様にして粉末を得た。この含硫黄チタン酸ストロンチウムの硫黄含量をＸ線光電子分光スペクトルから算出したところ、1.5％であった。本実施例で得られた含硫黄チタン酸ストロンチウムをＳ−ＳｒＴｉＯ３（４００℃）と略記する。
【００４４】
実施例１６
焼成条件を５００℃で３ｈｒにした他は実施例８と同様にして粉末を得た。この含硫黄チタン酸ストロンチウムの硫黄含量をＸ線光電子分光スペクトルから算出したところ、０．３％であった。本実施例で得られた含硫黄チタン酸ストロンチウムをＳ−ＳｒＴｉＯ３（５００℃）と略記する。
【００４５】
実施例１７
酸化ジルコニウム（和光製）２．００１０ｇとチオ尿素（ＷＡＫＯ製、ｍｉｎ．９８．０％）８．００５０ｇを１：４の比で混合した。その混合物を乳鉢に入れ、粒径が同じになるように擦り合わせながら均一に攪拌した。その混合物を焼成用のボートに移し電気炉（伸化電機製作所、型式：ＳＴ−０５）で焼成を行った。焼成は４００℃で３ｈｒ行った。焼成後、固まった黄色の物質を粉末状態になるまで粉砕した。これらの含硫黄酸化ジルコニウムの硫黄含量をＸ線光電子分光スペクトルから算出したところ、１．４％であった。本実施例で得られた含硫黄酸化ジルコニウムをＳ−ＺｒＯ２（４００℃）と略記する。図８に本実施例で得られた粉末の拡散反射吸収スペクトルを、後述する実施例１８で得られた粉末の拡散反射吸収スペクトルおよび市販の酸化ジルコニウム（ＺｒＯ２）の拡散反射吸収スペクトルと共に示した。図８に示されるように、これら粉末は何れも可視光域に吸収を持つことが分かる。
【００４６】
実施例１８
焼成条件を５００℃で３ｈｒにした他は実施例１７と同様にして粉末を得た。この含硫黄酸化ジルコニウムの硫黄含量をＸ線光電子分光スペクトルから算出したところ、０．１％であった。本実施例で得られた含硫黄酸化ジルコニウムをＳ−ＺｒＯ２（５００℃）と略記する。
【００４７】
実施例１９
酸化タンタル（和光製ｍｉｎ．９９．８％）２．０５９３ｇとチオ尿素（ＷＡＫＯ製、ｍｉｎ．９８．０％）８．２３６５ｇを１：４の比で混合した。その混合物を乳鉢に入れ、粒径が同じになるように擦り合わせながら均一になるまで攪拌した。その混合物を焼成用のボートに移し電気炉（伸化電機製作所、型式：ＳＴ−０５）で焼成を行った。焼成は３００℃で３ｈｒ行った。焼成後、固まった黄色の物質を粉末状態になるまで粉砕した。これらの含硫黄酸化タンタルの硫黄含量をＸ線光電子分光スペクトルから算出したところ、１．８％であった。本実施例で得られた含硫黄酸化タンタルをＳ−Ｔａ２Ｏ５（３００℃）と略記する。図９に本実施例で得られた粉末の拡散反射吸収スペクトルを、後述する実施例２０および２１で得られた粉末の拡散反射吸収スペクトルおよび市販の酸化タンタル（Ｔａ２Ｏ５）の拡散反射吸収スペクトルと共に示した。図９に示されるように、これら粉末は何れも可視光域に吸収を持つことが分かる。
【００４８】
実施例２０
焼成条件を４００℃で３ｈｒにした他は実施例１９と同様にして粉末を得た。この含硫黄酸化タンタルの硫黄含量をＸ線光電子分光スペクトルから算出したところ、１．５％であった。本実施例で得られた含硫黄酸化タンタルをＳ−Ｔａ２Ｏ５（４００℃）と略記する。
【００４９】
実施例２１
焼成条件を５００℃で３ｈｒにした他は実施例１９と同様にして粉末を得た。この含硫黄酸化ジルコニウムの硫黄含量をＸ線光電子分光スペクトルから算出したところ、０．５％であった。本実施例で得られた含硫黄酸化タンタルをＳ−Ｔａ２Ｏ５（５００℃）と略記する。
【００５０】
実施例２２、比較例６
実施例１４で得られた粉末について、メチレンブルーの酸化分解速度を指標にして酸化力を市販のチタン酸ストロンチウム（富士チタン工業製、ＨＰＳＴ−１）と比較した。まず、塩酸でph＝4に調整したメチレンブルー水溶液（０．０１ｍＭ）を作成した。その溶液を45ml採取し、実施例１４で得られたＳ−ＳｒＴｉＯ３（３００℃）を０．９ｇ加えた。触媒表面にメチレンブルーを充分に吸着させるために、アルミホイルで遮光して一晩（６〜１２ｈｒ）攪拌した。攪拌した混合溶液を3ml試験管に取り、５００Ｗのキセノンランプでそれぞれ１分、５分、１０分光照射を行った。光の波長はカットフィルターで３４０ｎｍ以下、または４２０ｎｍ以下、または４４０ｎｍ以下の波長の光をそれぞれカットした。光照射後と光照射前の混合溶液を採取し、遠心分離を二回行った後、メチレンブルーの吸光度をＵＶ−ＶＩＳスペクトル（ＳＨＩＭＡＺＵ ＵＶ−２５００ＰＣ）で測定した。測定した吸光度の中で６６３ｎｍ付近の吸収ピーク強度を時間でプロットし、各フィルターを用いた場合のメチレンブルーの分解速度を計算した。同様の操作を市販のチタン酸ストロンチウム０．９ｇで行い、メチレンブルーの分解速度を計算した。結果を図１０に示した。カットした波長に関わらず、Ｓ−ＳｒＴｉＯ３（３００℃）による分解速度は市販のチタン酸ストロンチウムに比べて速いことが分かり、特に、可視光（４４０ｎｍ以下カット）においてもＳ−ＳｒＴｉＯ３（３００℃）による光酸化反応が起きていることがわかる。
【００５１】
実施例２３、比較例７
実施例１９で得られた粉末について、メチレンブルーの酸化分解速度を指標にして酸化力を市販の酸化タンタル（和光製）と比較した。まず、塩酸でｐＨ＝４に調整したメチレンブルー水溶液（０．０２ｍＭ）作成した。その溶液を３５ｍｌ採取し、実施例１９で得られたＳ−Ｔａ２Ｏ５（３００℃）を０．５ｇ加えた。触媒表面にメチレンブルーを充分に吸着させるために、アルミホイルで遮光して一晩（６〜１２ｈｒ）攪拌した。攪拌した混合溶液を3ml試験管に取り、１０００Ｗのキセノンランプでそれぞれ１分、５分、１０分光照射を行った。光の波長はカットフィルターで３４０ｎｍ、４２０ｎｍ、４４０ｎｍ、５００ｎｍ以下の光をそれぞれカットした。実施例２４と同様の操作にてメチレンブルーの酸化速度を計算した。さらに、市販の酸化タンタル０．５ｇについても同様の操作をしてメチレンブルーの酸化速度を計算した。結果を図１１に示した。カットした波長に関わらず、Ｓ−Ｔａ２Ｏ５（３００℃）による分解速度は市販の酸化タンタルに比べて速いことが分かり、特に、５００ｎｍ以上の可視光においてもＳ−Ｔａ２Ｏ５（３００℃）による光酸化反応が起きていることがわかる。
【００５２】
【発明の効果】
本発明の含硫黄金属酸化物は、金属原子の一部が硫黄原子で置換されている新規な含硫黄金属酸化物であり、可視光に活性をもつ光酸化触媒として有用である。そして、本発明の含硫黄金属酸化物をアダマンタン等の脂環式炭化水素化合物の酸化反応の触媒として用いた場合には、従来の光酸化触媒を用いた場合よりも効率よくアダマンタノンやアダマンタノールを製造することができる。また、本発明の製造方法によれば、このような本発明の含硫黄金属酸化物を容易、かつ、低コストで製造することが可能である。
【図面の簡単な説明】
【図１】 本図は、チタン原子の一部が硫黄原子で置換されている含硫黄二酸化チタンの拡散反射吸収スペクトルである。
【図２】 本図は、実施例１の含硫黄チタン酸化物のＸ線光電子分光スペクトル（チタン２ｐ）である。
【図３】 本図は、実施例１の含硫黄チタン酸化物のＸ線光電子分光スペクトル（硫黄２ｐ）である。
【図４】 本図は、実施例１の含硫黄チタン酸化物のＸ線光電子分光スペクトル（酸素１ｓ）である。
【図５】 本図は、実施例８〜１１及び比較例１〜２の反応結果を示すグラフである。
【図６】 本図は、実施例１２〜１３および比較例３〜５の反応結果を示すグラフである。
【図７】 本図は、実施例１４〜１６で得られた含硫黄チタン酸ストロンチウムおよび、市販のチタン酸ストロンチウムの拡散反射吸収スペクトルである。
【図８】 本図は、実施例１７および１８で得られた含硫黄酸化ジルコニウムおよび、市販の酸化ジルコニウムの拡散反射吸収スペクトルである。
【図９】 本図は実施例１９〜２１で得られた含硫黄酸化タンタルおよび市販の酸化タンタルの拡散反射吸収スペクトルである。
【図１０】 本図は、実施例２２と比較例６の反応速度を示すグラフである。
【図１１】 本図は、実施例２３と比較例７の反応速度を示すグラフである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel sulfur-containing metal oxide useful as a photooxidation catalyst and a method for producing the same, and a method for producing an oxidized derivative by oxidizing an organic compound using the sulfur-containing metal oxide.
[0002]
[Prior art]
Titanium dioxide is well known as a photo-oxidation catalyst, but conventionally, its activity has been expressed only in the ultraviolet region. In recent years, many attempts have been made to express the activity in the visible light region. As a representative method, titanium dioxide into which metal ions are introduced by a high energy beam (see Patent Document 1), a layered titanate compound containing metal ions (see Patent Document 2), and clusters of metals or metal compounds are dispersed. As seen in titanium dioxide (see Patent Document 3) and the like, there is a method in which titanium and another metal coexist.
[0003]
In addition, recently, titanium dioxide having stable oxygen defects (see Patent Document 4), titanium dioxide in which nitrogen radicals are trapped (see Patent Document 5), and titanium nitride oxide doped with nitrogen (see Patent Document 6). As described above, a technique that does not use metal is attracting attention. Further, titanium dioxide doped with sulfur (see Patent Document 7) has also been reported, and it is said that the activity can be expressed in the visible light region by substituting oxygen with a sulfur anion by sputtering. Such sulfur-doped titanium dioxide has been calculated by Ryoji Asahi, Kenji Morikawa, and others, suggesting that it is active in visible light, but to replace oxygen with sulfur, replace it with nitrogen. Compared to this, extremely high energy is required, and sulfur doping is difficult (see Non-Patent Document 1). Furthermore, similarly to sulfur doping of other metal oxides, examples in which oxygen is substituted with sulfur anions are known (see Patent Documents 6 and 8).
[0004]
[Patent Document 1]
JP-A-9-262482
[Patent Document 2]
Japanese Patent No. 3046581
[Patent Document 3]
JP-A-11-104500
[Patent Document 4]
JP 2000-157841 A
[Patent Document 5]
JP 2001-190953 A
[Patent Document 6]
JP 2001-205094 A
[Patent Document 7]
JP 2001-205103 A
[Patent Document 8]
JP 2001-205104 A
[Non-Patent Document 1]
Science, 2001, 293, p. 269
[0005]
[Problems to be solved by the invention]
It is an object of the present invention to provide a novel photooxidation catalyst that exhibits its activity in the visible light region and a simple production method thereof.
[0006]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventor has intensively studied as a new concept that the activity can be expressed in the visible light region by substituting a titanium atom with a nonmetallic atom. As a result, a new finding was obtained that the sulfur-containing titanium oxide obtained by baking a mixture of titanium alkoxide and thiourea exhibits catalytic ability as an oxidation catalyst when irradiated with light in the visible light region. And when various analysis was carried out about the sulfur-containing titanium oxide obtained in this way, it became clear that a sulfur atom shows cationic property in this sulfur-containing titanium oxide. This means that the sulfur atom contained in the sulfur-containing titanium oxide is introduced in the form of replacing a titanium atom, and the sulfur-containing titanium oxide has a sulfur atom in a form of replacing with an oxygen atom. This means that the compound is completely different from the conventional sulfur-containing titanium oxide that has been introduced.
[0007]
Furthermore, the inventors have conceived and studied the introduction of sulfur atoms as cations instead of metals in other metal oxides, and as a result, it was relatively easy to introduce such sulfur atoms. It was confirmed that the metal oxide in which sulfur atoms were introduced as cations functioned as a photo-oxidation catalyst, and the present invention was completed.
[0008]
That is, the first aspect of the present invention is a sulfur-containing metal oxide containing a sulfur atom as a cation, in other words, a part of the metal atom is substituted with a sulfur atom, The metal oxide as the main component of the sulfur-containing metal oxide is a metal oxide containing at least one metal selected from the group consisting of titanium, zirconium and tantalum.Sulfur-containing metal oxideIt is. The sulfur-containing titanium oxide of the present invention may have some oxygen atoms missing or substituted with nitrogen atoms.
[0009]
The second aspect of the present inventionIncluding at least one metal alkoxide selected from the group consisting of titanium, zirconium and tantalumWith metal alcosideCyclic or acyclic thiourea (hereinafter also referred to as thioureas)Mixture withIn an atmosphere containing oxygenIt is a manufacturing method of the sulfur-containing metal oxide of this invention characterized by baking in the temperature range of 500 to 900 degreeC.
[0010]
The third aspect of the present inventionA method for producing a sulfur-containing metal oxide of the present invention in which the oxygen atom of the sulfur-containing metal oxide is not substituted with a nitrogen atom, comprising at least one metal selected from the group consisting of titanium, zirconium and tantalumMetal oxide andCyclic or acyclic thioureaMixture withIn an atmosphere containing oxygenBaking in a temperature range of 300 ° C to 500 ° CMethodIt is.
[0011]
Furthermore, the fourth invention is the sulfur-containing titanium oxide of the present invention in which some of the oxygen atoms are deficient or substituted with nitrogen atoms by firing titanium ammonium sulfate in a temperature range of 500 ° C. to 900 ° C. This is a method for manufacturing a product.
[0012]
Furthermore, the fifth aspect of the present invention providesSulfur-containing metal oxide of the present inventionA photo-oxidation catalyst comprising The sixth aspect of the present invention is a method for producing an alicyclic hydrocarbon derivative characterized in that an alicyclic hydrocarbon compound is oxidized using the photooxidation catalyst.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The sulfur-containing metal oxide of the present invention isA metal oxide containing at least one metal selected from the group consisting of titanium, zirconium and tantalum,Some of the metal atoms are replaced with sulfur atoms (in other words, containing sulfur atoms as positive ionic elements). By containing a sulfur atom as a cationic element, that is, in a state having a + (positive) charge, photooxidation is performed in comparison with a metal oxide not containing a sulfur atom in this form.catalystAs a result, the wavelength range of the working light for functioning as the light spreads, and the light in the visible light region can also be used as the working light. For example, depending on the sulfur content, absorption can be provided even at wavelengths of 600 nm or less.
[0014]
The sulfur-containing metal oxide of the present invention contains a sulfur atom in a state having a + (positive) charge., A metal oxide containing at least one metal selected from the group consisting of titanium, zirconium and tantalumIf so, the content of sulfur atoms is not particularly limited, but for the balance between absorbance in visible light (effective utilization of visible light when acting as a photocatalyst) and stability, the sulfur content is It is suitable that it is 0.1 mol%-10 mol% with respect to the total mol number of a sulfur atom. Also, the charge state of the sulfur atom is not particularly limited as long as it is cationic, but the peak attributed to sulfur 2p electrons when measured by X-ray photoelectron spectroscopy is 167 to 172 eV in terms of binding energy. Is preferred. Usually, it is known that a sulfur atom having a peak of 2p electrons in such a binding energy range exists as a hexavalent cation. Incidentally, when the sulfur-containing titanium oxide, which is one of the sulfur-containing oxides of the present invention, is measured by X-ray photoelectron spectroscopy, in addition to the peak based on the sulfur, a peak attributed to oxygen 1s electrons is 529 to A peak attributed to 535 eV and attributable to titanium 2p electrons is observed at 458 to 463 eV.
[0015]
The metal oxide as the main component of the sulfur-containing metal oxide of the present invention is, Photo-oxidation catalystIn terms of acting as titanium, zirconiumas well astantalumConsist ofAt least one selected from the groupMetal oxides containingParticularly preferred are titanium oxide, zirconium oxide, tantalum oxide or strontium titanate.
[0016]
The crystal system of the sulfur-containing metal oxide of the present invention is not particularly limited, and may be crystalline or amorphous. In the sulfur-containing metal oxide of the present invention, particularly sulfur-containing titanium oxide, a part of oxygen atoms may be lost or a part of oxygen atoms may be substituted with nitrogen atoms. For example, the composition of the preferred sulfur-containing titanium oxide of the present invention is specifically shown as follows.
[0017]
Ti0.999-0.9S0.001 to 0.1O2.0-1.9N0-0.1
In addition, when the sulfur-containing titanium oxide of the present invention in which some oxygen atoms are substituted with nitrogen atoms is measured by X-ray photoelectron spectroscopy, a peak attributed to 1 s electrons of nitrogen is observed at 396 to 398 eV.
[0018]
The sulfur-containing oxide of the present invention is(1) including at least one metal alkoxide selected from the group consisting of titanium, zirconium and tantalumWith metal alcosideCyclic or acyclic thioureaMixture withIn an atmosphere containing oxygenFiring in the temperature range of 500 ° C to 900 ° CIt can manufacture suitably. Further, the sulfur-containing metal oxide of the present invention in which the oxygen atom of the sulfur-containing metal oxide is not substituted with a nitrogen atom includes (2) at least one metal selected from the group consisting of titanium, zirconium and tantalum.Metal oxide andCyclic or acyclic thioureaMixture withIn an atmosphere containing oxygenIt can manufacture suitably by baking in the temperature range of 300 to 500 degreeC. For the sulfur-containing titanium oxide of the present invention,(3)It can also be produced by firing ammonium ammonium sulfate in a temperature range of 500 ° C to 900 ° C.
[0019]
the above(1)This method is not only simple, but also has the feature that the sulfur content can be easily adjusted. In this method, because the obtained target product is homogeneous, a metal alkoxide and thioureas are dissolved in an organic solvent to form a homogeneous solution, and then the organic solvent is distilled off under reduced pressure to obtain a powder. Is preferably calcined in the above temperature range. The metal alkoxide used here isA metal alkoxide containing at least one metal alkoxide selected from the group consisting of titanium, zirconium and tantalumAlthough not particularly limited, an alkoxide of a lower alcohol having 5 or less carbon atoms is preferable from the viewpoint of solubility, and tetraisopropoxide is particularly preferable from the viewpoint of availability. Also,As cyclic and acyclic thiourea (thioureas),In terms of availability, unsubstituted thiourea {S = C (NH2)2} Is particularly preferable.
[0020]
The amount ratio between the metal alkoxide and the thioureas is not particularly limited, but since the composition of the sulfur-containing oxide finally obtained is roughly determined by this amount ratio, it is based on the composition of the compound to be finally obtained. May be determined as appropriate. However, as will be described later, since sulfur atoms are burned out during firing, the amount of thioureas is preferably slightly larger than the calculated value. In addition, almost no nitrogen derived from thiourea is observed.
[0021]
The solvent is not particularly limited as long as it does not react with metal alkoxides or thioureas, aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as toluene and xylene, chlorine such as methylene chloride and chloroform. Hydrocarbons, esters such as ethyl acetate and isobutyl acetate, nitriles such as acetonitrile and butyronitrile, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol and isopropanol can be used. When thiourea is used for thioureas, alcohols are particularly preferred because of their solubility.
[0022]
The firing method is not particularly limited as long as the firing method is between 500 ° C. and 900 ° C. However, the higher the firing temperature and the longer the firing time, the more the sulfur content tends to decrease. Is preferably between 3 hours and 10 hours. Also firingIsAtmosphere containing oxygenDone inIt is most preferable to perform firing in the atmosphere from the viewpoint that no special apparatus is required.
[0023]
Above(2)The method is the same as the above except that a metal oxide is used instead of the metal alkoxide and the firing temperature is 300 to 500 ° C.(1)The method can be performed in substantially the same manner. In this method, thioureas are dissolved in an organic solvent.SetAfter thoroughly mixing the solution and raw material metal oxide powder to obtain a slurry, the organic solvent is distilled off under reduced pressure to obtain a powder, or thioureas are dissolved in the raw material metal oxide powder in an organic solvent.SetAfter removing the solvent by uniformly spraying the solution by spraying or the like, it may be fired at the above temperature range. Further, the metal oxide powder and thioureas can be directly mixed and fired without using an organic solvent. The latter method is convenient as an industrial production method because a sulfur-containing metal oxide can be obtained only by physical mixing and baking without using a solvent. Thioureas used(1)Cyclic and non-cyclic thioureas can be used in the same manner as in the case of the above, but unsubstituted thiourea {S = C (NH2)2} Is particularly preferable. Regarding firing conditions(1)As in the case of, the firing time may be appropriately adjusted according to the firing temperature.
[0024]
Also, the above(3)According to this method, sulfur-containing titanium dioxide in which a part of the titanium atom of the present invention is substituted with a sulfur atom and a part of an oxygen atom is substituted with a nitrogen atom can be easily produced. For example, an aqueous solution of titanium sulfate is neutralized with ammonia water or ammonia gas to precipitate ammonium sulfate ammonium, filtered and dried to obtain a powder, which is calcined at 600 ° C. for 3 hours at atmospheric pressure, and the above. Such a sulfur-containing titanium dioxide can be easily produced. Note that the higher the firing temperature and the longer the firing time during firing, the lower the sulfur and nitrogen contents. Therefore, the firing temperature and firing time may be adjusted so that the desired content is obtained.
[0025]
The sulfur-containing metal oxide of the present invention produced in this way not only functions as a photocatalyst, but also has a feature that it has activity in the visible light region where the metal oxide not containing sulfur does not show activity. Have. For this reason, it can use suitably as a photo-oxidation catalyst at the time of converting an alicyclic hydrocarbon compound, such as adamantane, into oxygen and a ketone by oxygen oxidation. Such a feature is expressed by substituting a metal atom with a nonmetallic element, and the nonmetallic element is not limited to sulfur. For example, when a titanium atom is substituted with an element other than S such as phosphorus, a material containing a nonmetallic element such as phosphorus may be used as a precursor before firing.
The alicyclic hydrocarbon compound that can be used as a raw material in the photooxidation reaction is not particularly limited, but adamantane is preferably used from the viewpoint of the usefulness of the product.
[0026]
Although the reaction method is not particularly limited, it is preferable that the alicyclic hydrocarbon compound is brought into contact with oxygen while irradiating light in a solvent in the presence of the sulfur-containing metal oxide of the present invention. In this case, the solvent is not particularly limited as long as it is less oxidized than the alicyclic hydrocarbon compound to be oxidized, but nitriles such as acetonitrile and butyronitrile can be preferably used. Further, the reaction method is not particularly limited, and it can be carried out either batchwise or flow-through. The catalyst amount is not particularly limited, and a wide range from 0.01 parts by weight to 5000 parts by weight with respect to 100 parts by weight of the alicyclic hydrocarbon can be applied. it can. The intensity and wavelength of light to be irradiated are not particularly limited, and the intensity matched to the amount of catalyst (that is, the catalyst absorbs all light) is recommended in terms of energy efficiency, and the catalyst can also absorb the wavelength. Although it will not specifically limit if it is a wavelength (including ultraviolet rays), it is desirable to select a wavelength in the visible light region in order to maximize the characteristics of the present catalyst. The reaction time and reaction temperature are not particularly limited, and may be appropriately determined depending on the progress of the reaction.
[0027]
【Example】
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
[0028]
Example 1
In 500 ml of ethanol, 15 g (53 mmol) of titanium tetraisopropoxide and 10 g (132 mmol, 2.5 eq. ToTi) of thiourea were mixed and stirred for 1 hour or more until evenly dissolved. This solution was distilled off under reduced pressure using an evaporator, taken out before being completely dried, and air-dried under atmospheric pressure. This powder was calcined in the atmosphere at 500 ° C. for 3 hours to obtain a yellow to white powder. When X-ray photoelectron spectroscopy measurement was performed on the obtained powder, peaks corresponding to Ti2p, S2p and O1s were observed at 459.7 eV, 169.0 eV and 531.3 eV, respectively. Was a sulfur-containing titanium oxide substituted with a sulfur atom. Moreover, when the composition was determined based on the intensity ratio of these peaks, the composition was Ti0.87S0.13O2.00Met. In addition, the sulfur-containing titanium oxide obtained in the present example was S-TiO.2Abbreviated as (500 ° C. 3 h).
[0029]
FIG. 1 shows the diffuse reflection absorption spectrum of each powder obtained in Example 1, the diffuse reflection absorption spectrum of the powder obtained in Examples 2-3 described later, and the diffuse reflection absorption of PT-101, which is commercially available titanium dioxide. Shown with spectrum. Moreover, the powder S-TiO obtained in Example 12The X-ray photoelectron spectroscopy spectra at (500 ° C. for 3 h) are shown in FIGS. As shown in FIG. 1, it can be seen that all of these powders have absorption in the visible light region.
[0030]
Example 2
A powder was obtained in the same manner as in Example 1 except that the firing conditions were 600 ° C. and 3 hours. From the X-ray photoelectron spectroscopy measurement, the obtained powder has a composition Ti0.90S0.10O2.00It was confirmed that this was a sulfur-containing titanium oxide in which the titanium atom was replaced with a sulfur atom. In addition, the sulfur-containing titanium oxide obtained in the present example was S-TiO.2Abbreviated as (600 ° C. 3 h).
[0031]
Example 3
A powder was obtained in the same manner as in Example 1 except that the firing conditions were 700 ° C. and 3 hours. From the X-ray photoelectron spectroscopy measurement, the obtained powder has a composition Ti0.91S0.09O2.00It was confirmed that this was a sulfur-containing titanium oxide in which the titanium atom was replaced with a sulfur atom. In addition, the sulfur-containing titanium oxide obtained in the present example was S-TiO.2Abbreviated as (700 ° C. 3 h).
[0032]
Example 4
A powder was obtained in the same manner as in Example 1 except that the firing conditions were 500 ° C. and 10 hours. From the X-ray photoelectron spectroscopy measurement, the obtained powder has a composition Ti0.88S0. 12O2.00It was confirmed that this was a sulfur-containing titanium oxide in which the titanium atom was replaced with a sulfur atom. In addition, the sulfur-containing titanium oxide obtained in the present example was S-TiO.2Abbreviated as (500 ° C., 10 hours).
[0033]
Example 5
A powder was obtained in the same manner as in Example 1 except that the firing conditions were 600 ° C. and 10 hours. From the X-ray photoelectron spectroscopy measurement, the obtained powder has a composition Ti0.90S0.10O2.00It was confirmed that this was a sulfur-containing titanium oxide in which the titanium atom was replaced with a sulfur atom. In addition, the sulfur-containing titanium oxide obtained in the present example was S-TiO.2Abbreviated as (600 ° C. 10 h).
[0034]
Example 6
30% Ti (SO4)2After diluting the
[0035]
Example 7
30% Ti (SO4)2After diluting the
[0036]
Reference example
TiCl4(99.0%) to 25% NH3An aqueous solution was added dropwise, and the pH was adjusted to around 7 to obtain a white suspension. After filtration under reduced pressure, it was washed 10 times with pure water on Nutsche. The white cake was dried at 107 ° C. overnight. The slightly yellowish agglomerated solid was crushed in a mortar and calcined at 600 ° C. for 3 hours in an ammonia stream (1 ml / min.) To obtain a yellow powder. From the X-ray photoelectron spectroscopy measurement, the obtained powder has a composition Ti1.00O1.99N0.01It was confirmed that this was a titanium oxide in which some of the oxygen atoms were substituted with nitrogen atoms. The sulfur-containing titanium oxide obtained in this example is abbreviated as TiNO.
[0037]
Examples 8-11 and Comparative Examples 1-2
To each of the six test tubes, 0.04 g of adamantane, 1.96 g of butyronitrile and 2.00 g of acetonitrile were added to obtain uniform solutions. The sulfur-containing titanium oxide of the present invention obtained in Examples 1, 4, 2, and 5 and commercially available titania (St-41 Comparative Example 1, P-25 Comparative Example 2) were added to each test tube, and further slurred. Larpiece was added and suspended. The amount of addition was determined by preliminary experiments by examining the amount of catalyst added to each powder so that the quantum yields can be compared, and searching for conditions that can absorb all of the light of the irradiation light. In addition, ultrasonic treatment was used for dissolution and suspension. The test tube was sealed with a silicone stopper and a flow seal. Oxygen (gas) was injected at 2 ml / min. Using an injection needle. And bubbled for 15 minutes. (At this time, the needle for pressure release was also stabbed.)
Light irradiation was performed on each test tube using a 1000 W xenon lamp. At this time, a short wavelength cut filter (cut below 440 nm) was used for wavelength control. During the reaction, the mixture was stirred with a magnetic stirrer.
[0038]
After the reaction, the catalyst and the solution were separated by centrifugation, and the product was evaluated for the solution. Analysis was performed by gas chromatograph and GCMASS.
[0039]
The results are shown in FIG. Here, St-41 and P-25 are commercially available titanium dioxide, and S-TiO.2Is sulfur-containing titanium dioxide in which some of the titanium atoms of the present invention are substituted with sulfur atoms. The parentheses indicate the firing conditions.
[0040]
As shown in FIG. 5, the S-TiO of the present invention.2Is clearly higher in activity when irradiated with visible light of 440 nm or less than commercially available titanium dioxide.
[0041]
Examples 12-13 and Comparative Examples 3-5
The powder obtained in Examples 6 and 7 was oxidized with adamantane as in Example 8. The results are shown in FIG. Here, St-41 and P-25 are commercially available titanium dioxide, and TiNO is a powder prepared in a reference example. As shown in FIG. 6, the sulfur-containing titanium oxide in which some of the titanium atoms of the present invention are substituted with sulfur atoms and some of the oxygen atoms are substituted with nitrogen atoms is visible at 440 nm or less. When irradiated with light, commercially available titanium dioxide or some of the titanium atoms are not substituted with sulfur atoms, but they are clearly more active than titanium oxides with some oxygen atoms substituted with nitrogen atoms. It turns out to be expensive.
[0042]
Example 14
Strontium titanate (manufactured by Fuji Titanium Industry Co., Ltd., HPST-1) 2.0011 g and thiourea (manufactured by WAKO, min. 98.0%) 8.0024 g were mixed at a ratio of 1: 4. The mixture was placed in a mortar and stirred until it was uniform while rubbing so that the particle size was the same. The mixture was transferred to a firing boat and fired in an electric furnace (Shinka Denki Seisakusho, model: ST-05). Firing was performed at 300 ° C. for 3 hours. After firing, the hardened yellow substance was pulverized until it became powdery. The sulfur content of this sulfur-containing strontium titanate was calculated from the X-ray photoelectron spectroscopic spectrum and found to be 1.5%. The sulfur-containing strontium titanate obtained in this example was converted to S-SrTiO.3Abbreviated as (300 ° C). FIG. 7 shows the diffuse reflection absorption spectrum of the powder obtained in this example. The diffuse reflection absorption spectrum of the powder obtained in Examples 15 to 16, which will be described later, and commercially available strontium titanate (SrTiO3) And the diffuse reflection absorption spectrum. As shown in FIG. 7, it can be seen that all of these powders have absorption in the visible light region.
[0043]
Example 15
A powder was obtained in the same manner as in Example 8 except that the baking conditions were 400 ° C. and 3 hours. The sulfur content of this sulfur-containing strontium titanate was calculated from the X-ray photoelectron spectroscopic spectrum and found to be 1.5%. The sulfur-containing strontium titanate obtained in this example was converted to S-SrTiO.3Abbreviated as (400 ° C).
[0044]
Example 16
A powder was obtained in the same manner as in Example 8 except that the baking conditions were changed to 500 ° C. for 3 hours. The sulfur content of this sulfur-containing strontium titanate was calculated from the X-ray photoelectron spectroscopic spectrum and found to be 0.3%. The sulfur-containing strontium titanate obtained in this example was converted to S-SrTiO.3Abbreviated as (500 ° C).
[0045]
Example 17
2.0010 g of zirconium oxide (manufactured by Wako) and 8.0050 g of thiourea (manufactured by WAKO, min. 98.0%) were mixed at a ratio of 1: 4. The mixture was placed in a mortar and stirred uniformly while rubbing so that the particle diameters were the same. The mixture was transferred to a firing boat and fired in an electric furnace (Shinka Denki Seisakusho, model: ST-05). Firing was performed at 400 ° C. for 3 hours. After firing, the hardened yellow substance was pulverized until it became powdery. The sulfur content of these sulfur-containing zirconium oxides was calculated from the X-ray photoelectron spectroscopic spectrum and found to be 1.4%. The sulfur-containing zirconium oxide obtained in this example was converted to S-ZrO.2Abbreviated as (400 ° C). FIG. 8 shows the diffuse reflection absorption spectrum of the powder obtained in this example, the diffuse reflection absorption spectrum of the powder obtained in Example 18 described later, and a commercially available zirconium oxide (ZrO).2) And the diffuse reflection absorption spectrum. As shown in FIG. 8, it can be seen that all of these powders have absorption in the visible light region.
[0046]
Example 18
A powder was obtained in the same manner as in Example 17 except that the baking conditions were changed to 500 ° C. for 3 hours. The sulfur content of the sulfur-containing zirconium oxide was calculated from the X-ray photoelectron spectrum and found to be 0.1%. The sulfur-containing zirconium oxide obtained in this example was converted to S-ZrO.2Abbreviated as (500 ° C).
[0047]
Example 19
2.0593 g of tantalum oxide (manufactured by Wako, min. 99.8%) and 8.2365 g of thiourea (manufactured by WAKO, min. 98.0%) were mixed at a ratio of 1: 4. The mixture was placed in a mortar and stirred until it was uniform while rubbing so that the particle size was the same. The mixture was transferred to a firing boat and fired in an electric furnace (Shinka Denki Seisakusho, model: ST-05). Firing was performed at 300 ° C. for 3 hours. After firing, the hardened yellow substance was pulverized until it became powdery. The sulfur content of these sulfur-containing tantalum oxides was calculated from the X-ray photoelectron spectroscopy spectrum and found to be 1.8%. The sulfur-containing tantalum oxide obtained in this example was converted to S-Ta.2O5Abbreviated as (300 ° C). FIG. 9 shows the diffuse reflection absorption spectrum of the powder obtained in this example, and the diffuse reflection absorption spectrum of the powder obtained in Examples 20 and 21 described later and a commercially available tantalum oxide (Ta2O5) And the diffuse reflection absorption spectrum. As can be seen from FIG. 9, these powders all have absorption in the visible light region.
[0048]
Example 20
A powder was obtained in the same manner as in Example 19 except that the firing condition was 3 hours at 400 ° C. The sulfur content of the sulfur-containing tantalum oxide was calculated from the X-ray photoelectron spectrum and found to be 1.5%. The sulfur-containing tantalum oxide obtained in this example was converted to S-Ta.2O5Abbreviated as (400 ° C).
[0049]
Example 21
A powder was obtained in the same manner as in Example 19 except that the baking conditions were 500 ° C. and 3 hours. The sulfur content of the sulfur-containing zirconium oxide was calculated from the X-ray photoelectron spectroscopy spectrum and found to be 0.5%. The sulfur-containing tantalum oxide obtained in this example was converted to S-Ta.2O5Abbreviated as (500 ° C).
[0050]
Example 22, Comparative Example 6
The oxidation power of the powder obtained in Example 14 was compared with that of commercially available strontium titanate (manufactured by Fuji Titanium Industry Co., Ltd., HPST-1) using the oxidative decomposition rate of methylene blue as an index. First, a methylene blue aqueous solution (0.01 mM) adjusted to ph = 4 with hydrochloric acid was prepared. 45 ml of the solution was collected and S-SrTiO obtained in Example 14 was used.30.9 g (300 ° C.) was added. In order to sufficiently adsorb methylene blue on the catalyst surface, the mixture was stirred overnight (6-12 hr) while being shielded from light with aluminum foil. The stirred mixed solution was placed in a 3 ml test tube and irradiated with a 500 W xenon lamp for 1 minute, 5 minutes, and 10 minutes, respectively. The wavelength of light was cut with a cut filter at wavelengths of 340 nm or less, 420 nm or less, or 440 nm or less. The mixed solution after light irradiation and before light irradiation was collected and centrifuged twice, and then the absorbance of methylene blue was measured by UV-VIS spectrum (SHIMAZU UV-2500PC). Among the measured absorbances, the absorption peak intensity around 663 nm was plotted with time, and the decomposition rate of methylene blue when each filter was used was calculated. The same operation was performed with 0.9 g of commercially available strontium titanate, and the decomposition rate of methylene blue was calculated. The results are shown in FIG. S-SrTiO regardless of the cut wavelength3It can be seen that the decomposition rate by (300 ° C.) is faster than that of commercially available strontium titanate. In particular, even in visible light (cut below 440 nm), S-SrTiO3It can be seen that the photo-oxidation reaction by (300 ° C.) occurs.
[0051]
Example 23, Comparative Example 7
The powder obtained in Example 19 was compared with a commercially available tantalum oxide (manufactured by Wako) using the oxidation decomposition rate of methylene blue as an index. First, a methylene blue aqueous solution (0.02 mM) adjusted to pH = 4 with hydrochloric acid was prepared. 35 ml of the solution was collected and the S-Ta obtained in Example 19 was collected.2O50.5 g (300 ° C.) was added. In order to sufficiently adsorb methylene blue on the catalyst surface, the mixture was stirred overnight (6-12 hr) while being shielded from light with aluminum foil. The stirred mixed solution was placed in a 3 ml test tube and irradiated with a 1000 W xenon lamp for 1 minute, 5 minutes, and 10 minutes, respectively. The light wavelength was cut at 340 nm, 420 nm, 440 nm, and 500 nm or less with a cut filter. The oxidation rate of methylene blue was calculated in the same manner as in Example 24. Further, the oxidation rate of methylene blue was calculated for 0.5 g of commercially available tantalum oxide by the same operation. The results are shown in FIG. S-Ta regardless of the cut wavelength2O5It can be seen that the decomposition rate by (300 ° C.) is faster than that of commercially available tantalum oxide.2O5It can be seen that the photo-oxidation reaction by (300 ° C.) occurs.
[0052]
【The invention's effect】
The sulfur-containing metal oxide of the present invention is a novel sulfur-containing metal oxide in which a part of the metal atom is substituted with a sulfur atom, and is useful as a photooxidation catalyst having activity in visible light. When the sulfur-containing metal oxide of the present invention is used as a catalyst for the oxidation reaction of an alicyclic hydrocarbon compound such as adamantane, adamantanone and adamantanol are more efficiently used than when a conventional photooxidation catalyst is used. Can be manufactured. Further, according to the production method of the present invention, such a sulfur-containing metal oxide of the present invention can be produced easily and at low cost.
[Brief description of the drawings]
FIG. 1 is a diffuse reflection absorption spectrum of sulfur-containing titanium dioxide in which some of the titanium atoms are substituted with sulfur atoms.
2 is an X-ray photoelectron spectroscopy spectrum (titanium 2p) of the sulfur-containing titanium oxide of Example 1. FIG.
3 is an X-ray photoelectron spectroscopy spectrum (sulfur 2p) of the sulfur-containing titanium oxide of Example 1. FIG.
4 is an X-ray photoelectron spectroscopy spectrum (oxygen 1s) of the sulfur-containing titanium oxide of Example 1. FIG.
FIG. 5 is a graph showing the reaction results of Examples 8-11 and Comparative Examples 1-2.
FIG. 6 is a graph showing the reaction results of Examples 12 to 13 and Comparative Examples 3 to 5.
FIG. 7 is a diffuse reflection absorption spectrum of sulfur-containing strontium titanate obtained in Examples 14 to 16 and commercially available strontium titanate.
FIG. 8 is a diffuse reflection absorption spectrum of sulfur-containing zirconium oxide obtained in Examples 17 and 18 and commercially available zirconium oxide.
FIG. 9 is a diffuse reflection absorption spectrum of sulfur-containing tantalum oxide obtained in Examples 19 to 21 and commercially available tantalum oxide.
FIG. 10 is a graph showing reaction rates of Example 22 and Comparative Example 6.
FIG. 11 is a graph showing the reaction rates of Example 23 and Comparative Example 7.
Claims (8)
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| JP2006082071A (en) * | 2004-02-20 | 2006-03-30 | Sekisui Jushi Co Ltd | Photocatalytic composition, building material for interior finish, coating material, synthetic resin molded body, method for utilizing photocatalyst and method for decomposing harmful substance |
| JP4523344B2 (en) * | 2004-06-16 | 2010-08-11 | 東邦チタニウム株式会社 | Method for producing titanium oxide dispersion |
| JP2006192318A (en) * | 2005-01-11 | 2006-07-27 | Sekisui Jushi Co Ltd | Photocatalyst composition |
| JP4639355B2 (en) * | 2005-08-23 | 2011-02-23 | 株式会社アトックス | Method for producing visible light responsive photocatalyst |
| EP2072582B1 (en) | 2006-10-13 | 2011-12-07 | Nitto Boseki CO., LTD. | Polymeric composition comprising metal alkoxide condensation product, organic silane compound and boron compound |
| JP5030735B2 (en) * | 2007-02-21 | 2012-09-19 | 国立大学法人九州工業大学 | N- and / or S-doped tubular titanium oxide particles and method for producing the same |
| JP4841506B2 (en) * | 2007-06-11 | 2011-12-21 | 東邦チタニウム株式会社 | Method for producing metal oxide |
| KR100935512B1 (en) * | 2008-05-15 | 2010-01-06 | 경북대학교 산학협력단 | Manufacturing method of TiO2 photocatalyst and TiO2 photocatalyst manufactured by the same |
| US9248432B2 (en) | 2011-06-27 | 2016-02-02 | The University Of Tokyo | Titanium oxide photocatalyst having copper compounds supported thereon, and method for producing same |
| WO2017043028A1 (en) * | 2015-09-07 | 2017-03-16 | 国立大学法人東京工業大学 | Catalyst material for organic compound synthesis and method for producing organic compound using same |
| WO2019142695A1 (en) * | 2018-01-16 | 2019-07-25 | 昭和電工株式会社 | Oxygen reduction catalyst |
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