JP2010207769A - 水素製造用光触媒 - Google Patents
水素製造用光触媒 Download PDFInfo
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- JP2010207769A JP2010207769A JP2009059370A JP2009059370A JP2010207769A JP 2010207769 A JP2010207769 A JP 2010207769A JP 2009059370 A JP2009059370 A JP 2009059370A JP 2009059370 A JP2009059370 A JP 2009059370A JP 2010207769 A JP2010207769 A JP 2010207769A
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- photocatalyst
- hydrogen
- clay mineral
- oxide
- metal oxide
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 103
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 69
- 239000001257 hydrogen Substances 0.000 title claims abstract description 69
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000002734 clay mineral Substances 0.000 claims abstract description 59
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 54
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims abstract description 28
- 239000002131 composite material Substances 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 50
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 32
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 31
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical group [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 31
- 229940112669 cuprous oxide Drugs 0.000 claims description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 24
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 24
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 16
- 235000019253 formic acid Nutrition 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 14
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 11
- 150000007524 organic acids Chemical class 0.000 claims description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 9
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 9
- 229910052723 transition metal Inorganic materials 0.000 claims description 9
- 150000003624 transition metals Chemical class 0.000 claims description 9
- 150000001768 cations Chemical class 0.000 claims description 8
- 229910000278 bentonite Inorganic materials 0.000 claims description 6
- 239000000440 bentonite Substances 0.000 claims description 6
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000008346 aqueous phase Substances 0.000 claims description 5
- 229910000269 smectite group Inorganic materials 0.000 claims description 5
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 claims description 4
- 229910021647 smectite Inorganic materials 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000010949 copper Substances 0.000 description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 229910021645 metal ion Inorganic materials 0.000 description 11
- 238000005341 cation exchange Methods 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000005342 ion exchange Methods 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000002524 electron diffraction data Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910018883 Pt—Cu Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- -1 Na + Chemical class 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- GOKIPOOTKLLKDI-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O.CC(O)=O GOKIPOOTKLLKDI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000009790 rate-determining step (RDS) Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000011882 ultra-fine particle Substances 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052626 biotite Inorganic materials 0.000 description 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical group OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052628 phlogopite Inorganic materials 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000002256 photodeposition Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 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
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Abstract
【解決手段】粘土鉱物に金属酸化物を担持させた複合体で構成され、光照射下で水素源となる有機物を分解して水素を発生させるために使用する水素製造用光触媒である。
【選択図】なし
Description
前記粘土鉱物の交換性陽イオンを銅(II)イオンに置換した後、該銅(II)イオンを、還元剤としてチオ硫酸ナトリウムを用いて銅(I)イオンに還元することを含む、製造方法。
ベントナイト(日本砿研製、津軽2号)10gを1000mlの蒸留水に分散し、この分散液を遠心分離することにより、ベントナイトに含有されるモンモリロナイトを精製分離した。
実施例1で得られたCu2O/MTを、20mlの5vol%エタノール水溶液に分散させ、塩化白金酸を白金(Pt)担持量が亜酸化銅に対して0.5wt%になるように加えた。その後、容器内をアルゴンガスで置換し、密閉した後にハロゲンランプ(280mW/cm2)を24時間照射することでPtを担持した。その後、遠心分離によってエタノールを除去し、不活性ガス中で乾燥させて、Ptが担持されたCu2O/MT(Pt−Cu2O/MT)を得た。
100mmol/lの硫酸銅(II)水溶液100mlに、チオ硫酸ナトリウム粉末20gを溶解させ、これに10mol/lの水酸化ナトリウム水溶液を10ml加えた。この溶液を攪拌しながら90℃に30分間保温した。得られた沈殿物を遠心分離によって分離し、不活性ガス中で乾燥させて、非担持の亜酸化銅粉末(Cu2O)を得た。
実施例1と同様にして、モンモリロナイトを精製分離した。
実施例3で得られたFe2O3/MTを、20mlの5vol%エタノール水溶液に分散させ、塩化白金酸をPt担持量が酸化鉄(III)に対して0.5wt%になるように加えた後、容器内をアルゴンガスで置換した後に密閉し、ハロゲンランプ(280mW/cm2)を24時間照射することでPtを担持した。その後、遠心分離によってエタノールを除去し、不活性ガス中で乾燥させて、Ptが担持されたFe2O3/MT(Pt−Fe2O3/MT)を得た。
三核酢酸鉄硝酸塩を600℃で10時間焼成し、非担持の酸化鉄(III)(Fe2O3)を得た。
(1)水素源としてアルコールを用いた場合
光触媒反応容器として、パイレックス(登録商標)ガラス製の容器(容積21ml)を用いた。これに10vol%のアルコール水溶液を入れ、Cu2Oを2.4mg含む量の光触媒試料(実施例1〜2で製造した試料の場合は22.4mg、比較例1で製造した試料の場合は2.4mg)を添加した後、ガラス容器内をアルゴンガス(純度99.999%)で置換した。その後、容器を密閉し、ハロゲンランプ(280mW/cm2)で光を照射し、24時間後に容器内のガスを採取し、ガスクロマトグラフ((株)島津製作所製、GC−14B)を用いて水素生成量を測定した。なお、アルコールとして、メタノール、エタノール、n−プロパノール、及びn−ブタノールを使用し、反応溶液のpHはそれぞれ、6.7(メタノール水溶液)、6.8(エタノール水溶液)、6.9(プロパノール水溶液)、及び6.5(ブタノール水溶液)であった。その結果を表1に示す。
10vol%のギ酸及び酢酸水溶液と、実施例1〜3及び比較例1〜2で製造した光触媒試料を用いた以外は、上記(1)と同様にして水素生成量を測定した。その結果を表2に示す。なお、光触媒の添加量は、実施例1〜2で製造した試料は、22.4mg、比較例1で製造した試料は、2.4mg、実施例3〜4で製造した試料は、20.6mg、比較例2で製造した試料は、0.6mgであった。また、反応溶液のpHは、2.5(酢酸水溶液)、及び2.1(ギ酸水溶液)であった。
Claims (14)
- 粘土鉱物に金属酸化物を担持させた複合体で構成され、光照射下で水素源となる有機物を分解して水素を発生させるために使用する水素製造用光触媒。
- 前記粘土鉱物が、スメクタイト族粘土鉱物である、請求項1に記載の光触媒。
- 前記スメクタイト族粘土鉱物が、ベントナイト又はモンモリロナイトである、請求項1又は2に記載の光触媒。
- 前記金属酸化物の粒子径が、5〜150nmである、請求項1〜3のいずれかに記載の光触媒。
- 前記金属酸化物が、亜酸化銅又は酸化鉄(III)である、請求項1〜4のいずれかに記載の光触媒。
- 前記有機物が、アルコール又は有機酸である、請求項1〜5のいずれかに記載の光触媒。
- 前記アルコールが、炭素数1〜4のアルコールであり、前記有機酸が酢酸又はギ酸である、請求項6に記載の光触媒。
- 前記金属酸化物が亜酸化銅であり、前記有機物が炭素数1〜4のアルコール、酢酸又はギ酸である、請求項7に記載の光触媒。
- 前記金属酸化物が酸化鉄(III)であり、前記有機物がギ酸であり、且つ前記光が可視光である、請求項7に記載の光触媒。
- 前記金属酸化物の表面に遷移金属触媒が担持されている、請求項1〜9のいずれかに記載の光触媒。
- 粘土鉱物に亜酸化銅を担持させた複合体。
- 請求項11に記載の複合体の製造方法であって、
前記粘土鉱物の交換性陽イオンを銅(II)イオンに置換した後、該銅(II)イオンを、還元剤としてチオ硫酸ナトリウムを用いて銅(I)イオンに還元することを含む、製造方法。 - 上記項11に記載の複合体からなる光触媒。
- 請求項1〜10及び請求項13のいずれかに記載の光触媒を用いて水素を製造する方法であって、光照射下で、水相中において該光触媒を有機物と接触させることにより水素を発生させる方法。
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012005928A (ja) * | 2010-06-22 | 2012-01-12 | Aomori Prefectural Industrial Technology Research Center | 粘土光触媒およびその製造方法 |
CN102464322A (zh) * | 2010-11-02 | 2012-05-23 | 中国科学院化学研究所 | 一种氧化亚铜粘土纳米复合物及其制备方法 |
JP2013221175A (ja) * | 2012-04-16 | 2013-10-28 | Tadatomo Suga | 金属触媒下及び不活性ガス雰囲気下で有機酸ガスを用いた表面酸化物除去方法及び接合装置 |
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6142813A (ja) * | 1984-07-31 | 1986-03-01 | 日本蚕毛染色株式会社 | 導電性無機材料 |
JPH06200189A (ja) * | 1992-12-28 | 1994-07-19 | Osaka Organic Chem Ind Ltd | 防汚塗料用顔料およびそれを用いてなる防汚塗料 |
JPH0959892A (ja) * | 1995-08-23 | 1997-03-04 | K G Pack Kk | 酸化チタン含有紙、段ボールおよび脱臭エレメント |
JPH09225318A (ja) * | 1996-02-23 | 1997-09-02 | Riken Corp | 水の光分解用触媒及びそれを用いた水素の製造方法 |
JPH09262473A (ja) * | 1996-03-29 | 1997-10-07 | Mitsubishi Heavy Ind Ltd | 酸化鉄光触媒とそれによる水素の製造方法 |
JPH09328311A (ja) * | 1996-05-31 | 1997-12-22 | Mitsubishi Chem Corp | イオン交換性層状珪酸塩の球状造粒物およびその製造法 |
JPH10244163A (ja) * | 1997-03-04 | 1998-09-14 | Nikon Corp | 可視光領域で触媒活性をもつ光触媒 |
JP2006326453A (ja) * | 2005-05-25 | 2006-12-07 | Tokyo Institute Of Technology | 酸化チタン含有スメクタイト光触媒複合材料 |
-
2009
- 2009-03-12 JP JP2009059370A patent/JP5548934B2/ja not_active Expired - Fee Related
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6142813A (ja) * | 1984-07-31 | 1986-03-01 | 日本蚕毛染色株式会社 | 導電性無機材料 |
JPH06200189A (ja) * | 1992-12-28 | 1994-07-19 | Osaka Organic Chem Ind Ltd | 防汚塗料用顔料およびそれを用いてなる防汚塗料 |
JPH0959892A (ja) * | 1995-08-23 | 1997-03-04 | K G Pack Kk | 酸化チタン含有紙、段ボールおよび脱臭エレメント |
JPH09225318A (ja) * | 1996-02-23 | 1997-09-02 | Riken Corp | 水の光分解用触媒及びそれを用いた水素の製造方法 |
JPH09262473A (ja) * | 1996-03-29 | 1997-10-07 | Mitsubishi Heavy Ind Ltd | 酸化鉄光触媒とそれによる水素の製造方法 |
JPH09328311A (ja) * | 1996-05-31 | 1997-12-22 | Mitsubishi Chem Corp | イオン交換性層状珪酸塩の球状造粒物およびその製造法 |
JPH10244163A (ja) * | 1997-03-04 | 1998-09-14 | Nikon Corp | 可視光領域で触媒活性をもつ光触媒 |
JP2006326453A (ja) * | 2005-05-25 | 2006-12-07 | Tokyo Institute Of Technology | 酸化チタン含有スメクタイト光触媒複合材料 |
Non-Patent Citations (2)
Title |
---|
KAKUTA, S. ET AL: "Correlation between Preparation Procedure of Fe2O3 Embedded in Clay and Its Photocatalytic Activity", TRANS. MATER. RES. SOC. JPN., vol. 32, no. 3, JPN6013023278, September 2007 (2007-09-01), pages 689 - 692, ISSN: 0002532216 * |
佐藤真理: "Pt/TiO2の光触媒作用 II.気相光コルベ反応(予稿)", 触媒, vol. 24, no. 4, JPN6013023280, 10 September 1982 (1982-09-10), pages 321 - 323, ISSN: 0002532217 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012005928A (ja) * | 2010-06-22 | 2012-01-12 | Aomori Prefectural Industrial Technology Research Center | 粘土光触媒およびその製造方法 |
CN102464322A (zh) * | 2010-11-02 | 2012-05-23 | 中国科学院化学研究所 | 一种氧化亚铜粘土纳米复合物及其制备方法 |
JP2014500788A (ja) * | 2010-11-04 | 2014-01-16 | 中国科学院理化技術研究所 | バイオマス誘導体をフォトカタリシス・改質して水素を製造するための半導体光触媒及びその製造と応用 |
JP2013221175A (ja) * | 2012-04-16 | 2013-10-28 | Tadatomo Suga | 金属触媒下及び不活性ガス雰囲気下で有機酸ガスを用いた表面酸化物除去方法及び接合装置 |
JP2016117810A (ja) * | 2014-12-19 | 2016-06-30 | 大建工業株式会社 | 不燃塗料組成物、それを用いた不燃性板材及び耐火性構造 |
CN110496624A (zh) * | 2019-08-22 | 2019-11-26 | 四川建筑职业技术学院 | 一种用于污水处理的复合材料及其制备方法 |
JP7399423B2 (ja) | 2020-06-09 | 2023-12-18 | 国立大学法人弘前大学 | 触媒電極、その製造方法およびそれを用いたギ酸酸化方法 |
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