JP2010184828A - 水素製造方法 - Google Patents
水素製造方法 Download PDFInfo
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- JP2010184828A JP2010184828A JP2009029494A JP2009029494A JP2010184828A JP 2010184828 A JP2010184828 A JP 2010184828A JP 2009029494 A JP2009029494 A JP 2009029494A JP 2009029494 A JP2009029494 A JP 2009029494A JP 2010184828 A JP2010184828 A JP 2010184828A
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 59
- 239000001257 hydrogen Substances 0.000 title claims abstract description 59
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 239000004065 semiconductor Substances 0.000 claims abstract description 58
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000001678 irradiating effect Effects 0.000 claims abstract description 7
- 150000001409 amidines Chemical class 0.000 claims abstract description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 38
- 239000000243 solution Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 25
- 230000015572 biosynthetic process Effects 0.000 description 12
- 239000000126 substance Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000004408 titanium dioxide Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- -1 nitrogen-containing compound Chemical class 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 230000027756 respiratory electron transport chain Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- OQLZINXFSUDMHM-UHFFFAOYSA-N Acetamidine Chemical compound CC(N)=N OQLZINXFSUDMHM-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 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 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- CPEOJEBZAIYHGD-UHFFFAOYSA-N 1,2-diazacycloundecene Chemical compound C1CCCCN=NCCCC1 CPEOJEBZAIYHGD-UHFFFAOYSA-N 0.000 description 1
- VWSLLSXLURJCDF-UHFFFAOYSA-N 2-methyl-4,5-dihydro-1h-imidazole Chemical compound CC1=NCCN1 VWSLLSXLURJCDF-UHFFFAOYSA-N 0.000 description 1
- BKCCAYLNRIRKDJ-UHFFFAOYSA-N 2-phenyl-4,5-dihydro-1h-imidazole Chemical compound N1CCN=C1C1=CC=CC=C1 BKCCAYLNRIRKDJ-UHFFFAOYSA-N 0.000 description 1
- LFCYHAXVBWPGQR-UHFFFAOYSA-N 2-propyl-4,5-dihydro-1h-imidazole Chemical compound CCCC1=NCCN1 LFCYHAXVBWPGQR-UHFFFAOYSA-N 0.000 description 1
- QDFXRVAOBHEBGJ-UHFFFAOYSA-N 3-(cyclononen-1-yl)-4,5,6,7,8,9-hexahydro-1h-diazonine Chemical compound C1CCCCCCC=C1C1=NNCCCCCC1 QDFXRVAOBHEBGJ-UHFFFAOYSA-N 0.000 description 1
- 0 CN(*)C(*)=N* Chemical compound CN(*)C(*)=N* 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- HZXMRANICFIONG-UHFFFAOYSA-N gallium phosphide Chemical compound [Ga]#P HZXMRANICFIONG-UHFFFAOYSA-N 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229940083254 peripheral vasodilators imidazoline derivative Drugs 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VFWRGKJLLYDFBY-UHFFFAOYSA-N silver;hydrate Chemical compound O.[Ag].[Ag] VFWRGKJLLYDFBY-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
【解決手段】 プロトン授与可能な電子授与性化合物及び水を含む溶液中に浸漬されたp型半導体酸化物に光エネルギーを照射することにより効率よく水素製造が可能となる。プロトン授与可能な電気授与性化合物が、含窒素共役系化合物であることが好ましく、含窒素共役系化合物中でもアミジン誘導体、含窒素6員環芳香族、含窒素5員環芳香族より選ばれた1種又は1種以上の組合せであることがより好ましい。
【選択図】図1
Description
磁気攪拌器4の上部に撹拌子3を入れた石英ガラスセル1を載置し、前記石英ガラスセル1中に電子授与性化合物水溶液中にp型半導体の粉末を分散させたp型半導体酸化物分散水溶液5を入れて、磁気撹拌子により撹拌しながら、光源から光を照射して反応をおこなった。
石英ガラスセル1は、上部にガス取り出し口6を有しており、そこから反応により発生したガスを採取してガスの分析に供した。
CuBi2O4:硝酸ビスマス5水和物の0.7mol/L酢酸溶液と硝酸銅3水和物の0.08mol/Lアセチルアセトン溶液を各々100℃に加熱し均質溶液を得た。両溶液を化学量論比となるように混合した後、溶剤を除去し、550℃で30分、大気中で加熱処理し、CuBi2O4粉末を得た。得られた粉末の粒径は、SEM観察より約40nmであった。
CuBi2O4と同様の方法により、CuNi2O4、CuNiO2粉末を合成した。各々の粒径は、約30nm、35nmであった。
NiO:アルドリッチ製試薬(ナノパウダー、99.8%)を使用した。粒径は約15nmであった。
石英ガラス製の上方照射型容器にプロトン授与可能な電子授与性化合物の10mM水溶液にp型半導体酸化物0.3gを入れ、攪拌しながら上部より光照射を行った。発生ガスを採取し、TCD検出器を用いたガスクロ分析を行い、水素ガス発生の有無を確認した。プロトン授与可能な電子授与性化合物の種類、半導体酸化物の種類、光照射条件、水素発生の状況を表1に示す。
本発明に関わる実施例では、明確なガス発生が認められ、ガスクロ分析により水素の発生が確認された。
p型半導体酸化物としてCu2Oを用い、プロトン授与可能な電子授与性化合物を用いずにXeランプにより光照射を行った。実施例1と同じ条件での光照射にもかかわらず明確な水素発生は認められなかった。
n型半導体酸化物としてTiO2(石原産業製、ST−02、光触媒グレード)、プロトン授与可能なプロトン授与可能な電子授与性化合物としてピリジン(10mM水溶液)を用い、高圧水銀ランプによる光照射を行った。TiO2の吸収が存在する波長の光照射にもかかわらず明確な水素発生は認められなかった。
2 石英ガラスセル
3 攪拌子
4 磁気攪拌器
5 p型半導体酸化物分散水溶液
6 ガス取り出し口
Claims (4)
- プロトン授与可能な電子授与性化合物の水溶液中に浸漬されたp型半導体酸化物に光エネルギーを照射することを特徴とする水素製造方法。
- 請求項1記載のプロトン授与可能な電気授与性化合物が、含窒素共役系化合物であることを特徴とする水素製造方法
- 請求項1又は2記載のプロトン授与可能な電気授与性化合物が、アミジン誘導体、含窒素6員環芳香族、含窒素5員環芳香族より選ばれた1種又は1種以上の組合せであることを特徴とする水素製造方法
- 請求項1記載の半導体酸化物が、銅、ニッケル及び銀より選ばれた1種又は1種以上の金属を含有するp型半導体酸化物であることを特徴とする請求項1乃至3のいずれかに記載の水素製造方法。
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113957394A (zh) * | 2021-09-27 | 2022-01-21 | 山东省科学院能源研究所 | 一种p型半导体薄膜氧化铋铜及其制备方法与应用 |
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JP2006223919A (ja) * | 2005-02-15 | 2006-08-31 | Tomohiro Akiyama | 機能性粉体および構造体 |
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Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS5855304A (ja) * | 1981-09-24 | 1983-04-01 | Buren Master Kk | 水分解物質及び水分解法 |
JPS59207801A (ja) * | 1983-05-12 | 1984-11-26 | Agency Of Ind Science & Technol | 水素の製造方法 |
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JP2003238104A (ja) * | 2002-02-18 | 2003-08-27 | Univ Tohoku | 水素生成光装置 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN113957394A (zh) * | 2021-09-27 | 2022-01-21 | 山东省科学院能源研究所 | 一种p型半导体薄膜氧化铋铜及其制备方法与应用 |
CN113957394B (zh) * | 2021-09-27 | 2023-09-26 | 山东省科学院能源研究所 | 一种p型半导体薄膜氧化铋铜及其制备方法与应用 |
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