JP2007125496A - Optical water decomposition catalyst and its manufacturing method - Google Patents
Optical water decomposition catalyst and its manufacturing method Download PDFInfo
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- JP2007125496A JP2007125496A JP2005320356A JP2005320356A JP2007125496A JP 2007125496 A JP2007125496 A JP 2007125496A JP 2005320356 A JP2005320356 A JP 2005320356A JP 2005320356 A JP2005320356 A JP 2005320356A JP 2007125496 A JP2007125496 A JP 2007125496A
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- water
- gallium nitride
- type gallium
- oxide
- catalyst
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 15
- 230000003287 optical effect Effects 0.000 title abstract 2
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 30
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 28
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims abstract description 21
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011701 zinc Substances 0.000 claims abstract description 21
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 19
- 239000011777 magnesium Substances 0.000 claims abstract description 19
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 18
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- NWAIGJYBQQYSPW-UHFFFAOYSA-N azanylidyneindigane Chemical compound [In]#N NWAIGJYBQQYSPW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000457 iridium oxide Inorganic materials 0.000 claims abstract description 6
- 229910003450 rhodium oxide Inorganic materials 0.000 claims abstract description 6
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims description 76
- 229910002601 GaN Inorganic materials 0.000 claims description 75
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 66
- 229910021529 ammonia Inorganic materials 0.000 claims description 31
- 239000002243 precursor Substances 0.000 claims description 26
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000003426 co-catalyst Substances 0.000 claims description 8
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 7
- 238000010304 firing Methods 0.000 claims description 7
- RFVVBBUVWAIIBT-UHFFFAOYSA-N beryllium nitrate Chemical compound [Be+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O RFVVBBUVWAIIBT-UHFFFAOYSA-N 0.000 claims description 6
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical group [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 claims description 6
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 5
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 5
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 5
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 5
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 5
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 229940044658 gallium nitrate Drugs 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 3
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 23
- 239000001301 oxygen Substances 0.000 abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 abstract description 23
- 239000001257 hydrogen Substances 0.000 abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 11
- -1 potassium nitride Chemical class 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract 1
- YJZATOSJMRIRIW-UHFFFAOYSA-N [Ir]=O Chemical class [Ir]=O YJZATOSJMRIRIW-UHFFFAOYSA-N 0.000 abstract 1
- 229910052804 chromium Inorganic materials 0.000 abstract 1
- 239000011651 chromium Substances 0.000 abstract 1
- 229910017052 cobalt Inorganic materials 0.000 abstract 1
- 239000010941 cobalt Substances 0.000 abstract 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 1
- 229910052742 iron Inorganic materials 0.000 abstract 1
- 229910052759 nickel Inorganic materials 0.000 abstract 1
- 229910052700 potassium Inorganic materials 0.000 abstract 1
- 239000011591 potassium Substances 0.000 abstract 1
- 239000010948 rhodium Substances 0.000 abstract 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- 230000000694 effects Effects 0.000 description 26
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 125000004429 atom Chemical group 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 8
- 239000010453 quartz Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000000295 emission spectrum Methods 0.000 description 6
- 150000004767 nitrides Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 238000005121 nitriding Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000012494 Quartz wool Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- QENHCSSJTJWZAL-UHFFFAOYSA-N magnesium sulfide Chemical compound [Mg+2].[S-2] QENHCSSJTJWZAL-UHFFFAOYSA-N 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 238000010672 photosynthesis Methods 0.000 description 2
- 230000029553 photosynthesis Effects 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 230000001678 irradiating effect Effects 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
- VSQYNPJPULBZKU-UHFFFAOYSA-N mercury xenon Chemical compound [Xe].[Hg] VSQYNPJPULBZKU-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/825—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with gallium, indium or thallium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- 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
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Abstract
Description
本発明は、ｐ型窒化ガリウム類を使用した光エネルギーを利用する水分解用の触媒に関する。 The present invention relates to a catalyst for water splitting using light energy using p-type gallium nitrides.
光エネルギーを利用して触媒反応を行う技術としては、固体触媒に光を照射して伝導帯に生成した電子で反応物を還元する技術、価電子帯で生成した正孔で反応物を酸化して生成物を得る技術等が知られている。
また、この技術を応用して、水を水素と酸素に完全に分解する光による水分解用触媒は、エネルギー変換の観点から注目を集めている。（例えば、非特許文献１〜３、特許文献１，２参照）
As a technology for performing a catalytic reaction using light energy, the solid catalyst is irradiated with light to reduce the reactant with electrons generated in the conduction band, and the reactant is oxidized with holes generated in the valence band. Techniques for obtaining products are known.
Moreover, a catalyst for water splitting by light that completely decomposes water into hydrogen and oxygen by applying this technique has attracted attention from the viewpoint of energy conversion. (For example, see Non-Patent
上記の非特許文献１には、水を水素と酸素に分解する触媒が開示されており、特にタンタルを含むアルカリやアルカリ度類金属のオキサイドが水の完全分解に対して高い活性を示すことが記載されている。また、特許文献１及び非特許文献２には、ｄ１０電子状態を持つゲルマニウム元素を含むナイトライド及びオキシナイトライドの水分解触媒作用について記載されている。
Non-Patent
さらに、非特許文献３には、可視光活性の水分解触媒の設計において、窒化ガリウムと酸化亜鉛の固溶体を使用することが記載されている。同文献には、この窒化ガリウムと酸化亜鉛の固溶体は水完全分解用触媒として機能するが、窒化ガリウム単独では水分解活性がみられないことが開示されている。
Furthermore, Non-Patent
特許文献２には、窒化物半導体への光照射によるガス発生方法が記載され、ガスの発生源が窒化物表面或いは接合された金属表面であることが開示されている。また、窒化ガリウムが水から水素と酸素を生成する触媒として機能することが記載されているが、化学量論的に水素と酸素を発生させるものではなく、多量の窒素が発生している。この現象は、窒化ガリウムが分解することに起因するものであり、したがってこの特許文献に記載の技術では、長期間安定に水から水素を得ることは困難である。
したがって、本発明はこれらの従来技術における問題点を解消して、長期間安定して、光照射により水を水素と酸素に高効率で分解することのできる水完全分解用触媒とその製造方法を提供することを目的とする。 Therefore, the present invention eliminates the problems in these prior arts, and provides a catalyst for water complete decomposition that can stably decompose water into hydrogen and oxygen by light irradiation with high efficiency and a method for producing the same. The purpose is to provide.
本発明者等は鋭意検討した結果、異種金属原子を添加したｐ型窒化ガリウムに、酸化ルテニウム等の助触媒を担持させることによって、上記課題が解決されることを発見し、本発明を完成したものである。 As a result of intensive studies, the present inventors have found that the above problem can be solved by supporting a promoter such as ruthenium oxide on p-type gallium nitride to which different metal atoms are added, and the present invention has been completed. Is.
すなわち、本発明は次の１〜１４の構成を採用するものである。
１．亜鉛、マグネシウム、ベリリウムから選択された金属原子を添加したｐ型窒化ガリウムに、酸化ルテニウム、酸化ニッケル、酸化コバルト、酸化鉄、酸化クロム、酸化ロジウム、酸化イリジウムから選択された助触媒を担持させたことを特徴とする光による水分解触媒。
２．亜鉛、マグネシウム、ベリリウムから選択された金属原子を添加したｐ型窒化ガリウムが、ｐ型窒化ガリウムインジウムであることを特徴とする１に記載の光による水分解触媒。
３．亜鉛、マグネシウム、ベリリウムから選択された金属原子の添加量が０．０００１〜７モル％であることを特徴とする１又は２に記載の光による水分解触媒。
４．助触媒が酸化ルテニウムであることを特徴とする１〜３のいずれかに記載の光による水分解触媒。
５．助触媒の担持量が０．１〜１０重量％であることを特徴とする１〜４のいずれかに記載の水分解触媒。
６．亜鉛、マグネシウム、ベリリウムから選択された金属原子を添加したｐ型窒化ガリウムの平均粒径が１０ｎｍ〜１０μｍであることを特徴とする１〜５のいずれかに記載の水分解触媒。
７．ガリウムに対する亜鉛、マグネシウム、ベリリウムから選択された金属の配合割合が０．０１〜２００モル％となるように、硫化ガリウム又は酸化ガリウムに、亜鉛、マグネシウム、ベリリウムから選択された金属原子を含む化合物を混合し、アンモニア気流下に焼成して得られたｐ型窒化ガリウムを、助触媒前駆体を含有する水又は有機溶媒溶液に浸漬後空気中で焼成することを特徴とする１〜６のいずれかに記載の光による水分解触媒の製造方法。
８．アンモニアの流量が５０〜１０００ｍＬ／分で、アンモニア気流下での焼成温度が８００〜１１００℃、焼成時間が１〜３０時間であることを特徴とする７に記載の水分解触媒の製造方法。
９．アンモニア気流下に焼成して得られたｐ型窒化ガリウムに対して、１〜５０モル％の硫化インジウムを添加した混合物を、アンモニア気流下で温度５００〜９００℃で０．５〜２４時間焼成して得られたｐ型窒化ガリウムインジウムを、助触媒前駆体を含有する水又は有機溶媒溶液に浸漬後空気中で焼成することを特徴とする７又は８に記載の水分解触媒の製造方法。
１０．助触媒前駆体となるトリルテニウムドデカカルボニルをテトラヒドロフランに溶解した溶液にｐ型窒化ガリウムを浸漬後、室温〜１００℃で１〜５時間還流し、さらに空気中で２００〜５００℃で１〜１０時間焼成することを特徴とする７〜９のいずれかに記載の水分解触媒の製造方法。
１１．硝酸亜鉛、硝酸マグネシウム、硝酸ベリリウムから選択された化合物と硝酸ガリウムを水に溶解し、アンモニア水を添加して得られた生成物を空気中で６００〜８００℃で焼成して前駆体を形成し、得られた前駆体をアンモニア気流下に焼成して得られたｐ型窒化ガリウムを、助触媒前駆体を含有する水又は有機溶媒溶液に浸漬後空気中で焼成することを特徴とする１〜６のいずれかに記載の光による水分解触媒の製造方法。
１２．アンモニアの流量が５０〜１０００ｍＬ／分で、アンモニア気流下での焼成温度が８００〜１１００℃、焼成時間が１〜３０時間であることを特徴とする１１に記載の水分解触媒の製造方法。
１３．アンモニア気流下に焼成して得られたｐ型窒化ガリウムに対して、１〜５０モル％の硫化インジウムを添加した混合物を、アンモニア気流下で温度５００〜９００℃で０．５〜２４時間焼成して得られたｐ型窒化ガリウムインジウムを、助触媒前駆体を含有する水又は有機溶媒溶液に浸漬後空気中で焼成することを特徴とする１１又は１２に記載の水分解触媒の製造方法。
１４．助触媒前駆体となるトリルテニウムドデカカルボニルをテトラヒドロフランに溶解した溶液にｐ型窒化ガリウムを浸漬後、室温〜１００℃で１〜５時間還流し、さらに空気中で２００〜５００℃で１〜１０時間焼成することを特徴とする１１〜１３のいずれかに記載の水分解触媒の製造方法。
That is, the present invention employs the following
1. Co-catalyst selected from ruthenium oxide, nickel oxide, cobalt oxide, iron oxide, chromium oxide, rhodium oxide and iridium oxide was supported on p-type gallium nitride to which a metal atom selected from zinc, magnesium and beryllium was added. A water-decomposing catalyst using light.
2. 2. The water-based water decomposition catalyst according to 1, wherein the p-type gallium nitride to which a metal atom selected from zinc, magnesium, and beryllium is added is p-type gallium indium nitride.
3. 3. The water-decomposing catalyst for light according to 1 or 2, wherein the addition amount of a metal atom selected from zinc, magnesium and beryllium is 0.0001 to 7 mol%.
4). The water-splitting catalyst by light according to any one of 1 to 3, wherein the promoter is ruthenium oxide.
5. 5. The water splitting catalyst according to any one of 1 to 4, wherein the supported amount of the promoter is 0.1 to 10% by weight.
6). 6. The water splitting catalyst according to any one of 1 to 5, wherein the p-type gallium nitride to which a metal atom selected from zinc, magnesium and beryllium is added has an average particle size of 10 nm to 10 μm.
7). A compound containing a metal atom selected from zinc, magnesium, and beryllium in gallium sulfide or gallium oxide so that the compounding ratio of the metal selected from zinc, magnesium, and beryllium to gallium is 0.01 to 200 mol%. Any one of 1 to 6, characterized in that p-type gallium nitride obtained by mixing and firing in an ammonia stream is immersed in water or an organic solvent solution containing a cocatalyst precursor and then fired in air. A method for producing a water splitting catalyst by light as described in 1.
8). 8. The method for producing a water splitting catalyst according to 7, wherein the ammonia flow rate is 50 to 1000 mL / min, the calcination temperature under an ammonia stream is 800 to 1100 ° C., and the calcination time is 1 to 30 hours.
9. A mixture obtained by adding 1 to 50 mol% indium sulfide to p-type gallium nitride obtained by firing in an ammonia stream is fired at a temperature of 500 to 900 ° C for 0.5 to 24 hours in an ammonia stream. The method for producing a water splitting catalyst according to 7 or 8, wherein the p-type gallium indium nitride obtained in the step is immersed in water or an organic solvent solution containing a cocatalyst precursor and then calcined in air.
10. After immersing p-type gallium nitride in a solution of triruthenium dodecacarbonyl as a co-catalyst precursor in tetrahydrofuran, the solution is refluxed at room temperature to 100 ° C. for 1 to 5 hours, and further in air at 200 to 500 ° C. for 1 to 10 hours. The method for producing a water splitting catalyst according to any one of 7 to 9, which is calcined.
11. A compound selected from zinc nitrate, magnesium nitrate and beryllium nitrate and gallium nitrate are dissolved in water, and a product obtained by adding aqueous ammonia is calcined in air at 600 to 800 ° C. to form a precursor. The p-type gallium nitride obtained by firing the obtained precursor in an ammonia stream is immersed in water or an organic solvent solution containing a promoter precursor and then fired in air. The method for producing a water splitting catalyst by light according to any one of 6.
12 12. The method for producing a water splitting catalyst according to 11, wherein the ammonia flow rate is 50 to 1000 mL / min, the calcining temperature under an ammonia stream is 800 to 1100 ° C., and the calcining time is 1 to 30 hours.
13. A mixture obtained by adding 1 to 50 mol% indium sulfide to p-type gallium nitride obtained by firing in an ammonia stream is fired at a temperature of 500 to 900 ° C for 0.5 to 24 hours in an ammonia stream. The method for producing a water-splitting catalyst according to 11 or 12, wherein the p-type gallium indium nitride obtained in the step is immersed in water or an organic solvent solution containing a promoter precursor and then calcined in air.
14 After immersing p-type gallium nitride in a solution of triruthenium dodecacarbonyl as a co-catalyst precursor in tetrahydrofuran, the solution is refluxed at room temperature to 100 ° C. for 1 to 5 hours, and further in air at 200 to 500 ° C. for 1 to 10 hours. It calcines, The manufacturing method of the water splitting catalyst in any one of 11-13 characterized by the above-mentioned.
本発明では、上記の構成を有する助触媒を担持した水分解用触媒を使用することによって、長期間安定して、光照射により水を水素と酸素に高効率で分解することが可能となった。本発明は、化石燃料等を全く使用せずに、クリーンなエネルギー源を製造する道を拓くとともに、油、排ガス等に含まれる環境汚染物質の光分解反応や、光合成反応にも適用可能な触媒を提供するもので、極めて実用的価値が高いものである。 In the present invention, by using a water splitting catalyst carrying a cocatalyst having the above-described structure, water can be decomposed into hydrogen and oxygen with high efficiency by light irradiation stably for a long period of time. . The present invention opens the way to producing clean energy sources without using any fossil fuels and the like, and is also applicable to photodecomposition reactions and photosynthesis reactions of environmental pollutants contained in oil, exhaust gas, etc. Providing a very high practical value.
本発明では、亜鉛、マグネシウム、ベリリウムから選択された金属原子を添加したｐ型窒化ガリウムに、酸化ルテニウム、酸化ニッケル、酸化コバルト、酸化鉄、酸化クロム、酸化ロジウム、酸化イリジウムから選択された助触媒を担持させることによって、光による水分解触媒を構成する。
亜鉛、マグネシウム、ベリリウムから選択された金属原子を添加したｐ型窒化ガリウムは、発光ダイオードやレーザーダイオードとして半導体分野では一般的に用いられているが、光による水完全分解用の触媒として該ｐ型窒化ガリウムを使用することは、これまで知られていない。
In the present invention, a promoter selected from ruthenium oxide, nickel oxide, cobalt oxide, iron oxide, chromium oxide, rhodium oxide and iridium oxide is added to p-type gallium nitride to which a metal atom selected from zinc, magnesium and beryllium is added. By supporting the water, a water-decomposing catalyst by light is constituted.
A p-type gallium nitride to which a metal atom selected from zinc, magnesium, and beryllium is added is generally used in the semiconductor field as a light-emitting diode or a laser diode. The use of gallium nitride has not been known so far.
本発明では、上記の異種原子を含むｐ型窒化ガリウムに、酸化ルテニウム、酸化ニッケル、酸化コバルト、酸化鉄、酸化クロム、酸化ロジウム、酸化イリジウムから選択された助触媒を担持させることによって、光エネルギーを利用して水を水素と酸素に分解する触媒としての機能が飛躍的に向上し、長期間安定に、ほぼ化学量論的に水を水素と酸素に分解することが可能となった。 In the present invention, the p-type gallium nitride containing different atoms is loaded with a promoter selected from ruthenium oxide, nickel oxide, cobalt oxide, iron oxide, chromium oxide, rhodium oxide, and iridium oxide, thereby producing light energy. As a catalyst for decomposing water into hydrogen and oxygen using water, the function as a catalyst has been dramatically improved, and it has become possible to decompose water into hydrogen and oxygen in a stable and almost stoichiometric manner for a long time.
本発明において、上記の異種原子を含むｐ型窒化ガリウムとは、亜鉛、マグネシウム、ベリリウムから選択された金属原子を、定法により、その添加量が０.０００１〜７モル％程度となるように添加した、化学式：ＩｎｘＧａ１−ｘＮ（ただし、０≦ｘ≦１）で表されるｐ型窒化ガリウム及びｐ型窒化ガリウムインジウムを表すものとする。このようなｐ型窒化ガリウムは、例えば、平均粒径が１０ｎｍ〜１０μｍ程度の粉末状のものとして使用することができる。 In the present invention, the above-mentioned p-type gallium nitride containing different atoms is a metal atom selected from zinc, magnesium, and beryllium added by a conventional method so that the addition amount is about 0.0001 to 7 mol%. P-type gallium nitride and p-type gallium indium nitride represented by the chemical formula: In x Ga 1-x N (where 0 ≦ x ≦ 1) are used. Such p-type gallium nitride can be used as a powder having an average particle size of about 10 nm to 10 μm, for example.
本発明では、この異種原子を含むｐ型窒化ガリウムに、好ましくは助触媒の担持量が０.１〜１０重量％程度となるように、酸化ルテニウム、酸化ニッケル、酸化コバルト、酸化鉄、酸化クロム、酸化ロジウム、酸化イリジウムから選択された助触媒を担持させることによって、光による水分解触媒を構成する。特に好ましい助触媒としては、酸化ルテニウムが挙げられる。 In the present invention, ruthenium oxide, nickel oxide, cobalt oxide, iron oxide, chromium oxide are preferably added to the p-type gallium nitride containing different atoms so that the supported amount of the promoter is about 0.1 to 10% by weight. By supporting a promoter selected from rhodium oxide and iridium oxide, a water splitting catalyst by light is formed. A particularly preferred promoter is ruthenium oxide.
次に、本発明の光による水分解触媒を製造する方法の１例について説明するが、以下の具体例は本発明を限定するものではない。
（１）硫化ガリウムあるいは酸化ガリウムに対して、硫化亜鉛、硫化マグネシウム、あるいは酸化ベリリウムを、ガリウムに対する亜鉛、マグネシウムあるいはベリリウムのモル比が０．０１〜２００ｍｏｌ％の範囲となるように混合した試料を前駆体とする。
あるいは、硝酸亜鉛、硝酸マグネシウム、硝酸ベリリウムから選択された化合物と硝酸ガリウムを水に溶解した水溶液に、アンモニア水を滴下して得られた生成物を空気中で６００〜８００℃の温度で焼成した試料を前駆体とすることもできる。
Next, an example of the method for producing a water-splitting catalyst by light of the present invention will be described, but the following specific examples do not limit the present invention.
(1) A sample in which zinc sulfide, magnesium sulfide, or beryllium oxide is mixed with gallium sulfide or gallium oxide so that the molar ratio of zinc, magnesium, or beryllium to gallium is in the range of 0.01 to 200 mol%. Let it be a precursor.
Or the product obtained by dripping ammonia water in the aqueous solution which melt | dissolved the compound selected from zinc nitrate, magnesium nitrate, and beryllium nitrate, and gallium nitrate in water was baked in the temperature of 600-800 degreeC in the air. A sample can also be used as a precursor.
（２）次に、回転機構を持つ、例えば長さ５０ｃｍ、内径２〜３ｃｍの石英炉心管で構成される窒化装置の中央に前駆体試料を導入し、前駆体の両端を石英ウールで固定し、高純度窒素ボンベ（純度９９．９９％以上）から前記石英炉心に窒素ガスを十分に流通させる。回転機構を備えたロータリーキルン型炉を用いることで、均質な窒化物を作製できる。次に、アンモニアボンベ（純度９９．８％以上）から前記石英炉心にアンモニアガスを５０〜１０００ｍＬ／分で流通させる。この時、アンモニアの流量は、マスフローコントローラーにより制御する。石英炉心管を毎分０．５〜１回転の速度で回転させ、試料付近を横型管状炉により７００〜１１００℃の温度に加熱する。得られた窒化ガリウムの特性は、Ｘ線回折パターン、紫外可視拡散反射スペクトル、および発光分光スペクトルにより測定する。 (2) Next, a precursor sample is introduced into the center of a nitriding apparatus having a rotating mechanism, for example, a quartz furnace core tube having a length of 50 cm and an inner diameter of 2 to 3 cm, and both ends of the precursor are fixed with quartz wool. Then, nitrogen gas is sufficiently circulated from the high purity nitrogen cylinder (purity 99.99% or more) to the quartz core. By using a rotary kiln type furnace equipped with a rotating mechanism, a homogeneous nitride can be produced. Next, ammonia gas is circulated from the ammonia cylinder (purity 99.8% or more) to the quartz core at 50 to 1000 mL / min. At this time, the flow rate of ammonia is controlled by a mass flow controller. The quartz furnace tube is rotated at a speed of 0.5 to 1 revolution per minute, and the vicinity of the sample is heated to a temperature of 700 to 1100 ° C. by a horizontal tubular furnace. The characteristics of the obtained gallium nitride are measured by an X-ray diffraction pattern, an ultraviolet-visible diffuse reflection spectrum, and an emission spectrum.
また、このようにして得られたｐ型窒化ガリウムに対して、１〜５０モル％の硫化インジウムを添加した混合物を、アンモニア気流下で温度５００〜９００℃で０．５〜２４時間焼成することにより、ｐ型窒化ガリウムインジウムを製造することができる。 In addition, the p-type gallium nitride thus obtained is baked at a temperature of 500 to 900 ° C. for 0.5 to 24 hours in an ammonia stream with 1 to 50 mol% of indium sulfide added. Thus, p-type gallium indium nitride can be manufactured.
（３）得られたｐ型窒化ガリウム或いはｐ型窒化ガリウムインジウムを、例えば、助触媒前駆体となるトリルテニウムドデカカルボニルをテトラヒドロフランに溶解した溶液に浸漬後、室温〜１００℃で１〜５時間還流し、さらに空気中で２００〜５００℃で１〜１０時間焼成することにより、目的とする光による水分解触媒を得る。
他の助触媒前駆体としては、硝酸ニッケル、塩化コバルト、塩化鉄、硝酸クロム、塩化ロジウム、塩化イリジウム等を使用することができ、これらの前駆体を１〜１０重量％程度となるように水又は有機溶媒に溶解した溶液にｐ型窒化ガリウム類を浸漬してもよい。
(3) The obtained p-type gallium nitride or p-type gallium nitride indium is immersed in a solution of triruthenium dodecacarbonyl as a co-catalyst precursor dissolved in tetrahydrofuran, and then refluxed at room temperature to 100 ° C. for 1 to 5 hours. Furthermore, the target water-decomposing catalyst by light is obtained by baking at 200 to 500 ° C. for 1 to 10 hours in air.
As other co-catalyst precursors, nickel nitrate, cobalt chloride, iron chloride, chromium nitrate, rhodium chloride, iridium chloride and the like can be used, and these precursors are used in an amount of about 1 to 10% by weight. Alternatively, p-type gallium nitrides may be immersed in a solution dissolved in an organic solvent.
以下、実施例により本発明をさらに説明するが、本発明の技術的範囲はこれら実施例によって何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further, the technical scope of this invention is not limited at all by these Examples.
（参考例１）
粉末状の硫化ガリウムを、回転機構を持つ、長さ５０ｃｍ、内径２〜３ｃｍの石英炉心管で構成される窒化装置の中央に導入し、その両端を石英ウールで固定した後に、高純度窒素ボンベ（純度９９．９９％以上）から前記石英炉心に窒素ガスを十分に流通させる。次に、アンモニアボンベ（純度９９．８％以上）から前記石英炉心にアンモニアガスを導入し、５００ｍＬ／分のアンモニア気流中、１０００℃で１５時間焼成して窒化する。これにより、無添加の窒化ガリウムが得られる。図６、７、８に、それぞれ異種金属原子無添加の窒化ガリウムのＸ線回折パターン、紫外可視拡散反射スペクトル、発光分光スペクトルを示す。結晶化度が高く、３７３ｎｍに発光中心を持つ高品質な窒化ガリウムが生成していることが判る。
(Reference Example 1)
Powdered gallium sulfide is introduced into the center of a nitriding apparatus composed of a quartz furnace core tube having a rotation mechanism and a length of 50 cm and an inner diameter of 2 to 3 cm. After fixing both ends with quartz wool, a high-purity nitrogen cylinder Nitrogen gas is sufficiently circulated through the quartz core from a purity of 99.99% or higher. Next, ammonia gas is introduced into the quartz core from an ammonia cylinder (purity of 99.8% or more), and nitriding is performed by baking at 1000 ° C. for 15 hours in an ammonia stream of 500 mL / min. Thereby, additive-free gallium nitride is obtained. FIGS. 6, 7, and 8 show the X-ray diffraction pattern, ultraviolet-visible diffuse reflection spectrum, and emission spectrum of gallium nitride without addition of different metal atoms, respectively. It can be seen that high-quality gallium nitride having a high crystallinity and having an emission center at 373 nm is produced.
この窒化ガリウムを、酸化ルテニウムの濃度が３．５重量％となるようにトリルテニウムドデカカルボニルをテルラフドロフランに溶かした溶液に浸し、６０℃の温度で４時間還流した後に、空気中、３５０℃で１．５時間焼成する。このようにして作製した酸化ルテニウム担持窒化ガリウム０．８ｇを蒸留水７００ｍＬ中に懸濁させ、４５０Ｗ高圧水銀ランプを光源として円筒形パイレックス（登録商標）製ジャケットを通して光を照射した。
図５に示すように、水素１μｍｏｌ／時間、酸素０μｍｏｌ／時間、窒素０μｍｏｌ／時間の生成活性であり、この異種金属原子無添加の窒化ガリウムには、水の完全分解反応に対する触媒活性は見られない。
This gallium nitride was immersed in a solution of triruthenium dodecacarbonyl dissolved in tellurofrofuran so that the concentration of ruthenium oxide was 3.5% by weight and refluxed at a temperature of 60 ° C. for 4 hours. Bake at 1.5 ° C. for 1.5 hours. 0.8 g of ruthenium oxide-supporting gallium nitride thus prepared was suspended in 700 mL of distilled water, and irradiated with light through a cylindrical Pyrex (registered trademark) jacket using a 450 W high-pressure mercury lamp as a light source.
As shown in FIG. 5, the production activity is 1 μmol / hour for hydrogen, 0 μmol / hour for oxygen, and 0 μmol / hour for nitrogen, and this gallium nitride without addition of different metal atoms shows catalytic activity for the complete decomposition reaction of water. Absent.
（実施例１）
粉末状の硫化ガリウムと硫化亜鉛を、ガリウムに対して亜鉛元素を２００％のモル比で混合し、参考例１と同様にして５００ｍＬ／分のアンモニア気流中、１０００℃で８時間焼成して窒化する。焼成時にほとんどの亜鉛成分が揮発し、亜鉛が数〜数十ｐｐｍの濃度で添加された窒化ガリウムが得られる。図６、７、８に亜鉛添加のｐ型窒化ガリウムのＸＲＤパターン、紫外可視拡散反射スペクトル、発光分光スペクトルを示す。亜鉛添加窒化ガリウムは無添加の窒化ガリウムと比較して、結晶化度はほぼ等しいが、吸収波長がわずかに長波長に移動し、発光中心が大きく長波長の４４０ｎｍに移動する。このようにｐ型特有の発光分光スペクトルを持つ窒化ガリウムが生成した。
このｐ型窒化ガリウムに、上記参考例１と同様の方法で酸化ルテニウムを担持させ、参考例１と同様の方法で光を照射した。図１に示すように、水素２０８μｍｏｌ／時間、酸素８８μｍｏｌ／時間、窒素４μｍｏｌ／時間の生成活性が見られ、水分解反応に対して高い光触媒活性を持つことが判明した。
Example 1
Powdered gallium sulfide and zinc sulfide are mixed with zinc element at a molar ratio of 200% with respect to gallium, and calcinated in an ammonia stream at 500 mL / min for 8 hours at 1000 ° C. in the same manner as in Reference Example 1. To do. Most of the zinc components are volatilized during firing, and gallium nitride to which zinc is added at a concentration of several to several tens of ppm is obtained. FIGS. 6, 7 and 8 show the XRD pattern, ultraviolet-visible diffuse reflection spectrum, and emission spectrum of the p-type gallium nitride added with zinc. Zinc-added gallium nitride has almost the same degree of crystallinity as non-added gallium nitride, but the absorption wavelength slightly shifts to a longer wavelength, and the emission center increases to a longer wavelength of 440 nm. Thus, gallium nitride having an emission spectrum specific to p-type was generated.
This p-type gallium nitride was loaded with ruthenium oxide by the same method as in Reference Example 1 and irradiated with light by the same method as in Reference Example 1. As shown in FIG. 1, production activity of 208 μmol / hour of hydrogen, 88 μmol / hour of oxygen, and 4 μmol / hour of nitrogen was observed, and it was found that the photocatalytic activity was high for water splitting reaction.
（比較例１）
比較のために、上記実施例１で得られた亜鉛添加ｐ型窒化ガリウムに、助触媒となる酸化ルテニウムを担持させずに、参考例１と同様の方法で光を照射したところ、水素２μｍｏｌ／時間、酸素０μｍｏｌ／時間、窒素０μｍｏｌ／時間の生成活性であり、水分解反応に対する活性は殆んど認められなかった。
(Comparative Example 1)
For comparison, the zinc-added p-type gallium nitride obtained in Example 1 above was irradiated with light in the same manner as in Reference Example 1 without carrying ruthenium oxide as a promoter, and
（実施例２）
粉末状の硫化ガリウムと硫化マグネシウムを、ガリウムに対するマグネシウム元素のモル比が３％ととなるように混合し、参考例１と同様にして５００ｍＬ／分のアンモニア気流中、１０００℃で１５時間焼成して窒化する。得られた前駆体を５０〜１０００ｍＬ／分のアンモニア気流中下、１０００℃、１５時間で焼成しマグネシウム添加ｐ型窒化ガリウムを得た。図６、７、８にマグネシウム添加の窒化ガリウムのＸＲＤパターン、紫外可視拡散スペクトル、発光分光スペクトルを示す。実施例１の亜鉛添加の窒化ガリウムと同様なｐ型窒化ガリウムが得られた。
このｐ型窒化ガリウムに、上記参考例１と同様の方法で酸化ルテニウムを担持させ、参考例１と同様の方法で光を照射した。図２に示すように、水素６６８μｍｏｌ／時間、酸素２８６μｍｏｌ／時間、窒素０μｍｏｌ／時間の生成活性が見られ、水完全分解反応に対して高い光触媒活性を持つことが判明した。
(Example 2)
Powdered gallium sulfide and magnesium sulfide are mixed so that the molar ratio of magnesium element to gallium is 3%, and calcined in an ammonia stream at 500 mL / min for 15 hours at 1000 ° C. in the same manner as in Reference Example 1. To nitride. The obtained precursor was calcined at 1000 ° C. for 15 hours in an ammonia stream of 50 to 1000 mL / min to obtain magnesium-added p-type gallium nitride. FIGS. 6, 7 and 8 show the XRD pattern, ultraviolet-visible diffusion spectrum, and emission spectrum of gallium nitride added with magnesium. A p-type gallium nitride similar to the zinc-added gallium nitride of Example 1 was obtained.
This p-type gallium nitride was loaded with ruthenium oxide by the same method as in Reference Example 1 and irradiated with light by the same method as in Reference Example 1. As shown in FIG. 2, production activity of 668 μmol / hour of hydrogen, 286 μmol / hour of oxygen, and 0 μmol / hour of nitrogen was found, and it was found that the photocatalytic activity was high for the complete water decomposition reaction.
（比較例２）
比較のために、上記実施例２で得られたマグネシウム添加ｐ型窒化ガリウムに、助触媒となる酸化ルテニウムを担持させずに、参考例１と同様の方法で光を照射したところ、水素５μｍｏｌ／時間、酸素０μｍｏｌ／時間、窒素０μｍｏｌ／時間の生成活性であり、水分解反応に対する活性は殆んど認められなかった。
(Comparative Example 2)
For comparison, the magnesium-added p-type gallium nitride obtained in Example 2 above was irradiated with light in the same manner as in Reference Example 1 without supporting ruthenium oxide as a cocatalyst. Production activity was as follows: time,
（実施例３）
実施例２と同じモル比で、硝酸ガリウムと硝酸マグネシウムを水に溶解させ、アンモニア水を滴下して得られた生成物を、空気中で６００〜８００℃の温度で１〜６０分間焼成して前駆体を製造した。得られた前駆体を、参考例１と同様にして５０〜１０００ｍＬ／分のアンモニア気流中、１０００℃で１５時間焼成することにより、実施例２のマグネシウム添加窒化ガリウムと同様なｐ型窒化ガリウムが得られた。
このｐ型窒化ガリウムに、上記参考例１と同様の方法で酸化ルテニウムを担持させ、参考例１と同様の方法で光を照射した。図３に示すように、水素３４１μｍｏｌ／時間、酸素１７３μｍｏｌ／時間、窒素０μｍｏｌ／時間の生成活性が見られ、水完全分解反応に対して高い光触媒活性を持つことが判明した。
(Example 3)
A product obtained by dissolving gallium nitrate and magnesium nitrate in water and dropping ammonia water at the same molar ratio as in Example 2 was calcined in air at a temperature of 600 to 800 ° C. for 1 to 60 minutes. A precursor was produced. The obtained precursor was baked at 1000 ° C. for 15 hours in an ammonia stream of 50 to 1000 mL / min in the same manner as in Reference Example 1 to obtain a p-type gallium nitride similar to the magnesium-added gallium nitride of Example 2. Obtained.
This p-type gallium nitride was loaded with ruthenium oxide by the same method as in Reference Example 1 and irradiated with light by the same method as in Reference Example 1. As shown in FIG. 3, production activities of hydrogen of 341 μmol / hour, oxygen of 173 μmol / hour, and nitrogen of 0 μmol / hour were observed, and it was found that the photocatalytic activity was high for the complete water decomposition reaction.
（比較例３）
比較のために、上記実施例３で得られたマグネシウム添加ｐ型窒化ガリウムに、助触媒となる酸化ルテニウムを担持させずに、参考例１と同様の方法で光を照射したところ、水素４μｍｏｌ／時間、酸素０μｍｏｌ／時間、窒素０μｍｏｌ／時間の生成活性であり、水分解反応に対する活性は殆んど認められなかった。
(Comparative Example 3)
For comparison, the magnesium-added p-type gallium nitride obtained in Example 3 was irradiated with light in the same manner as in Reference Example 1 without carrying ruthenium oxide as a promoter, and
（実施例４）
粉末状の硫化ガリウムと酸化ベリリウムを、ガリウムに対するベリリウム元素のモル比が３％となるように混合し、参考例１と同様にして５００ｍＬ／分のアンモニア気流中、１０００℃で１５時間焼成して窒化する。図６、７、８にベリリウム添加の窒化ガリウムのＸＲＤパターン、紫外可視拡散反射スペクトル、発光分光スペクトルを示す。実施例１の亜鉛添加の窒化ガリウムと同様なｐ型窒化ガリウムが得られた。
このｐ型窒化ガリウムに、上記参考例１と同様の方法で酸化ルテニウムを担持させ、参考例１と同様の方法で光を照射した。図４に示すように、水素２７８μｍｏｌ／時間、酸素１２５μｍｏｌ／時間、窒素０μｍｏｌ／時間の生成活性が見られ、水完全分解反応に対して高い光活性を持つことが示唆される。
Example 4
Powdered gallium sulfide and beryllium oxide were mixed so that the molar ratio of beryllium to gallium was 3%, and calcined at 1000 ° C. for 15 hours in an ammonia stream at 500 mL / min in the same manner as in Reference Example 1. Nitrid. FIGS. 6, 7 and 8 show the XRD pattern, ultraviolet-visible diffuse reflection spectrum, and emission spectrum of beryllium-added gallium nitride. A p-type gallium nitride similar to the zinc-added gallium nitride of Example 1 was obtained.
This p-type gallium nitride was loaded with ruthenium oxide by the same method as in Reference Example 1 and irradiated with light by the same method as in Reference Example 1. As shown in FIG. 4, formation activity of hydrogen of 278 μmol / hour, oxygen of 125 μmol / hour, and nitrogen of 0 μmol / hour is observed, suggesting that it has high photoactivity for water complete decomposition reaction.
（比較例４）
比較のために、上記実施例４で得られたベリリウム添加ｐ型窒化ガリウムに、助触媒となる酸化ルテニウムを担持させずに、参考例１と同様の方法で光を照射したところ、水素２μｍｏｌ／時間、酸素０μｍｏｌ／時間、窒素０μｍｏｌ／時間の生成活性であり、水分解反応に対する活性は殆んど認められなかった。
(Comparative Example 4)
For comparison, the beryllium-added p-type gallium nitride obtained in Example 4 was irradiated with light in the same manner as in Reference Example 1 without carrying ruthenium oxide as a cocatalyst. Production activity was as follows: time,
（実施例５）
実施例１で得られた亜鉛添加ｐ型窒化ガリウムに、ガリウムに対して硫化インジウムを３０％のモル比で混合し、参考例１と同様にして５００ｍＬ／分のアンモニア気流中、６３０℃で１０時間焼成して窒化する。得られたｐ型窒化ガリウムインジウムに、上記参考例１と同様の方法で酸化ルテニウムを担持させた。
この酸化ルテニウム担持亜鉛添加窒化ガリウムインジウム０．８ｇを蒸留水１０００ｍL中に懸濁させ、２００W水銀キセノンランプを光源として、円筒型パイレックス（登録商標）ジャケットを通して光を照射した。また、４２０ｎmまでの光を遮断できるカットフィルターを光源と懸濁液の間に導入して、光を照射した。その結果を図９に示す。
(Example 5)
The zinc-added p-type gallium nitride obtained in Example 1 was mixed with indium sulfide at a molar ratio of 30% with respect to gallium, and 10% at 630 ° C. in an ammonia stream at 500 mL / min in the same manner as in Reference Example 1. Bake for hours and nitride. Ruthenium oxide was supported on the obtained p-type gallium indium nitride by the same method as in Reference Example 1 above.
This ruthenium oxide-supported zinc-doped gallium indium nitride (0.8 g) was suspended in distilled water (1000 mL) and irradiated with light through a cylindrical Pyrex (registered trademark) jacket using a 200 W mercury xenon lamp as a light source. In addition, a cut filter capable of blocking light up to 420 nm was introduced between the light source and the suspension to irradiate the light. The result is shown in FIG.
図９にみられるように、酸化ルテニウム担持窒化ガリウムインジウムに、カットフィルターを用いずに光を照射した場合には、水素２９μｍｏｌ／時間、酸素９μｍｏｌ／時間、窒素０μｍｏｌ／時間の生成活性がみられた。一方、カットフィルターを導入して４２０ｎｍまでの光を遮断した場合には、水素７μｍｏｌ／時間、酸素３μｍｏｌ／時間、窒素０μｍｏｌ／時間の生成活性がみられた。
比較のために、実施例１で得られたインジウムを添加していない酸化ルテニウム担持亜鉛添加窒化ガリウムを使用して、上記と同様にして光を照射したところ、カットフィルターを用いずに光を照射した場合には、水素８２μｍｏｌ／時間、酸素３０μｍｏｌ／時間、窒素０μｍｏｌ／時間の生成活性がみられた。一方、カットフィルターを導入して４２０ｎｍまでの光を遮断した場合には、水素２μｍｏｌ／時間、酸素１μｍｏｌ／時間、窒素０μｍｏｌ／時間の生成活性がみられた。（図９参照）
酸化ルテニウム担持亜鉛添加窒化ガリウムに比べて、酸化ルテニウム担持亜鉛添加窒化ガリウムインジウムは、４２０ｎｍ以上の波長の光照射によってより高い触媒活性が得られていることから、インジウムを添加することによって、より長波長の光を吸収することが判明した。
As shown in FIG. 9, when ruthenium oxide-supported gallium indium nitride is irradiated with light without using a cut filter, production activity of hydrogen 29 μmol / hour,
For comparison, light was irradiated in the same manner as described above using the ruthenium oxide-supported zinc-added gallium nitride to which indium was not added obtained in Example 1, and light was irradiated without using a cut filter. In this case, the production activity of 82 μmol / hour of hydrogen, 30 μmol / hour of oxygen, and 0 μmol / hour of nitrogen was observed. On the other hand, when a cut filter was introduced to block light up to 420 nm, production activity of 2 μmol / hour of hydrogen, 1 μmol / hour of oxygen, and 0 μmol / hour of nitrogen was observed. (See Figure 9)
Compared to ruthenium oxide-supported zinc-doped gallium nitride, ruthenium oxide-supported zinc-added gallium nitride indium has a higher catalytic activity due to light irradiation with a wavelength of 420 nm or more. It has been found to absorb light of a wavelength.
（比較例５）
比較のために、上記実施例５で得られた亜鉛添加ｐ型窒化ガリウムインジウムに、助触媒となる酸化ルテニウムを担持させずに、参考例１と同様の方法で光を照射したところ、水素０μｍｏｌ／時間、酸素０μｍｏｌ／時間、窒素０μｍｏｌ／時間の生成活性であり、水分解反応に対する活性は認められなかった。
(Comparative Example 5)
For comparison, the zinc-added p-type gallium indium nitride obtained in Example 5 above was irradiated with light in the same manner as in Reference Example 1 without carrying ruthenium oxide as a cocatalyst. Per hour,
本発明の光による水分解触媒は、化石燃料等を全く使用せずに、クリーンなエネルギー源を製造する道を拓くものである。また、本発明で得られる触媒は、水の分解のみならず、エタノールや油等の有機物質の分解、或いは排ガス等に含まれる環境汚染物質の光分解反応や、各種の光合成反応等の幅広い分野にも適用可能なものである。 The water-based water splitting catalyst of the present invention opens the way for producing a clean energy source without using any fossil fuel or the like. Further, the catalyst obtained in the present invention is not only decomposed in water, but also in a wide range of fields such as decomposition of organic substances such as ethanol and oil, or photolysis reaction of environmental pollutants contained in exhaust gas, and various photosynthesis reactions. It is also applicable to.
Claims (14)
After immersing p-type gallium nitride in a solution of triruthenium dodecacarbonyl as a co-catalyst precursor in tetrahydrofuran, the solution is refluxed at room temperature to 100 ° C. for 1 to 5 hours, and further in air at 200 to 500 ° C. for 1 to 10 hours. It calcinates, The manufacturing method of the water splitting catalyst in any one of Claims 11-13 characterized by the above-mentioned.
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| WO2007139116A1 (en) | 2006-05-29 | 2007-12-06 | Denki Kagaku Kogyo Kabushiki Kaisha | Process for production of cross copolymers, cross copolymers obtained by the process, and use thereof |
| WO2011162372A1 (en) * | 2010-06-25 | 2011-12-29 | 国立大学法人京都工芸繊維大学 | Photocatalyst material and photocatalyst device |
| CN104209135A (en) * | 2013-05-31 | 2014-12-17 | 天津大学 | Catalyst for high-efficiency visible light excitation of water decomposition to prepare hydrogen gas and oxygen gas and preparation method thereof |
| CN110116015A (en) * | 2018-02-06 | 2019-08-13 | 西安交通大学 | Complete photochemical catalyst for decomposing water and its preparation method and application, photocatalysis decompose the reaction method and catalytic mixing liquid of water completely |
| CN110116015B (en) * | 2018-02-06 | 2020-05-19 | 西安交通大学 | Photocatalyst for completely decomposing water, preparation method and application thereof, reaction method for completely decomposing water through photocatalysis and catalytic mixed solution |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4982736B2 (en) | 2012-07-25 |
| WO2007052512A1 (en) | 2007-05-10 |
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