JP2022077351A - レドックスメディエータ及び光触媒システム - Google Patents
レドックスメディエータ及び光触媒システム Download PDFInfo
- Publication number
- JP2022077351A JP2022077351A JP2020188167A JP2020188167A JP2022077351A JP 2022077351 A JP2022077351 A JP 2022077351A JP 2020188167 A JP2020188167 A JP 2020188167A JP 2020188167 A JP2020188167 A JP 2020188167A JP 2022077351 A JP2022077351 A JP 2022077351A
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- JP
- Japan
- Prior art keywords
- redox mediator
- particles
- photocatalyst
- reduction
- metal complex
- 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.)
- Granted
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 143
- 239000002245 particle Substances 0.000 claims abstract description 183
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 67
- 229910052751 metal Inorganic materials 0.000 claims abstract description 60
- 239000002184 metal Substances 0.000 claims abstract description 59
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 56
- 230000003647 oxidation Effects 0.000 claims abstract description 50
- 150000002739 metals Chemical class 0.000 claims abstract description 23
- 230000000737 periodic effect Effects 0.000 claims abstract description 9
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims abstract 3
- 239000004065 semiconductor Substances 0.000 claims description 122
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 81
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 81
- 239000003054 catalyst Substances 0.000 claims description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims description 32
- 230000001699 photocatalysis Effects 0.000 claims description 32
- 239000012736 aqueous medium Substances 0.000 claims description 30
- 239000001257 hydrogen Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 9
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- 238000012546 transfer Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 229940006460 bromide ion Drugs 0.000 claims description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 5
- 229940006461 iodide ion Drugs 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 229910052702 rhenium Inorganic materials 0.000 abstract description 4
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical group O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 103
- 150000001875 compounds Chemical class 0.000 description 31
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 27
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 27
- 238000000034 method Methods 0.000 description 27
- 239000012488 sample solution Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 25
- 239000011701 zinc Substances 0.000 description 24
- 239000003446 ligand Substances 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- 239000000047 product Substances 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 17
- 239000010949 copper Substances 0.000 description 16
- -1 for example Chemical compound 0.000 description 15
- 230000001603 reducing effect Effects 0.000 description 15
- 239000003792 electrolyte Substances 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 239000010936 titanium Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 150000004763 sulfides Chemical class 0.000 description 12
- 125000001424 substituent group Chemical group 0.000 description 11
- 230000007423 decrease Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 125000005647 linker group Chemical group 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 8
- 150000004706 metal oxides Chemical class 0.000 description 8
- 229910052976 metal sulfide Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 150000004767 nitrides Chemical class 0.000 description 7
- 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 7
- 239000011164 primary particle Substances 0.000 description 7
- 229910001936 tantalum oxide Inorganic materials 0.000 description 7
- NBPGPQJFYXNFKN-UHFFFAOYSA-N 4-methyl-2-(4-methylpyridin-2-yl)pyridine Chemical compound CC1=CC=NC(C=2N=CC=C(C)C=2)=C1 NBPGPQJFYXNFKN-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000027756 respiratory electron transport chain Effects 0.000 description 6
- 229910052707 ruthenium Inorganic materials 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 229910052984 zinc sulfide Inorganic materials 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 229910052797 bismuth Inorganic materials 0.000 description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- GVGCUCJTUSOZKP-UHFFFAOYSA-N nitrogen trifluoride Chemical class FN(F)F GVGCUCJTUSOZKP-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 238000013032 photocatalytic reaction Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000005749 Copper compound Substances 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 150000001880 copper compounds Chemical class 0.000 description 4
- 150000002222 fluorine compounds Chemical class 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 150000002391 heterocyclic compounds Chemical class 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910001512 metal fluoride Inorganic materials 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052715 tantalum Inorganic materials 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- NYYLZXREFNYPKB-UHFFFAOYSA-N 1-[ethoxy(methyl)phosphoryl]oxyethane Chemical compound CCOP(C)(=O)OCC NYYLZXREFNYPKB-UHFFFAOYSA-N 0.000 description 3
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- 240000002329 Inga feuillei Species 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229910002367 SrTiO Inorganic materials 0.000 description 3
- 239000005083 Zinc sulfide Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- XSCHRSMBECNVNS-UHFFFAOYSA-N benzopyrazine Natural products N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 3
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- 150000002506 iron compounds Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- 150000003482 tantalum compounds Chemical class 0.000 description 3
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 3
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 3
- DRGAZIDRYFYHIJ-UHFFFAOYSA-N 2,2':6',2''-terpyridine Chemical compound N1=CC=CC=C1C1=CC=CC(C=2N=CC=CC=2)=N1 DRGAZIDRYFYHIJ-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- PTRATZCAGVBFIQ-UHFFFAOYSA-N Abametapir Chemical compound N1=CC(C)=CC=C1C1=CC=C(C)C=N1 PTRATZCAGVBFIQ-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910003071 TaON Inorganic materials 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- GJCOKGHYIMLMPB-UHFFFAOYSA-N [2-(4-methylpyridin-2-yl)pyridin-4-yl]methanol Chemical compound CC1=CC=NC(C=2N=CC=C(CO)C=2)=C1 GJCOKGHYIMLMPB-UHFFFAOYSA-N 0.000 description 2
- BVJRIMBTLVPCFB-UHFFFAOYSA-N [Fe+2].[O-2].[Ca+2].[O-2] Chemical compound [Fe+2].[O-2].[Ca+2].[O-2] BVJRIMBTLVPCFB-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 150000001722 carbon compounds Chemical class 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- CDZGJSREWGPJMG-UHFFFAOYSA-N copper gallium Chemical compound [Cu].[Ga] CDZGJSREWGPJMG-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 150000004715 keto acids Chemical class 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical class [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- 150000003682 vanadium compounds Chemical class 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- AATNZNJRDOVKDD-UHFFFAOYSA-N 1-[ethoxy(ethyl)phosphoryl]oxyethane Chemical compound CCOP(=O)(CC)OCC AATNZNJRDOVKDD-UHFFFAOYSA-N 0.000 description 1
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 1
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 1
- ZPSJGADGUYYRKE-UHFFFAOYSA-N 2H-pyran-2-one Chemical compound O=C1C=CC=CO1 ZPSJGADGUYYRKE-UHFFFAOYSA-N 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910018565 CuAl Inorganic materials 0.000 description 1
- 229910002535 CuZn Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
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- 229910052738 indium Inorganic materials 0.000 description 1
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 1
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- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
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- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
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- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
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- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
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- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
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- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
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- 235000011152 sodium sulphate Nutrition 0.000 description 1
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- 239000000725 suspension Substances 0.000 description 1
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 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
- 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
Landscapes
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
Abstract
Description
前記レドックスメディエータは、水性媒体中に溶解し、下記一般式
前記レドックスメディエータは、前記水性媒体中に溶解し、下記一般式
図1に、本実施形態に係る光触媒システムの構成を示す。光触媒システム1は、酸化光触媒粒子2と、還元半導体粒子3aを含んで構成される還元光触媒粒子3と、レドックスメディエータ(以下単に「メディエータ」ともいう)4と、を備える。メディエータ4は、酸化光触媒粒子2と還元光触媒粒子3との間で電子を伝達する。
酸化光触媒粒子2は、可視光の照射によって光触媒機能を発揮し、水の酸化反応を生起する半導体化合物(以下「酸化半導体」とも記載する)で構成された粒子であれば、特に限定されない。ここで、可視光とは波長λが360nm以上である光を意味する。酸化半導体は、価電子帯上端の電位が水の酸化(O2/H2O)電位(標準水素電極(SHE)に対して1.23V)より貴(ポジティブ)であるものが好ましい。
還元光触媒粒子3は、可視光の照射によって光触媒機能を発揮し、水の酸化反応を生起する半導体化合物(以下「還元半導体」とも記載する)からなる還元半導体粒子3aを含んで構成される。還元光触媒粒子3は、少なくとも還元半導体粒子3aを含むものであれば、特に限定されない。
還元半導体粒子3aを構成する還元半導体としては、還元半導体の伝導帯下端(CBM)の電位が、酸化光触媒粒子2を構成する酸化半導体の価電子帯上端(VBM)の電位より貴(ポジティブ)であるものが挙げられる。これにより、酸化光触媒粒子2において光励起した電子がメディエータ4を介して還元半導体粒子3aの価電子帯へ移動し、その電子が再び還元半導体粒子3aの伝導帯に光励起する、という2段階光励起システムが形成される。還元光触媒粒子3は、還元半導体のCBMの電位から酸化半導体のVBMの電位を差し引いた電位差が0.1V以上であるものが好ましい。
還元光触媒粒子3は、還元半導体粒子3aと金属錯体触媒3bとを含んで構成されていてもよい。金属錯体触媒3bとしては、金属と非金属の配位子とが結合した構造を有し、電子を利用することにより、物質(例えば、CO2やプロトン)の還元活性を示す化合物であれば特に制限なく使用できる。金属錯体触媒3bは、例えば、還元半導体粒子3aを構成する半導体化合物のCBMの準位が金属錯体触媒3bの最低空軌道(LUMO)の準位に対して+0.2V以下である化合物であればよい。電子移動の効率の観点から、還元半導体粒子3aのVBMの準位が金属錯体触媒3bのLUMOの準位よりも卑であることが好ましい。
本実施形態に係る光触媒システム1で使用されるメディエータ4は、酸化光触媒粒子2と還元光触媒粒子3との間で電子を伝達可能な化合物である。更に言えば、メディエータ4は、光触媒システム1を含有する水性媒体中において、酸化光触媒粒子2から電子e-を受け取ることで酸化体から還元体となり、且つ、還元光触媒粒子3(還元半導体粒子3a)に電子e-を引き渡すことで還元体から酸化体に戻ることができる化合物である。
水性媒体としては、水を主成分として含有する媒体であれば適宜使用可能である。水性媒体は、例えば、電解質を含有していてもよく、メタノール及びエタノール等の水溶性有機溶媒を含有していてもよい。
本実施形態に係る光触媒システム1は、水性媒体、酸化光触媒粒子2、還元光触媒粒子3及びメディエータ4を混合することによって得ることができる。例えば、酸化光触媒粒子2と還元光触媒粒子3とを混合し、メディエータ4を含有する水性媒体に添加することにより、本実施形態に係る光触媒システム1が形成される。
<バナジン酸ビスマス半導体(BiVO4)粒子の合成>
20mmolの硝酸ビスマス水和物(Bi(NO3)3・5H2O、関東化学株式会社製)、及び、10mmolの五酸化バナジウム(V2O5、和光純薬工業株式会社製)を0.5mol/Lの硝酸水溶液100mLに添加し、得られた混合液を室温で72時間撹拌した。生成した粒子をろ過した後、水で洗浄し、120℃で乾燥することにより、バナジン酸ビスマス半導体(BiVO4)からなる酸化光触媒粒子を得た。
硫化銅(II)(Cu2S、株式会社高純度化学研究所製)、硫化ガリウム(III)(Ga2S3、株式会社高純度化学研究所製)、及び、硫化亜鉛(ZnS、株式会社高純度化学研究所製)を、モル比がCu:Ga:Zn=0.3:0.36:1.4となる量で混合した。得られた混合物を石英管に入れ密封した後、1073Kで10時間焼成することにより結晶化させて、組成式(CuGa)0.3Zn1.4S2で表される複合金属硫化物半導体からなる還元半導体粒子を得た。
(1)Co(NO3)2・6H2O(和光純薬工業株式会社製)1.5mmol、及び、4,4’-ジメチル-2,2’-ビピリジン(東京化成工業株式会社製)4.5mmolをメタノールに溶解し、撹拌及び減圧濃縮した。次いで、得られた残渣を再結晶化することにより、[Co(4,4’-ジメチル-2,2’-ビピリジン)3](NO3)2(以下、[Co-1(+2)](NO3)2と称する場合がある)で表されるレドックスメディエータを合成した。
<実施例1>
0.1mMのレドックスメディエータ([Co-1(+2)](NO3)2)を含むNaHCO3水溶液4mLに、還元光触媒粒子としての(CuGa)0.3Zn1.4S2を2.7mg、酸化光触媒粒子としてのBiVO4を2,7mg添加して、試料液を調製した。
0.1mMのRu-dmpebpy/(CuGa)0.3Zn1.4S2を還元光触媒粒子として用いたこと以外は、実施例1と同様に試料液を調製し、CO2還元反応を評価した。
0.1mMの[Co-1(+3)](NO3)3をレドックスメディエータとして用いたこと以外は、実施例2と同様に試料液を調製し、実施例1と同様にCO2還元反応を評価した。
0.1mMの[Co-1(+2)](SO4)をレドックスメディエータとして用いたこと以外は、実施例2と同様に試料液を調製し、実施例1と同様にCO2還元反応を評価した。
0.1mMの[Co-1(+2)]Cl2をレドックスメディエータとして用いたこと以外は、実施例2と同様に試料液を調製し、実施例1と同様にCO2還元反応を評価した。
0.1mMの[Co-2(+2)]Cl2をレドックスメディエータとして用いたこと以外は、実施例2と同様に試料液を調製し、実施例1と同様にCO2還元反応を評価した。
0.1mMの[Co-3(+2)](NO3)2をレドックスメディエータとして用いたこと以外は、実施例1と同様に試料液を調製し、実施例1と同様にCO2還元反応を評価した。
0.1mMの[Co-R1(+2)](NO3)2をレドックスメディエータとして用いたこと以外は、実施例1と同様に試料液を調製し、実施例1と同様にCO2還元反応を評価した。
0.1mMの[Co-R1(+3)](NO3)3をレドックスメディエータとして用いたこと以外は、実施例1と同様に試料液を調製し、実施例1と同様にCO2還元反応を評価した。
0.02mMの[Co-R2(+2)](NO3)2をレドックスメディエータとして用いたこと以外は、実施例2と同様に試料液を調製し、実施例1と同様にCO2還元反応を評価した。
0.1mMの[Co-1(+2)]BF4をレドックスメディエータとして用いたこと以外は、実施例2と同様に試料液を調製し、実施例1と同様にCO2還元反応を評価した。
実施例2の試料液を用いたこと、光触媒性能の評価試験を行う際、光照射を行わずに暗室内で16時間反応を行ったこと以外は実施例1と同様にCO2還元反応を評価した。
レドックスメディエータを含まないこと以外は、実施例1と同様に試料液を調製し、実施例1と同様にCO2還元反応を評価した。
<実施例8>
実施例2で得られた試料液に対して、光照射時間を1時間、2時間、4時間、6時間、8時間及び16時間とした光照射試験を行い、生成物を分析及び定量したこと以外は、実施例1の方法に従って、CO2還元反応を評価した。
0.04質量%のRu-dmpebpy/(CuGa)0.3Zn1.4S2を還元光触媒粒子として用いたこと以外は、比較例1と同様に試料液を調製し、実施例8と同様にCO2還元反応を評価した。
比較例3で得られた試料液を用いたこと以外は、実施例8と同様にCO2還元反応を評価した。
<実施例9>
0.1mMのレドックスメディエータ([Co-1(+2)](NO3)2)を含む水4mLに、還元光触媒粒子としての(CuGa)0.3Zn1.4S2を2mg、酸化光触媒粒子としてのBiVO4を2mg添加して、試料液を調製した。
0.04質量%のRu-dmpebpy/(CuGa)0.3Zn1.4S2を還元光触媒粒子として用いたこと以外は、実施例9と同様に水分解反応を評価した。
0.02Mの[Co-R2(+2)](NO3)2をレッドクスメディエータとして用いたこと以外は、実施例9と同様に水分解反応を評価した。
Zスキーム型反応のうち酸化反応に伴う酸素(O2)を正確に定量するために、以下に示す流通式反応装置を用いた光触媒反応評価を行った。
NaHCO3を0.01Mの濃度で含有する電解質水溶液に、レドックスメディエータとして[Co-1(+2)](NO3)2を0.1mMの濃度となるように添加して、水性媒体を調製し、得られた水性媒体120mLをガラス製の容器に入れた。次いで、ガラス製の容器に、還元光触媒粒子としてのRu-dmpebpy/(CuGa)0.3Zn1.4S2を0.1g、酸化光触媒粒子としてのBiVO4を0.1g添加し、試料液を調製した。容器中の試料液に、CO2ガスを毎分15mLの流量で通気しながら、可視光(λ>420nm)を照射した。照射時間が所定時間を経過する毎に、容器内の気相成分に含まれるガス成分をガスクロマトグラフ(株式会社島津製作所製「GC-8A」)を用いて分析及び定量した。
Claims (6)
- 前記金属錯体レドックスメディエータは、硝酸イオン、硫酸イオン、炭酸イオン、塩化物イオン、臭化物イオン、ヨウ化物イオンから選択される少なくとも1つの対イオンを含むことを特徴とする請求項1に記載のレドックスメディエータ。
- 前記金属錯体レドックスメディエータは、硝酸イオン、硫酸イオン、炭酸イオン、塩化物イオン、臭化物イオン、ヨウ化物イオンから選択される少なくとも1つの対イオンを含むことを特徴とする請求項3に記載の光触媒システム。
- 前記還元光触媒粒子は、半導体粒子と金属錯体触媒とを含むことを特徴とする請求項3又は4に記載の光触媒システム。
- 前記物質の還元生成物は、二酸化炭素の還元生成物、一酸化炭素と水素を含む合成ガス、及び水素のうちのいずれか1つを含むことを特徴とする請求項3~5のいずれか1項に記載の光触媒システム。
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