CN102491989A - Iridium complex, preparation method of iridium complex, method for catalyzing and reducing water by using visible light and dye-sensitized solar cell - Google Patents
Iridium complex, preparation method of iridium complex, method for catalyzing and reducing water by using visible light and dye-sensitized solar cell Download PDFInfo
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- CN102491989A CN102491989A CN2011103818916A CN201110381891A CN102491989A CN 102491989 A CN102491989 A CN 102491989A CN 2011103818916 A CN2011103818916 A CN 2011103818916A CN 201110381891 A CN201110381891 A CN 201110381891A CN 102491989 A CN102491989 A CN 102491989A
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- iridium
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- benzothiazole
- phenyl
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 55
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000013067 intermediate product Substances 0.000 claims abstract description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 20
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 10
- XBHOUXSGHYZCNH-UHFFFAOYSA-N 2-phenyl-1,3-benzothiazole Chemical compound C1=CC=CC=C1C1=NC2=CC=CC=C2S1 XBHOUXSGHYZCNH-UHFFFAOYSA-N 0.000 claims abstract description 7
- LNBGXHQIKQOZOS-UHFFFAOYSA-N 2-phenyl-3-(trifluoromethyl)-2H-1,3-benzothiazole Chemical compound FC(N1C(SC2=C1C=CC=C2)C2=CC=CC=C2)(F)F LNBGXHQIKQOZOS-UHFFFAOYSA-N 0.000 claims abstract description 7
- PDVSHXSSPVXJNH-UHFFFAOYSA-N 2-phenyl-5-(trifluoromethyl)-1,3-benzothiazole Chemical compound N=1C2=CC(C(F)(F)F)=CC=C2SC=1C1=CC=CC=C1 PDVSHXSSPVXJNH-UHFFFAOYSA-N 0.000 claims abstract description 7
- IRMFOYGYLSBJNJ-UHFFFAOYSA-N 4,6-dimethyl-2-phenyl-5-(trifluoromethyl)-1,3-benzothiazole Chemical compound CC1=CC2=C(N=C(S2)C2=CC=CC=C2)C(=C1C(F)(F)F)C IRMFOYGYLSBJNJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 20
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 claims description 13
- 239000012046 mixed solvent Substances 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- 230000002829 reductive effect Effects 0.000 claims description 9
- 235000017550 sodium carbonate Nutrition 0.000 claims description 9
- 206010070834 Sensitisation Diseases 0.000 claims description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 230000008313 sensitization Effects 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000975 dye Substances 0.000 claims description 6
- 239000003480 eluent Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 230000001699 photocatalysis Effects 0.000 claims description 6
- 239000003504 photosensitizing agent Substances 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229960004418 trolamine Drugs 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229960001866 silicon dioxide Drugs 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 238000013375 chromatographic separation Methods 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 abstract 1
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 abstract 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 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
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- 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
Abstract
The invention provides an iridium complex, which has a visible light reactivity and can be used for rapidly preparing hydrogen through reduction by catalyzing water by using visible light. The invention further provides a preparation method of the iridium complex, a method for preparing hydrogen by catalyzing and reducing the water by using the visible light by means of the iridium complex and a dye-sensitized solar cell containing the iridium complex. The iridium complex comprises a chemical formula of Ir(L)2Hbpdc, wherein L is 3-trifluoromethyl-2-phenyl benzothiazole, 2-phenyl benzothiazole, 2-phenyl-5-(trifluoromethyl) benzothiazole or 4-N,N dimethyl-phenyl-5-(trifluoromethyl) benzothiazole, and Hbpdc is 4-carboxyl-4'-carboxylate-2,2'-bipyridyl. The preparation method of the iridium complex comprises the steps of: dissolving iridium trichloride and L in a first solvent, reacting to obtain an intermediate product Ir2(L)4Cl2, and reacting the intermediate product with 4-4'-dicarboxylic acid-2,2'-bipyridyl and sodium carbonate to obtain the iridium complex.
Description
Technical field
The present invention provides a kind of complex of iridium, its preparation method, and utilizes said complex of iridium to realize the method for visible light catalytic reductive water and the dye-sensitized solar cells that makes.
Background technology
Got into since 21 century, the consumption of fossil energy not only causes energy dilemma, and serious destruction the environment of human survival.Seek with development environment close friend type, reproducible green energy resource and become the human emphasis of paying close attention to.The calorific value that Hydrogen Energy has cleanliness without any pollution, hydrogen is high, have good burning performance, utilize characteristics such as form is many, store content is big; That sun power has is general, harmless, the characteristic of permanent use, and they are regarded as the most potential clean energy of 21 century.Can hydrogen act as a fuel widely-used, and key is process for making hydrogen.As the main path of scale operation hydrogen, brine electrolysis is the most feasible beyond doubt.Yet the Wasserstoffatoms in the water molecules combines very closely, will consume a large amount of electric power during electrolysis, and the energy that is produced than burning hydrogen itself is also many.It is that energy by light makes water decomposition that photochemical catalyzing prepares hydrogen, is chemical energy with solar energy converting, so this technology has received attracting attention of scientific circles as what from water, extract hydrogen.Conventional semiconductor material has the performance that photo catalytic reduction water prepares hydrogen, yet it has the visible light of absorption ability, and catalytic rate is characteristic slowly.Simultaneously, seeking excellent photocatalyst is hydrocarbon polymer (such as methane) with carbon dioxide reduction, not only can solve Climatic issues, can also alleviating energy crisis.In addition; Design is the current research focus of device research also becoming of electric energy with sending out solar energy converting; Dye-sensitized solar cells is that a kind of preparation technology is simple, and electrooptical device with low cost utilizes this battery to utilize sun power also to become the emphasis of people's work.In view of above situation; Research and development have visible light-responded, can be fast the water reduction are prepared hydrogen and be that the catalyzer of hydrocarbon polymer is chemical energy with solar energy converting and is that the device of electric energy becomes research focus instantly with solar energy converting with carbon dioxide reduction.
Summary of the invention
The present invention provides a kind of complex of iridium, have visible light-responded, be a kind of can be fast with the catalyzer of water reduction preparation hydrogen.
The present invention also provides the preparation method of said complex of iridium.
The present invention also provides with said complex of iridium and realizes that as photosensitizers the visible light catalytic reductive water prepares the method for hydrogen.
The present invention also provides the dye-sensitized solar cells that contains said complex of iridium.
Said complex of iridium, its chemical formula are Ir (L)
2Hbpdc, wherein L is 3-trifluoromethyl-2-phenyl benzothiazole, 2-phenyl benzothiazole; 2-phenyl-5-(trifluoromethyl) benzothiazole or 4-N; N dimethyl--phenyl-5-(trifluoromethyl) benzothiazole, Hbpdc be 4-carboxyl-4 '-carboxylate radical-2,2 '-dipyridyl.
The structural formula of said complex of iridium does
Title complex 1
Title complex 2
Title complex 3
Title complex 4
The preparation method of said complex of iridium does, iridous chloride and L are dissolved in first solvent, and after the back flow reaction, cooling, purifying obtains intermediate product Ir
2(L)
4Cl
2, with intermediate product and 4 ,-4 '-dicarboxylicacid-2,2 '-dipyridyl, yellow soda ash be dissolved in second solvent, and in the reaction of protection of inert gas refluxed, cooling, purifying obtains said complex of iridium.Above-mentioned first solvent and second solvent need to satisfy making reactants dissolved, and the requirement that is enough to make the complex reaction generation under the solvent refluxing temperature.According to the difference of reactant, selecting the first suitable solvent and second solvent is state of the art, and first solvent and second solvent can be identical or different.Preferably; L is 3-trifluoromethyl-2-phenyl benzothiazole; When 2-phenyl benzothiazole or 2-phenyl-5-(trifluoromethyl) benzothiazole, first solvent is the mixed solvent of ethylene glycol ethyl ether and water, and the volume ratio of ethylene glycol ethyl ether and water is 3: 1; Second solvent is the mixed solvent of methyl alcohol and methylene dichloride, and the volume ratio of methyl alcohol and methylene dichloride is 1: 1; L is 4-N, and during N dimethyl--phenyl-5-(trifluoromethyl) benzothiazole, first solvent is the mixed solvent of ethylene glycol ethyl ether and water, and the volume ratio of ethylene glycol ethyl ether and water is 3: 1, and second solvent is an ethylene glycol ethyl ether.Further preferred, L is 3-trifluoromethyl-2-phenyl benzothiazole, when 2-phenyl benzothiazole or 2-phenyl-5-(trifluoromethyl) benzothiazole; With iridous chloride; Ligand L was dissolved in the mixed solvent of 24ml ethylene glycol ethyl ether and water in 1: 2 in molar ratio, and the volume ratio of ethylene glycol ethyl ether and water is 3: 1, and back flow reaction is spent the night; After being cooled to room temperature, purifying obtains intermediate product Ir
2(L)
4Cl
2With intermediate product and 4 ,-4 '-dicarboxylicacid-2,2 '-dipyridyl, yellow soda ash be dissolved in the mixed solvent of methyl alcohol and methylene dichloride in 1: 1.2: 8 ratio of proportioning; The volume ratio of methyl alcohol and methylene dichloride is 1: 1; Spend the night in the reaction of protection of inert gas refluxed, be cooled to room temperature, purifying obtains said complex of iridium; L is 4-N; During N dimethyl--phenyl-5-(trifluoromethyl) benzothiazole; 1mmol iridous chloride and 2.0mmol L are dissolved in the mixed solvent of 24ml ethylene glycol ethyl ether and water; Wherein the volume ratio of ethylene glycol ethyl ether and water is 3: 1, and back flow reaction is spent the night, and is cooled to room temperature, purifying obtains intermediate product Ir
2(L)
4Cl
2, with intermediate product and 4 ,-4 '-dicarboxylicacid-2,2 '-dipyridyl, 1: 1.2: 8 in molar ratio ratio of yellow soda ash be dissolved in the ethylene glycol ethyl ether, spends the night in the reaction of protection of inert gas refluxed, be cooled to normal temperature after, purifying obtains said complex of iridium.
Preferably, after iridous chloride and the ligand L back flow reaction, cool to room temperature revolves solvent that to do the back be that 3: 1 ETHYLE ACETATE is that eluent separates with normal hexane with volume ratio in silicagel column, collects red stream section, with solvent revolve dried after, drying obtains intermediate product Ir
2(L)
4Cl
2, with intermediate product and 4 ,-4 '-dicarboxylicacid-2,2 '-dipyridyl and yellow soda ash back flow reaction after, be cooled to room temperature, be that 1: 1 methyl alcohol and methylene dichloride is that eluent carries out chromatographic separation with volume ratio, purifying obtains said complex of iridium.
A kind ofly can realize that as photosensitizers the visible light catalytic reductive water prepares hydrogen with said complex of iridium.Reported in the prior art that some photosensitizers realization visible light catalytic reductive water prepares the method for hydrogen; The present invention can adopt the method for these existing photo catalytic reduction water; Just substitute photosensitizers of the prior art with complex of iridium according to the invention; For example can be, with complex of iridium, trolamine (TEOA), K
2PtCl
4Add (10 μ M complex of iridium, 0.28M TEOA, 0.02mM K in the aqueous solution
2PtCl
4, 0.135M LiCl transfers pH to neutral with concentrated hydrochloric acid, and photo catalytic reduction water prepares hydrogen under visible light radiation.Said complex of iridium is a photosensitizers, and TEOA is a sacrifice agent, K in the solution
2PtCl
4The colloidal platinum that generates after the illumination is a catalyzer.TEOA, K
2PtCl
4Consumption be prior art.
A kind of with the dye-sensitized solar cells of said complex of iridium as dyestuff.Preferably, the titanium oxide of complex of iridium dye sensitization is the light anode, and platinum electrode is a counter electrode, I
-/ I
3 -Be ionogen.
The invention has the beneficial effects as follows: prepare hydrogen with traditional complex of iridium photo catalytic reduction water and compare; The invention provides a series of complex of iridium; Can in the aqueous solution, prepare hydrogen by the visible light catalytic reductive water; Avoided using the organic solvent of high density, both simplified reaction system, can reduce cost again.
Embodiment
Embodiment 1: complex of iridium synthetic
With iridous chloride (III), cyclic metal complexes L joined in the mixed solvent of 24ml ethylene glycol ethyl ether and water (V/V, 3: 1) in 1: 2 in molar ratio; Behind the back flow reaction 24h, cool to room temperature, with solvent revolve do the back in silicagel column with ETHYLE ACETATE and normal hexane ((V/V; 3: 1) be the eluent isolation of intermediate products; It is short to collect red stream, with solvent revolve do after, drying obtains intermediate product Ir
2(L)
4Cl
2With double-core intermediate product and 4 ,-4 '-dicarboxylicacid-2,2 '-dipyridyl; Yellow soda ash joins in second solvent in 1: 1.2: 8 ratio of proportioning that (for title complex 1-3, second solvent is (V/V, 1: 1) in the mixed solvent of methyl alcohol and methylene dichloride; For title complex 4, the second solvents is the ethylene glycol ethyl ethers ethereal solution), at nitrogen protection refluxed reaction 24h; Be cooled to room temperature; Mixed solvent (V/V, 1: 1) with methyl alcohol and methylene dichloride separates for eluent carries out chromatographic column, obtains orange/yellow solid sample Ir (L)
2Hbpdc.
When described ligand L was a 3-trifluoromethyl-2-phenyl benzothiazole, product was a title complex 1:
1H NMR (500MHz, CD
3COOD): δ δ 9.33 (2H, s), 8.40 (2H, s), 8.22 (4H, m), 8.10 (2H, d), 7.49 (2H, m), 7.20-7.27 (4H, J=8.5, d), 6.66 (2H, J=6.5, d), 6.38 (2H, J=8.5, d). ultimate analysis, measured value: C
40H
21F
6IrN
4O
4S
2: C, 48.51; H, 2.12; N, 5.60; Calculated value: C, 48.43; H, 2.13; N, 5.65.ESI MS:991.00 (m
+).
When described ligand L was the phenyl benzothiazole, product was a title complex 2:
1H NMR (500MHz, CD
3COOD): δ 9.29 (2H, s), 8.41 (2H, J=8.5, d), 8.18 (2H, J=6.5, d); 8.01 (2H, J=8.0, d), 7.94 (2H, J=6.5, d), 7.41 (2H; J=6.5, t), 7.17 (4H, m), 6.94 (2H, J=9.0, t); 6.48 (2H, J=8.0, d), 6.33 (2H, J=10, d). ultimate analysis, measured value: IrC
38H
23O
4N
4S
2: C, 53.21; H, 2.82; N, 6.60; Calculated value: C, 53.32; H, 2.71; N, 6.55.ESI MS:855,92 (m
+).
When described ligand L was 2-phenyl-5-(trifluoromethyl) benzothiazole, product was a title complex 3:
1H NMR (500MHz, CD
3COOD): δ 9.38 (2H, s), 8.57 (2H, J=8.0, d), 8.25 (4H, m), 8.04 (2H, J=6.5, d), 7.68 (2H, J=8.0, d), 7.23 (2H, J=8.5, t), 7.02 (2H, J=6.5, t), 6.51 (2H, J=6.0, d), 6.35 (2H, s).Ultimate analysis, measured value: C
40H
21F
6IrN
4O
4S
2: C, 48.51; H, 2.12; N, 5.60; Calculated value: C, 48.43; H, 2.13; N, 5.65.ESI MS:990.92 (m
+).
Described ligand L is 4-N, N dimethyl--phenyl-5-(trifluoromethyl) benzothiazole, and product is a title complex 4:
1H NMR (500MHz, CD
3COOD): δ 9.35 (2H, s), 8.63 (2H, J=8.0, d), 8.28 (2H, d), 8.12 (2H, J=6.5, d), 7.82 (2H, J=8.0, s), 7.52 (2H, J=8.5, t), 6.66 (2H, J=6.5, d), 6.25 (2H, J=6.0, d), 5.80 (2H, s).Ultimate analysis, measured value: C
44H
31F
6IrN
6O
4S
2: C, 47.82; H, 2.98; N, 7.63; Calculated value: C, 48.02; H, 2.90; N, 7.80:ESI MS:1076.75 (m
+).
Embodiment 2:
Complex of iridium photo catalytic reduction water prepares hydrogen in the homogeneous catalysis system: 2.7 μ mol complex of iridium are joined contain the 0.28M trolamine, 0.02mM K
2PtCl
4, in the neutral aqueous solution of 0.135M LiCl (270ml), after the reactor drum air drained, (λ＞420nm), the hydrogen that reaction generates was through the chromatography of gases quantitative analysis in irradiation under the xenon lamp of 300W.The system at title complex 1,2,3,4 place generates hydrogen behind illumination 20h amount is respectively 2027 μ mol, 175 μ mol, 55 μ mol, 9 μ mol, and wherein to go out the efficient of hydrogen be present in the aqueous solution, report the highest to title complex 1.
Embodiment 3:
The optically catalytic TiO 2 reductive water of complex of iridium sensitization in the nonhomogeneous system prepares hydrogen: titanium oxide is placed in the saturated methanol solution of title complex; Lucifuge stirred after 24 hours; The titanium oxide that sensitization is good is solid-state to filter out, and drying obtains powdered sample.The titanium oxide solid (amount that the titanium oxide of title complex 1,2,3,4 sensitizations contains complex of iridium is respectively 2.17 μ mol, 3.01 μ mol, 2.56 μ mol, 3.34 μ mol) of 0.1g complex of iridium sensitization is joined and contains the 0.28M trolamine, 0.02mM K
2PtCl
4, in the neutral aqueous solution of 0.135M LiCl (270ml), after the reactor drum air drained, (λ＞420nm), the hydrogen of generation was through the chromatography of gases quantitative analysis in irradiation under the xenon lamp of 300W.The system at title complex 1,2,3,4 places generates hydrogen behind illumination 20h amount is respectively 1253 μ mol, 403 μ mol, 131 μ mol, 512 μ mol.
Embodiment 4:
The application of complex of iridium in the dye-sensitized solar cells device: the TiCl that the FTO glass of wash clean is soaked at 40mM
4In the solution, in 70 ℃ down heating after 20 minutes with deionized water and alcohol flushing.At the titanium deoxide slurry of scraping one deck 80 μ m that is coated with on glass, after 125 ℃ of dryings, put into retort furnace then,, be coated with the titanium deoxide slurry of scraping one deck 80 μ m more in the above, heat 20 minutes postcooling to room temperature in 450 ℃ in 450 ℃ of heating 20 minutes.It is soaked in the TiCl of 40mM once more
4In the solution, in 70 ℃ down heating transfer to after 20 minutes in the muffle furnace in 500 ℃ of sintering, be cooled to room temperature after, titanium dioxide photoelectrode is soaked in the complex of iridium dyestuff of 0.5mM, water flushing behind the 24h is 30 ℃ of dryings.With the titanium dioxide photoelectric level after the sensitization is anode, and platinized platinum is a negative electrode, I
-/ I
3 -(1.0MBMII, 50mM Lil, 30mM I
2, 0.5M 4-tert .-butylpyridine, solvent is acetonitrile and valeronitrile, V: V=85: 15) be ionogen assembling becoming nano-crystalline titanium dioxide dye-sensitized solar cells device.Be that the open circuit voltage of anodic dye cell device to test gained is respectively 0.510V, 0.500V, 0.490V, 0.489V with the titanium dioxide photoelectrode after complex of iridium 1,2,3,4 sensitizations respectively; Short-circuit current density is respectively 2.227mA cm
-2, 3.720mA cm
-2, 2.348mA cm
-2, 3.015mA cm
-2Photoelectric transformation efficiency η is respectively 0.76%, 1.39%, 0.82%, 1.09%.
Claims (10)
1. a complex of iridium is characterized in that, its chemical formula is Ir (L)
2Hbpdc, wherein L is 3-trifluoromethyl-2-phenyl benzothiazole, 2-phenyl benzothiazole; 2-phenyl-5-(trifluoromethyl) benzothiazole or 4-N; N dimethyl--phenyl-5-(trifluoromethyl) benzothiazole, Hbpdc be 4-carboxyl-4 '-carboxylate radical-2,2 '-dipyridyl.
2. complex of iridium as claimed in claim 1, its structural formula does
Perhaps,
Perhaps,
Perhaps,
3. the preparation method of claim 1 or 2 described complex of iridium is characterized in that, iridous chloride and L are dissolved in first solvent, and after the back flow reaction, cooling, purification obtain intermediate product Ir
2(L)
4Cl
2, with intermediate product and 4 ,-4 '-dicarboxylicacid-2,2 '-dipyridyl, yellow soda ash be dissolved in second solvent, and in the reaction of protection of inert gas refluxed, cooling, purifying obtains said complex of iridium.
4. the preparation method of complex of iridium as claimed in claim 3; It is characterized in that L is 3-trifluoromethyl-2-phenyl benzothiazole, when 2-phenyl benzothiazole or 2-phenyl-5-(trifluoromethyl) benzothiazole; 1mmol iridous chloride and 2.0mmol L are joined in the mixed solvent of 24ml ethylene glycol ethyl ether and water; Wherein the volume ratio of ethylene glycol ethyl ether and water is 3: 1, and back flow reaction is spent the night, and is cooled to room temperature, purifying obtains intermediate product Ir
2(L)
4Cl
2With intermediate product and 4;-4 '-dicarboxylicacid-2,2 '-dipyridyl, 1: 1.2: 8 in molar ratio ratio of yellow soda ash join in the mixed solvent of methyl alcohol and methylene dichloride, and the volume ratio of methyl alcohol and methylene dichloride is 1: 1; Spend the night in protection of inert gas refluxed reaction, be cooled to normal temperature after, purifying obtains said complex of iridium.
5. the preparation method of complex of iridium as claimed in claim 3; It is characterized in that L is 4-N, during N dimethyl--phenyl-5-(trifluoromethyl) benzothiazole; 1mmol iridous chloride and 2.0mmol L are dissolved in the mixed solvent of 24ml ethylene glycol ethyl ether and water; Wherein the volume ratio of ethylene glycol ethyl ether and water is 3: 1, and back flow reaction is spent the night, and is cooled to room temperature, purifying obtains intermediate product Ir
2(L)
4Cl
2, with intermediate product and 4 ,-4 '-dicarboxylicacid-2,2 '-dipyridyl, 1: 1.2: 8 in molar ratio ratio of yellow soda ash be dissolved in the ethylene glycol ethyl ether, spends the night in the reaction of protection of inert gas refluxed, be cooled to normal temperature after, purifying obtains said complex of iridium.
6. like the preparation method of claim 4 or 5 described complex of iridium; It is characterized in that, after iridous chloride and the ligand L back flow reaction, cool to room temperature; Solvent revolved to do the back be that 3: 1 ETHYLE ACETATE is that eluent separates with normal hexane with volume ratio in silicagel column; Collect red stream section, with solvent revolve do after, drying obtains intermediate product Ir
2(L)
4Cl
2, with intermediate product and 4 ,-4 '-dicarboxylicacid-2,2 '-dipyridyl and yellow soda ash back flow reaction after, be cooled to room temperature, be that 1: 1 methyl alcohol and methylene dichloride is that eluent carries out chromatographic separation with volume ratio, purifying obtains described complex of iridium.
7. realize that as photosensitizers the visible light catalytic reductive water prepares the method for hydrogen with claim 1 or 2 said complex of iridium for one kind.
8. visible light catalytic reductive water as claimed in claim 7 prepares the method for hydrogen, it is characterized in that said complex of iridium, trolamine, K
2PtCl
4Add in the aqueous solution, transfer pH to neutral with concentrated hydrochloric acid, photo catalytic reduction water prepares hydrogen under visible light radiation.
9. one kind with claim 1 or the 2 said complex of iridium dye-sensitized solar cells as dyestuff.
10. said dye-sensitized solar cells as claimed in claim 9 is characterized in that, the titanium oxide of said complex of iridium dye sensitization is the light anode, and platinum electrode is a counter electrode, I
-/ I
3 -Be ionogen.
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| CN106732783A (en) * | 2016-12-07 | 2017-05-31 | 盐城工学院 | A kind of heterogeneous iridium pyridine complex visible light catalyst and preparation method and application |
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