CN102532170A - Monovalent copper complex, preparation method thereof, method for catalyzing and reducing carbon dioxide by utilizing visible light and dye-sensitized solar cell - Google Patents
Monovalent copper complex, preparation method thereof, method for catalyzing and reducing carbon dioxide by utilizing visible light and dye-sensitized solar cell Download PDFInfo
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- CN102532170A CN102532170A CN2011104318486A CN201110431848A CN102532170A CN 102532170 A CN102532170 A CN 102532170A CN 2011104318486 A CN2011104318486 A CN 2011104318486A CN 201110431848 A CN201110431848 A CN 201110431848A CN 102532170 A CN102532170 A CN 102532170A
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- copper complex
- univalent copper
- carbon dioxide
- visible light
- dye
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- 150000004699 copper complex Chemical class 0.000 title claims abstract description 47
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 21
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000010949 copper Substances 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 23
- 206010070834 Sensitisation Diseases 0.000 claims description 19
- 230000008313 sensitization Effects 0.000 claims description 19
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 16
- 239000000975 dye Substances 0.000 claims description 13
- 230000003197 catalytic effect Effects 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000007146 photocatalysis Methods 0.000 claims description 5
- 230000001699 photocatalysis Effects 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229960001866 silicon dioxide Drugs 0.000 claims description 4
- 239000003480 eluent Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- 150000003624 transition metals Chemical class 0.000 abstract description 2
- 239000003446 ligand Substances 0.000 abstract 2
- VQIHSHZMUBTRMU-UHFFFAOYSA-N 6-methyl-2-(6-methylpyridin-2-yl)-3,4-diphenylpyridine Chemical group C1(=CC=CC=C1)C1=C(C(=NC(=C1)C)C1=NC(=CC=C1)C)C1=CC=CC=C1 VQIHSHZMUBTRMU-UHFFFAOYSA-N 0.000 abstract 1
- 229920001651 Cyanoacrylate Polymers 0.000 abstract 1
- 230000031700 light absorption Effects 0.000 abstract 1
- 238000011160 research Methods 0.000 description 6
- 235000011089 carbon dioxide Nutrition 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 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
- 230000009467 reduction Effects 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 239000002002 slurry 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
- 0 CC(*(C*1)=C(C=C(C)C(C)=CC=C(C)C=C(O)[Zn])C(C=C(C)c2ccc(C=C(O)[Zn])cc2)=*(C(C)=C)N*(c(C)ccc2)c2-c2*1c(C)cc(-c1ccc(C=C(*)O)cc1)c2)=C Chemical compound CC(*(C*1)=C(C=C(C)C(C)=CC=C(C)C=C(O)[Zn])C(C=C(C)c2ccc(C=C(O)[Zn])cc2)=*(C(C)=C)N*(c(C)ccc2)c2-c2*1c(C)cc(-c1ccc(C=C(*)O)cc1)c2)=C 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N Cc1ccc(C)cc1 Chemical compound Cc1ccc(C)cc1 URLKBWYHVLBVBO-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
- 229920002472 Starch Polymers 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- XBVLXSQOCZMOFV-UHFFFAOYSA-N carbonic acid oxygen(2-) titanium(4+) Chemical compound [O--].[O--].[Ti+4].OC(O)=O XBVLXSQOCZMOFV-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention relates to a monovalent copper complex, a preparation method of the monovalent copper complex, a method for catalyzing and reducing carbon dioxide by utilizing visible light and a dye-sensitized solar cell which takes the monovalent copper complex as dye. The chemical formula of the monovalent copper complex is Cu (N^N) 2PF6, wherein the ligand N^N is 4, 4'-(4-cyano acrylate) diphenyl-6, 6'- dimethyl-2, 2'- bipyridyl. The preparation method of the monovalent copper complex comprises the steps of reacting Cu (CH3CN) 4PF6 with the ligand N^N in a mole ratio of 1:2, cooling, purifying and obtaining the Cu (N^N) 2PF6. The transition metal Cu based complex provided by the invention has good light absorption ability; in addition, by utilizing the titanium dioxide sensitized by the copper complex, the method for preparing methane through catalyzing and reducing the carbon dioxide by utilizing the visible light is realized.
Description
Technical field
The present invention relates to the method and the dye-sensitized solar cells of a kind of univalent copper complex, its preparation method, visible light catalytic reducing carbon dioxide.
Background technology
Human traditional fossil energy is used on a large scale, achieved and accelerated the modern high speed process of current world economy, but also make energy carrier when 21 century faces by rapid consumption so that exhausted crisis, bring the global warming problem.Highlight day by day in Climatic issues, under the international overall background that energy dilemma receives much concern, the development low-carbon economy, the development and use new forms of energy are built consensus in the whole world.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.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; Electrooptical device with low cost utilizes this battery to utilize sun power also to become the emphasis of researcher's work.Utilize sunshine when solving global greenhouse effect, to bring the new energy for inflammable gass such as carbon monoxide, methane in addition to carbon dioxide reduction; If this advanced person's photocatalysis technology can drop into practical application; " just can pass through photosynthesis; glucide such as synthetic starch and sucrose are the same from carbonic acid gas, for through the synthetic practicability blaze the trail of artificial light " with the synthetic useful matter of carbonic acid gas as plant.Solving aspect Climatic issues and the energy dilemma also with significant.The dyestuff that conventional dyes sensitization battery uses is based on the heavy metal ruthenium complexe, and this type dyestuff is not only based on noble metal, but also can bring heavy metal contamination.Therefore, develop low price, free of contamination new dye has very important significance; In addition, the material of traditional photochemical catalysis research carbon dioxide reduction is based on semiconductor material, yet it has the visible light of absorption ability, and catalytic rate is characteristic slowly.In view of above situation, research and development have visible light-responded, can realize soon that carbon dioxide reduction is that the catalyzer of hydrocarbon polymer is chemical energy with solar energy converting and is that the molecular device of electric energy becomes research focus instantly with solar energy converting.
Summary of the invention
The present invention provides a kind of univalent copper complex, can be used for the visible light catalytic reducing carbon dioxide and prepare methane and dye-sensitized solar cells.
The present invention also provides the preparation method of above-mentioned univalent copper complex.
The present invention also provides the method that realizes the visible light catalytic reducing carbon dioxide with above-mentioned univalent copper complex as catalyzer.
The present invention also provides with the dye-sensitized solar cells of above-mentioned univalent copper complex as dyestuff.
Said univalent copper complex, its chemical formula are Cu (N^N)
2PF
6, wherein part N^N be 4,4 '-two (to alpha-cyanoacrylate) phenyl-6,6 '-dimethyl--2,2 '-dipyridyl.This complex structure characteristic is that the plane at 2 N^N coordination places is vertical each other, and the central copper atom is a four-coordination, and cupprous positive charge is neutralized by the hexafluoro-phosphate radical negatively charged ion.Its structural formula is as follows:
The preparation method of said univalent copper complex does, with Cu (CH
3CN)
4PF
6With the reaction in 1: 2 in molar ratio of N^N part, cooling, purification obtain Cu (N^N)
2PF
6This reaction type is a known response, and concrete operation can be: with 0.5mmol Cu (CH
3CN)
4PF
6Join to react in 1: 1 (v/v) mixed solvent of 30ml methylene dichloride and methyl alcohol with 1mmol N^N part and spend the night; Cool to room temperature; It is the eluent separated product that solvent is revolved dried back mixture with acetate and methyl alcohol 1: 2 (v/v) in silicagel column; It is short to collect red stream, with solvent revolve do after, drying obtains scarlet product C u (N^N)
2PF
6
Said univalent copper complex can be used as catalyzer and realizes that the visible light catalytic reducing carbon dioxide prepares the method for methane.Concrete operation can be: the titanium oxide with described univalent copper complex sensitization realizes that as catalyzer the visible light photocatalysis reducing carbon dioxide prepares methane.Preferably, the amount of univalent copper complex is 30～50 μ mol/g in the titanium oxide of described univalent copper complex sensitization.The preparation method of the titanium oxide of wherein said univalent copper complex sensitization is following: titanium oxide is placed in the saturated methanol solution of said univalent copper complex, and lucifuge stirs the titanium oxide that obtains sensitization.
A kind of said univalent copper complex can obtain dye-sensitized solar cells as dyestuff.Preferred scheme is: the titanium oxide of said univalent copper complex 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: compare with the dyestuff ruthenium complexe dyestuff that the dye-sensitized solar cells of tradition research uses, the invention provides a kind of title complex, have good extinction ability based on transition metal copper; In addition; The titanium oxide of the title complex sensitization of this copper of process has realized that the visible light catalytic reducing carbon dioxide prepares the method for methane, further research is explored have positive pushing effect with title complex as photosensitizers with in photochemical catalyzing reducing carbon dioxide field.
Description of drawings
Fig. 1 is: the titanium dioxide carbonic acid gas of univalent copper complex and univalent copper complex sensitization generates the methane rate profile;
Fig. 2 is: based on the sensitization solar cell current voltage characteristic of univalent copper complex dyestuff.
Embodiment
Embodiment 1: part synthetic:
With 1mmol4,4 '-two (to aldehyde radical) phenyl-6,6 '-dimethyl--2; 2 '-dipyridyl, 2.98mmol alpha-cyanoacrylate, 0.1ml piperidines join in the 10ml chloroformic solution; The mixed-liquor return reaction is spent the night; Forming the yellowish brown solid, filter and obtain solid, is the eluent separated product with ETHYLE ACETATE in silicagel column.Productive rate (71%).
1H NMR (500MHz, CDCl
3): 10.13 (2H, s), 8.57 (2H, s), 8.05 (4H, J=8.5, d), 7.95 (4H, J=6.5, d), 7.50 (2H, S), 8.77 (4H, s), 2.76 (6H, s).
Embodiment 2: univalent copper complex synthetic:
With 0.5mmol Cu (CH
3CN)
4PF
6With 1mmol N^N [4,4 '-two (to alpha-cyanoacrylate) phenyl-6,6 '-dimethyl--2,2 '-dipyridyl].Part N^N joined (v/v in the mixed solvent of 30ml methylene dichloride and methyl alcohol in 1: 2 in molar ratio; 1: 1) reaction spends the night, cool to room temperature, with solvent revolve do the back in silicagel column with acetate and methyl alcohol (v/v; 1: 2) be the washing and dehydrating integrated machine separated product; It is short to collect red stream, with solvent revolve do after, drying obtains scarlet product C u (N^N)
2PF
6, (N^N) be 4,4 '-two (to alpha-cyanoacrylate) phenyl-6,6 '-dimethyl--2,2 '-dipyridyl.
1H NMR (500MHz, CF
3COOD): δ 8.93 (4H, s), 8.85 (4H, s), 8.59 (4H, s), 8.47 (8H, J=8.5, d), 8.29 (8H, J=6.5, d), 3.26 (12H, S) .IR (KBr, cm
-1), 3396,2217,1628,1570,1544,1389,1356,1195,1015,834,724. ultimate analyses, measured value CuC
64N
8H
44O
8PF
6: 61.08; H, 3.62; N, 8.92; Calculated value CuC
64N
8H
44O
8PF
6: C, 60.93; H, 3.52; N, 8.88.
Embodiment 3: the application of univalent copper complex in the visible light photocatalysis reducing carbon dioxide:
0.1g embodiment 2 gained univalent copper complex pressed powder samples are positioned in the glass reactor; The reactor drum air is found time; Feed carbonic acid gas air pressure in the system is reached a normal atmosphere; Injection 0.4ml deionized water in system, then with system illumination under xenon lamp (300W), respectively in interlude in the abstraction reaction bottle 1.0ml gaseous sample import to and carry out composition analysis in the chromatography of gases.Result (Fig. 1) shows, in copper complex solid sample catalystsystem, is 9 μ mol/g through producing methane concentration behind the 9h.
Embodiment 4: the application of the titanium oxide of univalent copper complex sensitization in the visible light photocatalysis reducing carbon dioxide:
The titanium oxide pressed powder sample of 0.1g embodiment 2 gained univalent copper complex sensitizations is positioned over (specimen preparation process: the 0.25g titania powder is incorporated in the univalent copper complex 10ml methanol solution appearance of 1mM in the glass reactor; Lucifuge is behind 50 ℃ of whip attachment 24h; Solid filtering is come out,, obtain the titanium dioxide sample of univalent copper complex sensitization with 70 ℃ of oven dry; The amount that sample contains univalent copper complex is 40 μ mol/g); The reactor drum air is found time, feed carbonic acid gas air pressure in the system is reached a normal atmosphere, injection 0.4ml deionized water in system; Then with system illumination under xenon lamp (300W), respectively in interlude in the abstraction reaction bottle 1.5ml gaseous sample import to and carry out composition analysis in the chromatography of gases.Result (Fig. 1) shows that in the titanium oxide pressed powder sample catalystsystem of copper complex sensitization, producing methane concentration behind the illumination 30h is 170 μ mol/g.
Embodiment 5: the application of univalent copper complex 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 univalent copper complex 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
-/ 1
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.The open circuit voltage of test gained is 0.57V; Short-circuit current density is 4.69mA cm
-2Packing factor is 78.8%; Photoelectric transformation efficiency η is respectively 2.2%.
Claims (10)
1. univalent copper complex, its chemical formula is Cu (N^N)
2PF
6, wherein part N^N be 4,4 '-two (to alpha-cyanoacrylate) phenyl-6,6 '-dimethyl--2,2 '-dipyridyl.
2. univalent copper complex as claimed in claim 1 is characterized in that its structural formula does
3. the preparation method of claim 1 or 2 described univalent copper complexs is characterized in that, with Cu (CH
3CN)
4PF
6With the reaction in 1: 2 in molar ratio of N^N part, cooling, purification obtain Cu (N^N)
2PF
6
4. the preparation method of univalent copper complex as claimed in claim 3 is characterized in that, with 0.5mmolCu (CH
3CN)
4PF
6Join to react in 1: 1 (v/v) mixed solvent of 30ml methylene dichloride and methyl alcohol with 1mmol N^N part and spend the night; Cool to room temperature; It is the eluent separated product that solvent is revolved dried back mixture with acetate and methyl alcohol 1: 2 (v/v) in silicagel column; It is short to collect red stream, with solvent revolve do after, drying obtains scarlet product C u (N^N)
2PF
6
5. realize that as catalyzer the visible light catalytic reducing carbon dioxide prepares the method for methane with claim 1 or 2 said univalent copper complexs for one kind.
6. visible light catalytic reducing carbon dioxide as claimed in claim 5 prepares the method for methane, it is characterized in that, realizes that as catalyzer the visible light photocatalysis reducing carbon dioxide prepares methane with the titanium oxide of described univalent copper complex sensitization.
7. visible light catalytic reducing carbon dioxide as claimed in claim 5 prepares the method for methane, it is characterized in that, the amount of univalent copper complex is 30～50 μ mol/g in the titanium oxide of described univalent copper complex sensitization.
8. visible light catalytic reducing carbon dioxide as claimed in claim 6 prepares the method for methane; It is characterized in that; The preparation method of the titanium oxide of described univalent copper complex sensitization is following: titanium oxide is placed in the saturated methanol solution of said univalent copper complex, and lucifuge stirs the titanium oxide that obtains sensitization.
9. one kind with claim 1 or the 2 said univalent copper complexs 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 univalent copper complex dye sensitization is the light anode, and platinum electrode is a counter electrode, I
-/ I
3 -Be ionogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110431848.6A CN102532170B (en) | 2011-12-21 | 2011-12-21 | Monovalent copper complex, preparation method thereof, method for catalyzing and reducing carbon dioxide by utilizing visible light and dye-sensitized solar cell |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110431848.6A CN102532170B (en) | 2011-12-21 | 2011-12-21 | Monovalent copper complex, preparation method thereof, method for catalyzing and reducing carbon dioxide by utilizing visible light and dye-sensitized solar cell |
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| Publication Number | Publication Date |
|---|---|
| CN102532170A true CN102532170A (en) | 2012-07-04 |
| CN102532170B CN102532170B (en) | 2014-04-02 |
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| CN103864823A (en) * | 2014-03-14 | 2014-06-18 | 洛阳师范学院 | Cu (I) coordination polymer green light emitting material and synthesis method thereof |
| CN104607251A (en) * | 2015-02-10 | 2015-05-13 | 洛阳师范学院 | Frame compound catalyst material containing mixed valence Cu and preparation method thereof |
| CN109096069A (en) * | 2018-09-14 | 2018-12-28 | 郑州大学 | Sensitizing dyestuff solar battery light anode is in photocatalytic synthesis at the application in function small molecule compound |
| JP2022129732A (en) * | 2021-02-25 | 2022-09-06 | 株式会社豊田中央研究所 | Carbon dioxide reduction catalyst, carbon dioxide reduction device, and artificial photosynthesis device |
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| WO2011149620A2 (en) * | 2010-05-25 | 2011-12-01 | Lawrence Livermore National Security, Llc | Synthesis of triazole-based and imidazole-based zinc catalysts |
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| WO2011149620A2 (en) * | 2010-05-25 | 2011-12-01 | Lawrence Livermore National Security, Llc | Synthesis of triazole-based and imidazole-based zinc catalysts |
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| CN103864823A (en) * | 2014-03-14 | 2014-06-18 | 洛阳师范学院 | Cu (I) coordination polymer green light emitting material and synthesis method thereof |
| CN103864823B (en) * | 2014-03-14 | 2016-08-24 | 洛阳师范学院 | A kind of Cu (I) coordination polymer green luminescent material and synthetic method thereof |
| CN104607251A (en) * | 2015-02-10 | 2015-05-13 | 洛阳师范学院 | Frame compound catalyst material containing mixed valence Cu and preparation method thereof |
| CN109096069A (en) * | 2018-09-14 | 2018-12-28 | 郑州大学 | Sensitizing dyestuff solar battery light anode is in photocatalytic synthesis at the application in function small molecule compound |
| CN109096069B (en) * | 2018-09-14 | 2022-06-28 | 郑州大学 | Application of sensitized dye solar cell photo-anode in photo-catalytic synthesis of functional small molecular compound |
| JP2022129732A (en) * | 2021-02-25 | 2022-09-06 | 株式会社豊田中央研究所 | Carbon dioxide reduction catalyst, carbon dioxide reduction device, and artificial photosynthesis device |
| JP7291165B2 (en) | 2021-02-25 | 2023-06-14 | 株式会社豊田中央研究所 | Carbon dioxide reduction catalyst, carbon dioxide reducer, and artificial photosynthesis device |
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