CN102532170B - 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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- CN102532170B CN102532170B CN201110431848.6A CN201110431848A CN102532170B CN 102532170 B CN102532170 B CN 102532170B CN 201110431848 A CN201110431848 A CN 201110431848A CN 102532170 B CN102532170 B CN 102532170B
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- copper complex
- univalent copper
- visible light
- carbon dioxide
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- 150000004699 copper complex Chemical class 0.000 title claims abstract description 49
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 21
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 13
- 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 44
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 21
- 239000010949 copper Substances 0.000 claims abstract description 15
- 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 27
- 206010070834 Sensitisation Diseases 0.000 claims description 19
- 230000008313 sensitization Effects 0.000 claims description 19
- 239000000975 dye Substances 0.000 claims description 13
- 230000003197 catalytic effect Effects 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 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
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000007146 photocatalysis Methods 0.000 claims description 5
- 230000001699 photocatalysis Effects 0.000 claims description 5
- 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
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 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
- 239000000523 sample Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 7
- 235000011089 carbon dioxide Nutrition 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000011160 research Methods 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
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- 238000005286 illumination Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 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
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 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
- 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
- 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
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 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
- 238000011161 development Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011010 flushing procedure 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
- 238000010422 painting 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
- 230000008569 process Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 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
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
- 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
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 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
The mankind use on a large scale to traditional fossil energy, achieve and have accelerated the modern high speed process of current world economy, but also making energy carrier face when consuming consequently exhausted crisis rapidly and bring global warming problem in 21 century.In Climatic issues, day by day highlight, under the international overall background that energy dilemma receives much concern, development low-carbon economy, develops new forms of energy and builds consensus in the whole world.That sun power has is general, harmless, the feature of permanent use, and they are regarded as the most potential clean energy of 21 century.Design and the device research that can to send out solar energy converting be electric energy also become current study hotspot, 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 in addition sunlight that carbon dioxide reduction has been brought to the new energy for inflammable gass such as carbon monoxide, methane when solving global greenhouse effect, if this advanced person's photocatalysis technology can drop into practical application, " just can pass through photosynthesis as plant; the carbohydrate such as synthetic starch and sucrose is the same from carbonic acid gas, for synthesizing by artificial light the practical blaze the trail of the synthetic useful matter of carbonic acid gas ".Solving aspect Climatic issues and energy dilemma also by significant.The dyestuff that conventional dyes sensitization battery is used is based on heavy metal ruthenium complexe, and this class 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 semiconductor material, yet it has the visible ray of absorption ability, and catalytic rate is feature slowly.In view of above situation, research and development have visible light-responded, and the catalyzer that can realize soon carbon dioxide reduction and be hydrocarbon polymer is chemical energy by solar energy converting and by solar energy converting, is electric energy molecular device becomes study hotspot instantly.
Summary of the invention
The invention provides a kind of univalent copper complex, can prepare methane and dye-sensitized solar cells for visible light catalytic reducing carbon dioxide.
The present invention also provides the preparation method of above-mentioned univalent copper complex.
The present invention also provides usings above-mentioned univalent copper complex and as catalyzer, realizes the method for visible light catalytic reducing carbon dioxide.
The present invention also provides usings the dye-sensitized solar cells of above-mentioned univalent copper complex as dyestuff.
Described univalent copper complex, its chemical formula is Cu (N^N)
2pF
6, wherein part N^N is 4,4 '-bis-(to alpha-cyanoacrylate) phenyl-6,6 '-dimethyl-2,2 '-dipyridyl.This complex structure feature is that the plane at 2 N^N coordination places is mutually vertical, and central copper atom is four-coordination, and cupprous positive charge is neutralized by hexafluoro-phosphate radical negatively charged ion.Its structural formula is as follows:
The preparation method of described univalent copper complex is, by Cu (CH
3cN)
4pF
6with the reaction in 1: 2 in molar ratio of N^N part, cooling, purification obtains Cu (N^N)
2pF
6.This reaction type is known response, and concrete operation can be: by 0.5mmol Cu (CH
3cN)
4pF
6join in 1: 1 (v/v) mixed solvent of 30ml methylene dichloride and methyl alcohol and react and spend the night with 1mmol N^N part, cool to room temperature, the mixture of acetic acid and methyl alcohol 1: 2 (v/v) of take in silicagel column after solvent is spin-dried for is eluent separated product, collect red stream short, after solvent is spin-dried for, the dry scarlet product C u (N^N) that obtains
2pF
6.
Described univalent copper complex can be used as catalyzer and realizes the method that visible light catalytic reducing carbon dioxide is prepared methane.Concrete operation can be: the titanium dioxide of described univalent copper complex sensitization of usining is realized visible light photocatalysis reducing carbon dioxide as catalyzer and prepared methane.Preferably, in the titanium dioxide of described univalent copper complex sensitization, the amount of univalent copper complex is 30～50 μ mol/g.The preparation method of the titanium dioxide of wherein said univalent copper complex sensitization is as follows: titanium dioxide is placed in the methanol solution that described univalent copper complex is saturated, and lucifuge stirs the titanium dioxide that obtains sensitization.
A kind of described univalent copper complex can obtain dye-sensitized solar cells as dyestuff.Preferred scheme is: the titanium dioxide of described univalent copper complex dye sensitization is light anode, and platinum electrode is to electrode, I
-/ I
3 -for 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 is used, the invention provides a kind of title complex based on transition metal copper, the extinction ability having had; In addition, through the titanium dioxide of the title complex sensitization of this copper, realized the method that visible light catalytic reducing carbon dioxide is prepared methane, further research and probe has been had to positive pushing effect with title complex as photosensitizers with in photochemical catalyzing reducing carbon dioxide field.
Accompanying drawing explanation
Fig. 1 is: the titanium dioxide carbonic acid gas of univalent copper complex and univalent copper complex sensitization generates methane rate profile;
Fig. 2 is: the sensitization solar cell current voltage characteristic based on univalent copper complex dyestuff.
Embodiment
Embodiment 1: part synthetic:
By 1mmol4,4 '-bis-(to aldehyde radical) phenyl-6,6 '-dimethyl-2,2 '-dipyridyl, 2.98mmol alpha-cyanoacrylate, 0.1ml piperidines joins in 10ml chloroformic solution, mixed-liquor return reaction is spent the night, form yellowish brown solid, filter and obtain solid, in silicagel column, take ethyl acetate as eluent separated product.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:
By 0.5mmol Cu (CH
3cN)
4pF
6with 1mmol N^N[4,4 '-bis-(to alpha-cyanoacrylate) phenyl-6,6 '-dimethyl-2,2 '-dipyridyl].Part N^N joins (v/v in the mixed solvent of 30ml methylene dichloride and methyl alcohol for 1: 2 in molar ratio, 1: 1) react and spend the night, cool to room temperature, after solvent is spin-dried in silicagel column with acetic acid and methyl alcohol (v/v, 1: 2) be washing and dehydrating integrated machine separated product, collect red stream short, after solvent is spin-dried for, the dry scarlet product C u (N^N) that obtains
2pF
6, (N^N) be 4,4 '-bis-(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 visible light photocatalysis reducing carbon dioxide:
0.1g embodiment 2 gained univalent copper complex solid powder samples are positioned in glass reactor, air in reactor is found time, pass into carbonic acid gas air pressure in system is reached to a normal atmosphere, in system, inject 0.4ml deionized water, then by system illumination under xenon lamp (300W), in interlude, in abstraction reaction bottle, 1.0ml gaseous sample imports to and in chromatography of gases, carries out composition analysis respectively.Result (Fig. 1) shows, in copper complex solid sample catalyst system, after 9h, producing methane concentration is 9 μ mol/g.
Embodiment 4: the application of the titanium dioxide of univalent copper complex sensitization in visible light photocatalysis reducing carbon dioxide:
The titanium dioxide solid powder sample of 0.1g embodiment 2 gained univalent copper complex sensitizations is positioned over to (sample preparation process: 0.25g titania powder is incorporated in the univalent copper complex 10ml methanol solution sample of 1mM in glass reactor, lucifuge is after 50 ℃ of whip attachment 24h, by solid filtering out, with 70 ℃ of oven dry, obtain the titanium dioxide sample of univalent copper complex sensitization, sample is 40 μ mol/g containing the amount of univalent copper complex), air in reactor is found time, pass into carbonic acid gas air pressure in system is reached to a normal atmosphere, in system, inject 0.4ml deionized water, then by system illumination under xenon lamp (300W), in interlude, in abstraction reaction bottle, 1.5ml gaseous sample imports to and in chromatography of gases, carries out composition analysis respectively.Result (Fig. 1) shows, in the titanium dioxide solid powder sample catalyst system of copper complex sensitization, after illumination 30h, producing methane concentration is 170 μ mol/g.
Embodiment 5: the application of univalent copper complex in dye-sensitized solar cells device:
The TiCl that the FTO glass of wash clean is soaked at 40mM
4in solution, at 70 ℃, heat after 20 minutes with deionized water and alcohol flushing.Then in painting on glass, scrape the titanium deoxide slurry of one deck 80 μ m, at 125 ℃, put into retort furnace after dry, in 450 ℃ of heating 20 minutes, then be coated with the titanium deoxide slurry of scraping one deck 80 μ m in the above, in 450 ℃ of heating, after 20 minutes, be cooled to room temperature.It is soaked in to the TiCl of 40mM again
4in solution, heat and after 20 minutes, transfer in muffle furnace in 500 ℃ of sintering at 70 ℃, be cooled to after room temperature, titanium dioxide photoelectrode is soaked in the univalent copper complex dyestuff of 0.5mM, after 24h, water rinses, dry at 30 ℃.The titanium dioxide photoelectric level of take after sensitization is anode, and platinized platinum is 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) for ionogen is assembled into 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
-2; Packing factor is 78.8%; Photoelectric transformation efficiency η is respectively 2.2%.
Claims (9)
1. a univalent copper complex, its chemical formula is Cu (N^N)
2pF
6, its structural formula is:
Wherein part N^N is 4,4'-bis-(to alpha-cyanoacrylate) phenyl-6,6'-dimethyl-2,2'-dipyridyl.
2. the preparation method of univalent copper complex claimed in claim 1, is characterized in that, by Cu (CH
3cN)
4pF
6with 1 ︰ 2 reactions in molar ratio of N^N part, cooling, purification obtains Cu (N^N)
2pF
6.
3. the preparation method of univalent copper complex as claimed in claim 2, is characterized in that, by 0.5mmol Cu (CH
3cN)
4pF
6join in 1 ︰ 1v/v mixed solvent of 30ml methylene dichloride and methyl alcohol and react and spend the night with 1mmol N^N part, cool to room temperature, the mixture of acetic acid and methyl alcohol 1 ︰ 2v/v of take in silicagel column after solvent is spin-dried for is eluent separated product, collect red stream section, after solvent is spin-dried for, the dry scarlet product C u (N^N) that obtains
2pF
6.
4. using univalent copper complex described in claim 1 and realize as catalyzer the method that visible light catalytic reducing carbon dioxide is prepared methane for one kind.
5. visible light catalytic reducing carbon dioxide as claimed in claim 4 is prepared the method for methane, it is characterized in that, the titanium dioxide of described univalent copper complex sensitization of usining is realized visible light photocatalysis reducing carbon dioxide as catalyzer and prepared methane.
6. visible light catalytic reducing carbon dioxide as claimed in claim 4 is prepared the method for methane, it is characterized in that, in the titanium dioxide of described univalent copper complex sensitization, the amount of univalent copper complex is 30～50 μ mol/g.
7. visible light catalytic reducing carbon dioxide as claimed in claim 5 is prepared the method for methane, it is characterized in that, the preparation method of the titanium dioxide of described univalent copper complex sensitization is as follows: titanium dioxide is placed in the methanol solution that described univalent copper complex is saturated, and lucifuge stirs the titanium dioxide that obtains sensitization.
8. using described in claim 1 univalent copper complex as the dye-sensitized solar cells of dyestuff for one kind.
9. described dye-sensitized solar cells as claimed in claim 8, is characterized in that, the titanium dioxide of described univalent copper complex dye sensitization is light anode, and platinum electrode is to electrode, I
-/ I
3 -for ionogen.
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|---|---|---|---|
| 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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|---|---|---|---|
| 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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| 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 |
| CN104607251B (en) * | 2015-02-10 | 2017-01-25 | 洛阳师范学院 | Frame compound catalyst material containing mixed valence Cu and preparation method thereof |
| 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 |
| 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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| Biljana Bozic-Weber, et al..The intramolecular aryl embrace: from light emission to light absorption.《Dalton Trans.》.2011,第40卷12584-12594. |
| Effects of sol–gel procedures on the photocatalysis of Cu/TiO2 in CO2 photoreduction;I-Hsiang Tseng, et al.;《Journal of Catalysis》;20041231;第221卷;432-440 * |
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| Yong-Jun Yuan, et al..Visible-Light-Driven H2 Generation from Water and CO2 Conversion by Using a Zwitterionic Cyclometalated Iridium(III) Complex.《Chem. Eur. J.》.2011,第17卷12891-12895. |
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