CN112858423A - 乙烯基钌配合物氧化电聚合薄膜的制备及其光电催化氧还原 - Google Patents
乙烯基钌配合物氧化电聚合薄膜的制备及其光电催化氧还原 Download PDFInfo
- Publication number
- CN112858423A CN112858423A CN202011618747.5A CN202011618747A CN112858423A CN 112858423 A CN112858423 A CN 112858423A CN 202011618747 A CN202011618747 A CN 202011618747A CN 112858423 A CN112858423 A CN 112858423A
- Authority
- CN
- China
- Prior art keywords
- vinyl
- film
- ruthenium complex
- photo
- electropolymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000012327 Ruthenium complex Substances 0.000 title claims abstract description 26
- HLQMBZMIEPDGLN-UHFFFAOYSA-N C1C=[Ru]1 Chemical compound C1C=[Ru]1 HLQMBZMIEPDGLN-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 230000003197 catalytic effect Effects 0.000 title abstract description 4
- 230000033116 oxidation-reduction process Effects 0.000 title abstract description 4
- 230000003647 oxidation Effects 0.000 title description 6
- 238000007254 oxidation reaction Methods 0.000 title description 6
- 239000010408 film Substances 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 10
- 230000009467 reduction Effects 0.000 claims abstract description 9
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000010409 thin film Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 13
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 21
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 abstract description 19
- 239000000243 solution Substances 0.000 abstract description 12
- 238000002474 experimental method Methods 0.000 abstract description 5
- 229920006254 polymer film Polymers 0.000 abstract description 5
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 8
- 230000004044 response Effects 0.000 description 8
- -1 vinyl pyridine ruthenium complexes Chemical class 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000007832 Na2SO4 Substances 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000001548 drop coating Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000002468 redox effect Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000003115 supporting electrolyte Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DKEFXFSHBYIQBW-UHFFFAOYSA-N 2-(3,6,8-tripyridin-2-ylpyren-1-yl)pyridine Chemical compound N1=CC=CC=C1C(C1=CC=C23)=CC(C=4N=CC=CC=4)=C(C=C4)C1=C2C4=C(C=1N=CC=CC=1)C=C3C1=CC=CC=N1 DKEFXFSHBYIQBW-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- GCXGHQXLQHQRSG-UHFFFAOYSA-N 3-ethenyl-2-pyridin-2-ylpyridine Chemical class C=CC1=CC=CN=C1C1=CC=CC=N1 GCXGHQXLQHQRSG-UHFFFAOYSA-N 0.000 description 1
- QBFNGLBSVFKILI-UHFFFAOYSA-N 4-ethenylbenzaldehyde Chemical compound C=CC1=CC=C(C=O)C=C1 QBFNGLBSVFKILI-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000004608 ZINDO calculation Methods 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007787 long-term memory Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229940110728 nitrogen / oxygen Drugs 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F130/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F130/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/02—Electrolytic coating other than with metals with organic materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/36—Glass electrodes
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/4163—Systems checking the operation of, or calibrating, the measuring apparatus
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Analytical Chemistry (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
本发明首次公开了一种含乙烯基钌配合物的氧化电聚合薄膜的制备方法、电化学和光电化学的性质，采用简单的电化学的方法使乙烯基单核钌配合物在ITO电极上形成聚合物薄膜，该聚合物薄膜在二氯甲烷溶液中具有较好的稳定性，电化学结果显示具有较好的氧化还原性质和较低的电荷转移电阻。光电实验结果显示聚合3圈的薄膜具有显著的阴极光电流性质和氧气还原的催化性质。当偏压为0V时，随着电子给体氢醌的浓度的增加，聚合3圈的薄膜展现出光电流极性光开关的特性，由阴极光电流转变成较高的阳极光电流(光电流密度)2.58μA(9.22μA/cm2)。在加入0.84mM氢醌的0.1M Na2SO4水溶液中，聚合3圈的薄膜的单色光光电转化效率值高达0.605％。因此，本发明中的含乙烯基的钌配合物氧化电聚合薄膜的制备方法是首次报道的例子，在能量转换领域有着广泛的应用前景。
Description
技术领域
本发明属于电化学领域，涉及含乙烯基钌配合物首次通过氧化电聚合制备薄膜的方法及其电化学和光电化学性质。
背景技术
近年来，金属配合物薄膜修饰电极在电致变色、太阳能转换、染料敏化太阳能电池、水催化氧化和二氧化碳催化还原等方面的应用引起了广泛的关注。常见的修饰电极的方法主要有共价自组装、层层自组装、电聚合、电喷射、旋涂和滴涂[C.X.Zhang,T.Yang,H.J.Yin,L.H.Gao,K.Z.Wang,Electrodeposited thiophene-containing organic smallmolecule-modified ITO electrode with highly efficient photoelectricconversion and photoelectrochemical oxygen reduction.Electrochim.Acta,2020,362,137150-137161]。其中，旋涂和滴涂这两种方法主要适用于溶解度较好的聚合物。相比较之下，电聚合具有以下优点：(1)单体不需要太好的溶解度；(2)单体可以在电极表面实现原位电聚合；(3)聚合操作简单；(4)可以通过改变聚合圈数控制聚合膜的厚度；(5)通过改变电化学参数进行掺杂[H.Yin,T.Yang,K.Z.Wang,J.Tong,S.Y.Yu,Unusualphotoelectrochemical properties of electropolymerized films of atriphenylamine-containing organic small molecule.Langmuir,2019,35,12620-12629]。常见的电聚合基团主要有：噻吩基，咔唑基，乙烯基，吡咯基，三苯胺基及其他芳香胺等。其中，文献报道的乙烯基金属配合物主要是采用还原电聚合的方法制备薄膜。
Meyer和其他作者早在1981年就首次报道了乙烯基取代配体的Ru配合物和铁配合物通过还原电聚合制备了具有电化学活性的薄膜[H.D.
P.Denisevich,M.
T.J.Meyer,R.W.Murray,Rectifying interfaces using two-layer films ofelectrochemically polymerized vinylpyridine and vinylbipyridine complexes ofruthenium and iron on electrodes.J.Am.Chem.Soc.,1981,103,1-5]。之后，涌现出了很多含乙烯基的金属配合物还原电聚合薄膜修饰电极的制备、电化学性质研究及在电催化、电分析、相分离、化学发光和CO2还原等方面的应用[H.D.
Coordination chemistryin two dimensions:chemistry modified electrodes.Coord.Chem.Rev.,1988,86,135-189]。近年来，钟课题组制备了一系列乙烯基吡啶钌配合物，通过还原电聚合在电极表面组装膜，并研究了其近红外电致变色等性质[Y.W.Zhong,C.J.Yao,H.J.Nie,Electropolymerized films of vinyl-substituted polypyridine complexes:synthesis,characterization,and applications.Coord.Chem.Rev.2013,257,1357-1372]。例如，电聚合薄膜Poly-[Ru2(vtpy)2(tpb)]2+[C.J.Yao,Y.W.Zhong,H.D.
J.Yao，Near-IR electrochromism in electropolymerized films of abiscyclometalated ruthenium complex bridged by1,2,4,5-tetra(2-pyridyl)benzene.J.Am.Chem.Soc.,2011,133,20720-20723]和poly-[Ru2(vtpy)2(tppyr)]2+[C.J.Yao,J.Yao,Y.W.Zhong,Metallopolymeric films based on a biscyclometalatedruthenium complex bridged by 1,3,6,8-tetra(2-pyridyl)pyrene:applications innear-infrared electrochromic windows.Inorg.Chem.,2012,51,6259-6263]表现出良好的电化学稳定性和三色可调近红外电致变色，且响应时间短、长时记忆和较好的对比度；最近他们组也观察到乙烯基环金属钌胺配合物还原电聚合薄膜展示了多态近红外电致变色，优异的对比度(1070nm处为52％，700nm处为76％)，长保留时间和信息存储性能以及近红外电致变色性质[B.B.Cui,J.H.Tang,J.N.Yao,Y.W.Zhong,A Molecular platform formultistate near-infrared electrochromism and flip-flop,flip-flap-flop,andternary memory.Angew.Chem.Int.Ed.,2015,54,9192-9197]。目前为止，已经报导的乙烯基金属配合物的电聚合制备薄膜修饰电极采用的都是还原电聚合，而还原电聚合实验中的电解液需要严格的除氧操作。有的乙烯基金属配合物的还原电聚合薄膜不太稳定，且电化学活性变差[H.J.Nie,J.Y.Shao,J.Wu,J.Yao,Y.W.Zhong,Synthesis and reductiveelectropolymerization of metal complexes with5,5′-divinyl-2,2′-bipyridine.Organometallics,2012,31,6952-6959]。
发明内容
本发明是首次由乙烯基Ru(II)配合物单体通过氧化电聚合的方法在铟-锡氧化物(ITO)导电玻璃和玻碳电极上制备了薄膜，该薄膜具有较好的稳定性，良好的氧化还原性质和较大的光电响应；且随着电子给体氢醌浓度的增加，该薄膜展现出了光电流极性开关的性质。
本发明的技术方案如下：
本发明所提供的含乙烯基钌配合物电聚合薄膜，在三电极体系的电解池中加入溶解含有0.8mM乙烯基钌配合物的0.1M六氟合磷酸四丁基铵的CH2Cl2溶液中，通过氧化电聚合的方法将乙烯基钌配合物沉积到工作电极表面。改变聚合过程的扫描圈数，可以得到不同厚度的聚合物薄膜。所述乙烯基钌配合物由阳离子部分和阴离子(抗衡离子)两部分组成，其中阳离子部分为[RuL3]2+,阴离子部分为无机盐阴离子(ClO4 2-,PF6 2-或Cl-)，配体L的结构如下式所示，其中R1＝H或苯基：
具体地，乙烯基钌配合物的分子式为[RuL3](PF6)2，结构如下式所示，其中R1＝H或苯基：
本发明还提供上述乙烯基钌配合物聚合薄膜的氧化电聚合方法、电化学及光电化学性质。
与现有技术相比，本发明的有益效果在于：
这是首次发现乙烯基钌配合物能通过氧化电聚合的方法在ITO和玻碳电极上制备薄膜。其中ITO/ploy-Ru膜在0.1M的二氯甲烷中比较稳定，连续重复扫描100圈之后，峰电流衰减约23％。本发明测定了ITO/ploy(Ru)膜的紫外可见吸收光谱、氧化还原性质、电化学阻抗性质及光电化学性质(光电流大小、通氮气/氧气之后的光电流响应、电子给体氢醌存在下光电流极性开光性质及光电转换效率)。由此可见，本发明中的乙烯基钌配合物聚合薄膜在能量转换领域和光电催化领域具有潜在的应用前景。
附图说明
图1[RuL3](PF6)2溶液的循环伏安图，铂电极为辅助电极，银丝为预参比电极，扫速为0.1V/s；(a)ITO为工作电极，连续扫描5圈，(b)玻碳电极为工作电极，连续扫描10圈。
图2聚合薄膜ITO/ploy(Ru)n(n＝1～5)的紫外可见吸收光谱，插图为300nm和456nm处的吸光度与膜聚合圈数n的线性关系图。
图3[RuL3](PF6)2电聚合3圈所得聚合薄膜ITO/ploy(Ru)3的在0.1M六氟合磷酸四丁基铵的二氯甲烷溶液中扫描100圈后的循环伏安图。
图4不同扫速下聚合薄膜在0.1M六氟合磷酸四丁基铵的二氯甲烷溶液中的循环伏安图：(a)ITO/ploy(Ru)1，扫描速率范围0.01～0.09V/s和(b)ITO/ploy(Ru)2，扫描速率范围0.01～0.1V/s。插图为峰电流与扫描速率的线性关系。
图5(a)聚合薄膜ITO/ploy(Ru)n(n＝1～5)在5mM[Fe(CN)6]3-/4-0.1M的Na2SO4水溶液中的电化学阻抗谱图，(b)拟合电化学阻抗谱图的等效电路。
图6(a)不同聚合圈数的聚合薄膜ITO/ploy(Ru)n(n＝1～5)在偏压-0.4V下的光电流响应图,插图为薄膜的光电流与不同聚合圈数的关系图；(b)ITO/ploy(Ru)3在不同偏压下的光电流响应图，插图为光电流与偏压的关系图。
图7-0.4V偏压下，聚合薄膜ITO/ploy(Ru)3在空气、氧气和氮气平衡的0.1M Na2SO4溶液中的光电流响应图。
图8(a)0V偏压下，电子给体氢醌(H2Q)浓度变化对聚合薄膜ITO/ploy(Ru)3在0.1MNa2SO4溶液中的光电流密度的影响,(b)从阴极到阳极的光电流极性开关图。
图9 0V偏压下，聚合薄膜ITO/ploy(Ru)3在的紫外可见吸收光谱和在0.84mM氢醌的Na2SO4溶液中的光电流工作谱的对比图。
具体实施方式
下面通过实施例对本发明进一步说明。
实施例一、配体L(R1＝苯基)的制备
配体L的合成路线如下所示：
210mg(1.0mmol)的二酮，198mg(1.5mmol)的对乙烯基苯甲醛，770mg醋酸铵，93mg(1mmol)的苯胺和10mL的醋酸放于50mL圆底烧瓶中，氮气保护下，110℃反应12h。冷却至室温，加入150mL的水，用氨水将溶液pH调制中性，产生浅黄色沉淀，抽滤，得粗产品。粗产品经二氯甲烷/乙腈＝1：3(V/V)重结晶，得到浅黄色晶体，真空干燥，产量：270mg，产率：67.8％。
氢核磁共振谱(δH，ppm，400MHz，d-CDCl3)：9.20(d,J＝4.4Hz,1H),9.16(d,J＝8.4Hz,1H),9.05(d,J＝4.4Hz,1H),7.76(dd,J1＝8.4Hz,J2＝4.4Hz,1H),7.69-7.62(m,3H),7.56-7.52(m,4H),7.44(d,J＝8.4Hz,1H),7.35(t,1H),7.33(t,1H),7.29(dd,J1＝8.4Hz,J2＝4.4Hz,1H),6.67(dd,J1＝17.6Hz,J2＝10.8Hz,1H),5.76(d,J＝17.6Hz,1H),5.29(d,J＝10.8Hz,1H)。
质谱(Triple TOFTM 5600+MS in CH3OH)：计算值,m/z＝399.15(M+H+)；实验值,m/z＝399.42(M+H+,100％)。
元素分析C27H18N4·0.9H2O:理论值：C,78.20；H,4.81；N,13.51；实验值:C,78.15；H,4.43；N，13.31。
实施例二、乙烯基钌配合物[RuL3](PF6)2的制备(R1＝苯基)
钌配合物[RuL3](PF6)2的合成路线如下所示：
将171mg(0.429mmol)的配体L和34mg(0.13mmol)的RuCl3·3H2O同时加入25mL的乙醇溶液中，氮气保护下回流24h，然后冷却到室温。反应液经过滤后，浓缩的粗产品。粗产品通过硅胶柱层析，以v/v(CH3CN/MeOH)＝15:1,为洗脱剂，收集橘黄色色带得到红色固体。红色固体经过乙腈/乙醚扩散重结晶后得到约120mg纯品，产率：58.3％。
氢核磁共振谱(δH，ppm，400MHz，d-DMSO)：9.21～9.14(m,3H),8.09～8.02(m,3H),7.98～7.91(m,3H),7.85～7.66(m,18H),7.59～7.54(m,6H),7.50～7.46(m,9H),7.43～7.35(m,3H),6.74～6.67(m,3H),5.89(d,J＝17.84Hz,3H),5.32(d,J＝11.28Hz,3H)。
质谱(Triple TOFTM 5600+MS in CH3OH)：计算值,m/z＝648.18([M–2PF6]2+)；实验值,m/z＝648.71([M–2PF6]2+,100％)。
元素分析C81H54F12N12P2Ru·2.3H2O:理论值：C,59.77；H,3.63；N,10.33；实验值:C,59.74；H,3.68；N,10.30。
实施例三、乙烯基钌配合物电聚合薄膜的制备
1.ITO导电玻璃的清洗。按照文献[H.Yin,T.Yang,K.Z.Wang,J.Tong,S.Y.Yu,Unusual photoelectrochemical properties of electropolymerized films of atriphenylamine-containing organic small molecule.Langmuir,2019,35,12620-12629]中的方法进性清洗。
2.乙烯基钌配合物氧化电聚合薄膜修饰电极的方法
在含0.8mM乙烯基钌配合物的电解质溶液(0.1M六氟合磷酸四丁基铵的二氯甲烷溶液)中，先通入氮气20min以除去电解液中的氧气，采用三电极体系(ITO或玻碳电极为工作电极，铂丝为辅助电极，银丝为参比电极)，固定扫速为0.1V/s，在电位范围0V～2.0V内分别扫描1圈，2圈，3圈，4圈，5圈等可制备不同圈数的薄膜。
实施例四、电聚合薄膜的表征、电化学及光电化学性质
(一)电聚合薄膜的表征
从氧化电聚合过程中的循环伏安图(见图1)中可以看出，随着聚合圈数的增加，峰电流呈现增大的趋势，说明单体在ITO导电玻璃上和玻碳电极上都聚合成膜。
通过测定ITO/ploy(Ru)n(n＝1～5)的紫外可见吸收光谱(见图2)，发现随着聚合圈数的增加，在300nm处和456nm处的吸光度也呈现增长的趋势，说明钌配合物成功的沉积到ITO电极上。且1～3层紫外可见光谱显示360nm处出现新的吸收峰，与单体[RuL3](PF6)2的紫外可见吸收光谱相比，这是一个新的吸收带，说明ITO电极上的薄膜结构与单体不同。
(二)电化学性质
所有的电化学性质测试都在CHI-660D电化学工作站中进行，采用三电极体系，铂丝为辅助电极，电聚合薄膜ITO/ploy(Ru)n为工作电极，银丝为预参比电极，之后用二茂铁(E°＝+0.425V versus SCE)做内标[C.J.da Cunha,E.S.Dodsworth,M.A.Monteiro,A.B.P.Lever,Bis(2,2′-bipyridine)(1,2-diimino-9,10-anthraquinone)-ruthenium(II)derivatives:A ZINDO analysis of a redox series involving coupled protonand electron transfers.Inorg.Chem.,1999,38,5399-5409]。电解液为0.1M二氯甲烷溶液。
聚合薄膜ITO/ploy(Ru)3的稳定性实验(见图3)显示，在0.1V/s的扫描速率下，重复扫描100圈之后，损失率约为23％。
通过测定ITO/ploy(Ru)1和ITO/ploy(Ru)2的循环伏安图(见图4)发现电聚合薄膜具有良好的氧化还原性质。
电化学阻抗实验是在支持电解质为含5mM[Fe(CN)6]3-/4-0.1M的Na2SO4水溶液中进行测试，图5(b)为拟合EIS谱的等效电路图。
(三)光电化学性质
光电化学性质测试均采用光源为500W超高压球形氙灯高亮度光源系统(北京畅拓科技有限公司)；在CHI-660D电化学工作站上测定电聚合薄膜的光电流-时间曲线(I-t曲线)，电极面积为0.282cm2，支持电解液为0.1M硫酸钠溶液。
在同一偏压(-0.4V)下，测定不同聚合圈数的电聚合薄膜ITO/ploy(Ru)n(n＝1～5)的光电流-时间曲线(见图6a)，发现在白光重复“开/关”循环下快速产生了可重复的光电流响应。其中聚合3圈(n＝3)的聚合薄膜具有最大阴极光电流(电流密度)：2.25μA(8.04μA/cm2)。
通过施加不同的偏压，测定聚合薄膜ITO/ploy(Ru)3的光电流-时间曲线(见图6b)，发现所加的偏压越负，该电聚合薄膜的光电流越大，充分说明该聚合薄膜产生的是阴极光电流。
为了研究电子给体(氢醌，H2Q)和电子受体(O2)对聚合薄膜的光电流响应的影响，测定在H2Q和O2存在下，聚合薄膜ITO/ploy(Ru)3的光电流-时间曲线。试验结果(见图7)表明在氧气饱和的电解液体系中，ITO/ploy(Ru)3的光电流增强到9.56μA，是氮气饱和的电解液体系中的4.7倍。随着氢醌浓度的增加，聚合薄膜ITO/ploy(Ru)3的光电流极性从阴极转向阳极，并在氢醌浓度为0.84mM时，达到最大的阳极光电流(电流密度)2.58μA(9.22μA/cm2)。
乙烯基钌配合物电聚合薄膜的单色光转换效率(IPCE)按下列公式1计算：
Jsc为光电流密度的大小(mW·cm-2)，
是特定波长下入射光的强度(mA·cm-2),λ是入射单色光波长(nm)。
通过测定在偏压为0V和氢醌浓度为0.84mM时电聚合薄膜ITO/ploy(Ru)3在不同波长单色光下的光电转换效率IPCE值为0.605％(见图9)。
Claims (3)
1.一种含乙烯基的钌配合物[RuL3](PF6)2，其特性在于其结构如下式所示：
2.如权利要求1所述的乙烯基单核钌配合物的电聚合薄膜制备方法，其特性在于通过氧化电聚合方法将含乙烯基钌配合物聚合到ITO导电玻璃或玻碳电极上得到的薄膜。
3.权利要求1所述的乙烯基钌配合物的薄膜修饰电极在光电转换和光电化学氧还原领域中的应用。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011618747.5A CN112858423B (zh) | 2020-12-31 | 2020-12-31 | 乙烯基钌配合物氧化电聚合薄膜的制备及其光电催化氧还原 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011618747.5A CN112858423B (zh) | 2020-12-31 | 2020-12-31 | 乙烯基钌配合物氧化电聚合薄膜的制备及其光电催化氧还原 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112858423A true CN112858423A (zh) | 2021-05-28 |
| CN112858423B CN112858423B (zh) | 2023-02-24 |
Family
ID=75998975
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011618747.5A Active CN112858423B (zh) | 2020-12-31 | 2020-12-31 | 乙烯基钌配合物氧化电聚合薄膜的制备及其光电催化氧还原 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112858423B (zh) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005259687A (ja) * | 2004-02-13 | 2005-09-22 | Kochi Univ | 色変換フィルタおよびそれを用いた有機ｅｌディスプレイ |
| CN102924384A (zh) * | 2011-08-12 | 2013-02-13 | 财团法人工业技术研究院 | 含乙烯基的咪唑衍生物及其在电致发光元件中的用途 |
| CN106946884A (zh) * | 2017-03-22 | 2017-07-14 | 浙江工业大学 | A‑π‑A`化合物及其制备方法与应用 |
| CN108676149A (zh) * | 2018-03-30 | 2018-10-19 | 北京师范大学 | 一种钌配合物薄膜的高效电化学聚合制备和应用 |
| CN110294855A (zh) * | 2019-07-09 | 2019-10-01 | 北京师范大学 | 基于噻吩功能化的钌(ⅱ)配合物3d电聚合薄膜 |
| CN110400910A (zh) * | 2018-04-24 | 2019-11-01 | 北京工商大学 | 一种杂多配合物/钌配合物电聚合薄膜的制备及其光电性能 |
-
2020
- 2020-12-31 CN CN202011618747.5A patent/CN112858423B/zh active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005259687A (ja) * | 2004-02-13 | 2005-09-22 | Kochi Univ | 色変換フィルタおよびそれを用いた有機ｅｌディスプレイ |
| CN102924384A (zh) * | 2011-08-12 | 2013-02-13 | 财团法人工业技术研究院 | 含乙烯基的咪唑衍生物及其在电致发光元件中的用途 |
| US20130041153A1 (en) * | 2011-08-12 | 2013-02-14 | Chien-Hong Cheng | Derivatives having vinyl group and its use in electroluminescent element |
| CN106946884A (zh) * | 2017-03-22 | 2017-07-14 | 浙江工业大学 | A‑π‑A`化合物及其制备方法与应用 |
| CN108676149A (zh) * | 2018-03-30 | 2018-10-19 | 北京师范大学 | 一种钌配合物薄膜的高效电化学聚合制备和应用 |
| CN110400910A (zh) * | 2018-04-24 | 2019-11-01 | 北京工商大学 | 一种杂多配合物/钌配合物电聚合薄膜的制备及其光电性能 |
| CN110294855A (zh) * | 2019-07-09 | 2019-10-01 | 北京师范大学 | 基于噻吩功能化的钌(ⅱ)配合物3d电聚合薄膜 |
Non-Patent Citations (6)
Also Published As
| Publication number | Publication date |
|---|---|
| CN112858423B (zh) | 2023-02-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Seo et al. | Coumarin dyes containing low-band-gap chromophores for dye-sensitised solar cells | |
| Chen et al. | New ruthenium complexes containing oligoalkylthiophene‐substituted 1, 10‐phenanthroline for nanocrystalline dye‐sensitized solar cells | |
| Pastore et al. | Computational modeling of stark effects in organic dye-sensitized TiO2 heterointerfaces | |
| Ji et al. | Photoinduced electron transfer dynamics of cyclometalated ruthenium (II)–naphthalenediimide dyad at NiO photocathode | |
| Dinçalp et al. | Effect of side chain substituents on the electron injection abilities of unsymmetrical perylene diimide dyes | |
| Mikroyannidis et al. | New photosensitizer with phenylenebisthiophene central unit and cyanovinylene 4-nitrophenyl terminal units for dye-sensitized solar cells | |
| Cogal et al. | Asymmetric phthalocyanine derivatives containing 4-carboxyphenyl substituents for dye-sensitized solar cells | |
| Athanas et al. | Co-sensitization of ruthenium (II) dye-sensitized solar cells by coumarin based dyes | |
| Duan et al. | New organic dyes containing tert-Butyl-capped N-Arylcarbazole moiety for Dye-sensitized solar cells | |
| Abdellah et al. | Visible light photoredox catalysis for the synthesis of new chromophores as co-sensitizers with benchmark N719 for highly efficient DSSCs | |
| Fang et al. | Novel diyne-bridged dyes for efficient dye-sensitized solar cells | |
| Chen et al. | The effect of different alkyl chains on the photovoltaic performance of D–π–A porphyrin-sensitized solar cells | |
| Karjule et al. | Heterotriangulene-based unsymmetrical squaraine dyes: synergistic effects of donor moieties and out-of-plane branched alkyl chains on dye cell performance | |
| Park et al. | Effect of regioisomeric substitution patterns on the performance of quinoxaline-based dye-sensitized solar cells | |
| Qiao et al. | Effect of π-spacers and anchoring groups on the photovoltaic performances of ullazine-based dyes | |
| Deng et al. | Two polymeric metal complexes based on polycarbazole containing complexes of 8-hydroxyquinoline with Zn (II) and Ni (II) in the backbone: Synthesis, characterization and photovoltaic applications | |
| Kabanakis et al. | Synthesis of novel semi-squaraine derivatives and application in efficient dye-sensitized solar cells | |
| KR20120099026A (ko) | 치환 바이피리딜기를 갖는 이핵 루테늄 착물 색소를 갖는 광전 변환 소자, 및 광화학 전지 | |
| Yu et al. | Restrain recombination by spraying pyrolysis TiO2 on NiO film for quinoxaline-based p-type dye-sensitized solar cells | |
| Yang et al. | A 3D electropolymerized thin film based on a thiophene-functionalized Ru (II) complex: Electrochemical and photoelectrochemical insights | |
| Nasr-Esfahani et al. | Fabrication and characterization of a new dye sensitized solar cell with a new Schiff base cobalt complex as a redox mediator | |
| Al-horaibi et al. | Novel Squaraine dyes for high-performance in dye-sensitized solar cells: Photophysical properties and adsorption behavior on TiO2 with different anchoring groups | |
| Yin et al. | Oxidative electropolymerization films of a styrene-appending ruthenium complex with highly performed electrochemical, solar photoelectric conversion and photoelectrochemical oxygen reduction properties | |
| CN117658899A (zh) | 双吡啶作为桥联基团的卟啉聚合物薄膜及其制备方法与应用 | |
| CN112858423B (zh) | 乙烯基钌配合物氧化电聚合薄膜的制备及其光电催化氧还原 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |