CN111253774A - 一类含有苯氧基长碳链的二噻吩并吡咯功能染料及应用 - Google Patents
一类含有苯氧基长碳链的二噻吩并吡咯功能染料及应用 Download PDFInfo
- Publication number
- CN111253774A CN111253774A CN202010215380.6A CN202010215380A CN111253774A CN 111253774 A CN111253774 A CN 111253774A CN 202010215380 A CN202010215380 A CN 202010215380A CN 111253774 A CN111253774 A CN 111253774A
- Authority
- CN
- China
- Prior art keywords
- dye
- mmol
- long carbon
- dithienopyrrole
- containing phenoxy
- 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.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 title claims abstract description 8
- BKYWEUVIGUEMFX-UHFFFAOYSA-N 4h-dithieno[3,2-a:2',3'-d]pyrrole Chemical compound S1C=CC2=C1NC1=C2SC=C1 BKYWEUVIGUEMFX-UHFFFAOYSA-N 0.000 title claims abstract description 5
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 12
- 239000003504 photosensitizing agent Substances 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 239000000370 acceptor Substances 0.000 abstract description 5
- 230000003595 spectral effect Effects 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 31
- 239000011521 glass Substances 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- WQXGWJYOTIQXRB-UHFFFAOYSA-N 4-(2-ethylhexoxy)aniline Chemical compound CCCCC(CC)COC1=CC=C(N)C=C1 WQXGWJYOTIQXRB-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920003182 Surlyn® Polymers 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- -1 (2-ethylhexyl) oxy Chemical group 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- ZYGAMJLTPLERBC-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid propan-2-ol Chemical compound B(O)(O)OC(C)(C)C(C)(C)O.C(C)(C)O ZYGAMJLTPLERBC-UHFFFAOYSA-N 0.000 description 1
- ZLNFACCFYUFTLD-UHFFFAOYSA-N (4-ethoxycarbonylphenyl)boronic acid Chemical compound CCOC(=O)C1=CC=C(B(O)O)C=C1 ZLNFACCFYUFTLD-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 1
- UKSZBOKPHAQOMP-UHFFFAOYSA-N 1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1.C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1 UKSZBOKPHAQOMP-UHFFFAOYSA-N 0.000 description 1
- 125000000389 2-pyrrolyl group Chemical group [H]N1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- KBRZCEVRNLKHAZ-UHFFFAOYSA-N 3-bromo-2-(3-bromothiophen-2-yl)thiophene Chemical compound C1=CSC(C2=C(C=CS2)Br)=C1Br KBRZCEVRNLKHAZ-UHFFFAOYSA-N 0.000 description 1
- FEOWHLLJXAECMU-UHFFFAOYSA-N 4,7-dibromo-2,1,3-benzothiadiazole Chemical compound BrC1=CC=C(Br)C2=NSN=C12 FEOWHLLJXAECMU-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- 239000005964 Acibenzolar-S-methyl Substances 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- YIYFFLYGSHJWFF-UHFFFAOYSA-N [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 YIYFFLYGSHJWFF-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical group C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000002165 photosensitisation Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
- C07D495/14—Ortho-condensed systems
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Abstract
一类含有苯氧基长碳链的二噻吩并吡咯功能染料及应用，其属于精细化工和光电化学材料的技术领域。染料的结构是以二噻吩并吡咯的衍生物为电子供体含有用来传递电子的
桥以及电子受体的功能性染料。该类染料具有良好的光谱吸收能力，并且在电池中具有良好的光稳定性及热稳定性，因此该类染料可以作为光敏染料用于染料敏化太阳能电池中。
Description
技术领域
本发明是关于一类含有苯氧基长碳链的二噻吩并吡咯功能染料及应用，其属于精细化工和光电化学材料的技术领域。
背景技术
随着当前社会的发展，煤，石油和天然气等不可再生能源正在不断地被消耗，并且伴随着大量的空气污染问题，因此可再生能源开始逐渐吸引众多研究学者的关注。太阳能作为一种取之不尽用之不竭的能源，每年到达地球表面的能量约为1.892×1013吨，并且在利用过程中不会产生任何污染问题。
1991年Grätzel团队首次提出将金属联吡啶化合物吸附在纳米多孔的半导体TiO2膜上制作而成染料敏化太阳能电池，开启了染料敏化太阳能电池发展的新篇章。在这一类光伏器件中，光敏染料作为器件的引擎发动机，起着至关重要的作用。起初著名的光敏染料，例如N3，N719等都是以钌金属作为配合物（M. Grätzel, et al. J. Am. Chem. Soc.,1993, 115, 6382和M. Grätzel, et al.Chem., Commun., 1997,1705），但是由于金属钌成本过高，随后人们开始逐渐报道锌卟啉类的光敏剂，并一度达到了13%的光电转化效率（M. Grätzel, et al. Nature Chemistry,6, 242–247(2014)）。但是由于其产率较低，往往最终收率不到10%，限制了染料敏化太阳能电池的规模化生产及应用。
二十一世纪，人们开始将目光转向纯有机类光敏染料的开发，基于供体-π桥-受体的纯有机光敏染料，由于其结构可调性，环境友好及较大的摩尔消光系数逐渐受到关注。噻吩作为良好性能的光电材料，成本廉价易于获得。基于此，本文设计了一类含有苯氧基长碳链的二噻吩并吡咯功能染料，该类化合物具有体积小，易于合成，具有光谱吸收宽、产率高等特点。
发明内容
目前应用在染料敏化太阳能电池的光敏剂，金属类染料成本昂贵，有机类染料的结构过于复杂，制备流程产率低，为了进一步降低成本，我们设计了一类含有苯氧基长碳链的二噻吩并吡咯功能染料。
本发明采用的技术方案：本发明提供了一种新型功能染料，其具体结构式如下：
其中，R1为C4-C10的直链烷烃或支链烷烃；R2为C1-C10的直链烷烃或支链烷烃；R4为H、C3-C10的直链烷烃或支链烷烃。
其合成路线如下:
该染料作为光敏剂用于染料敏化太阳能电池中。其制作步骤：首先用洗洁精将玻璃表面擦洗，去除污迹和灰尘，随后将清洗好的导电玻璃导电面朝上依次放入到洗洁精溶液，水，丙酮以及乙醇溶液中，在超声波清洗机中依次清洗三十分钟。随后取出2 mL的 TiCl4水溶液，再加入100 mL去离子水，搅拌均匀后放入洗好的玻璃基底，在70℃的烘箱内加热40min后清洗取出，并在500℃下烧结。然后采用丝网印刷的方法制备TiO2薄膜，清洗网板，将TiO2浆料取出，用刮板轻刮一次，再将玻璃导电面朝上放置在网板下面，轻刮一次，随后放在乙醇氛围中1分钟，再转移至500℃烘箱5 min。反复五次后，将TiO2浆料换为TPP200印刷一次，随后在500℃下烧结。冷却后将玻璃取出，放在配制好敏化的染浴中，在黑暗，干燥密封环境下敏化。最后，敏化完成后打开热封机，取出玻璃基底，用Surlyn 热封膜将电池的阳极以及对电极贴合，之后通过对电解预留的小孔抽真空灌装电解质，随后再用Surlyn 热封膜与玻璃封孔，电池器件制作完成。
本发明的有益效果，本发明提供了一类新型有机功能的光敏染料，以苯并噻二唑为连接体，将二噻吩并吡咯与苯甲酸连接在一起，具有宽光谱吸收，原材料成本低廉等特点。经实验测得，该类染料可以做到可见光区域内大范围的光谱吸收，在经过二氧化钛的吸收后，光谱吸收基本与溶液一致。将该类染料应用在染料敏化太阳能电池中后获得7.7%的光电转化效率，由电池的IPCE（单色光转换效率）可以看出，在500 nm到600 nm之间一度达到了90%以上，表明基于该类染料的电池器件具有良好的光吸收能力以及光电转换能力。
附图说明
图1为染料的紫外可见光谱图，染料溶度为1×10-5mol/L，溶剂为色谱纯的二氯甲烷，实验数据已去空白，仪器型号为Lambda 35。
图2为染料吸附在二氧化钛膜上的紫外可见光谱图，仪器型号为Lambda 35。
图3为基于染料器件的J-V图，测试是在一个标准太阳光强下进行，仪器型号为Oriel Sol3A及Keithly 2420。
图4为基于染料器件的IPCE图，太阳能电池的单色光转化效率（IPCE）是指太阳能电池在照射时的电荷载流子数目与照射在太阳能电池表面一定能量的光子数目的比值，可以检测出电池对不同波长光的响应强度。
图5为染料敏化太阳能电池的结构示意图：其中：
101 导电玻璃
102 吸附了该类染料的纳米二氧化钛颗粒
103 铂电极。
具体实施方式
实施例1（E）-4-（5-（7-（5-（2-（4,6-双（4-（（（2-乙基己基）氧基）苯基））-4H-二硫代[3,2 b：2'， 3'-d]吡咯-2-基）乙烯基）-4-己基噻吩-2-基）苯并[1,2,5]噻二唑-4-基）-3-己基噻吩-2-基）苯甲酸的合成
（1）染料π桥及受体的合成
杜瓦瓶内加入乙醇溶液，倒入液氮冷却至-78℃，在圆底烧瓶内加入色谱纯的四氢呋喃30mL，三己基噻吩（（2 g，11.9 mmol）以及磁子后放入杜瓦瓶内，抽真空并置换氮气三次，保持体系温度不变，持续搅拌一小时，随后逐滴加入正丁基锂（7.4 mL），结束后继续搅拌一小时后加入异丙醇频哪醇硼酸酯（1.4 g，11.9 mmol），反应过夜搅拌萃取后过柱纯化。
随后将产物转移至圆底烧瓶，加入4,7-二溴-2,1,3-苯并噻二唑（1.75 g，6mmol），四三苯基膦钯（0.75 g，0.6 mmol），DMF50 mL，碳酸钾（4.15 g，30 mmol），升温回流并搅拌过夜，萃取后过柱纯化。然后将产物（1 g，2.1 mmol）转移其圆底烧瓶内，冰水浴下逐渐加入NBS（0.35 g，2 mmol），随后搅拌过夜，萃取后经过硅胶柱纯化，后在产物（0.8 g，1.7mmol）中加入DMF30 mL，四三苯基膦钯（0.2 g，0.17 mmol），4-乙氧羰基苯硼酸（0.3 g，1.7mmol），碳酸钾（1.17 g，8.5 mmol），升温回流并搅拌过夜，萃取后过柱纯化得到红色产物（0.904 g）。
（2）4-（（2-乙基己基）氧基）苯胺的合成
对硝基苯酚（2g，14.3 mmol），溴代异性烷（2.76 g,14.3 mmol），氢氧化钾（1.2 g，21.45 mmol）加入乙醇溶液中，升温回流并搅拌过夜，然后萃取过柱纯化。将纯化后的产物与钯碳在氢气氛围下反应，溶剂为四氢呋喃，反应结束后萃取过柱，得到4-（（2-乙基己基）氧基）苯胺（2.2 g）。
（3）染料供体的合成
将3,3'-二溴-2,2'-联噻吩（1 g，3.1 mmol），4-（（2-乙基己基）氧基）苯胺（0.68 g，3.1mmol），双二亚苄基丙酮钯（0.052 g，0.093 mmol），叔丁醇钾（1.04 g，9.3 mmol），(±)-2,2'-双-(二苯膦基)-1,1'-联萘（2.3 g，0.372 mmol）加入到甲苯溶液中，搅拌回流过夜后，萃取并除去溶剂，过柱纯化，得到产物。随后将产物转移至圆底烧瓶内并加入色谱纯的THF30 mL，反应在冰浴下进行，持续搅拌一小时，随后逐渐加入NBS（0.36 g，2mmol），随后反应常温过夜搅拌，萃取后过柱纯化。然后将产物（0.5 g，1.3 mmol）转移至圆底烧瓶，加入四三苯基膦钯（0.075 g，0.065 mmol），DMF50 mL，碳酸钾（（0.9 g，6.5 mmol），4-（（2-乙基己基）氧基）苯胺（0.3 g，1.3 mmol）后，升温回流并搅拌过夜，萃取后过柱纯化得到供体0.535g。
（4）染料的合成
染料供体（（0.5 g，0.85 mmol），受体π桥及受体基团（0.523 g，0.85 mmol），加入到圆底烧瓶内，加入溶剂二氯乙烷，将三氯氧磷及DMF一比五比例配好后在冰水浴条件下逐滴加入到圆底烧瓶内部，随后将体系保温半小时后，升高温度至60℃，搅拌过夜后，萃取并过柱纯化。将产物转移至圆底烧瓶内，加入四氢呋喃30mL与水10 mL，随后回流搅拌36小时，萃取过柱，得到最终染料0.775 g。
实施例2 太阳能电池器件的制作
染料敏化太阳能电池的组成分为光阳极，对电极以及电解质三个部分。电池的制作分为以下几步：
（1）导电玻璃基底的清洗
首先用洗洁精将玻璃表面擦洗，去除污迹和灰尘。随后将清洗好的导电玻璃导电面朝上依次放入到洗洁精溶液，水，丙酮以及乙醇溶液中，在超声波清洗机中依次清洗三十分钟。
（2）TiCl4致密层的制备
取出2 mL的 TiCl4水溶液，再加入100 mL去离子水，搅拌均匀后放入洗好的玻璃基底，在70℃的烘箱内加热40 min后清洗取出，并在500℃下烧结。
（3）TiO2膜的制备
采用丝网印刷的方法，首先清洗网板，随后将TiO2浆料取出，用刮板轻刮一次，随后将玻璃导电面朝上放置在网板下面，轻刮一次，随后放在乙醇氛围中1分钟，再转移至500℃烘箱5min。反复五次后，将TiO2浆料换为TPP200印刷一次，随后在500℃下烧结
（4）TiO2膜的敏化
将玻璃取出，放在配制好敏化的染浴中，在黑暗，干燥密封环境下敏化。
（5）电解质的灌装与太阳能电池的封装
打开热封机，取出玻璃基底，用Surlyn热封膜将电池的阳极以及对电极贴合，之后通过对电极预留的小孔抽真空灌装电解质，随后再用Surlyn热封膜与玻璃封孔，电池器件制作完成。电解质的配方为0.6 M 的1,2-二甲基-3-正丙基咪吐碘盐（DMPII），0.25 M LiI，0.02M I2及0.1 M四丁基碘化铵（TBAI）溶于色谱纯乙睛溶液中。
经实验测得，该类染料可以做到可见光区域内大范围的光谱吸收（图1），在经过二氧化钛的吸收后，光谱吸收基本与溶液一致（图2）。将该类染料应用在染料敏化太阳能电池中后获得7.7%的光电转化效率（图3），由电池的IPCE（单色光转换效率）可以看出（图4），在500 nm到600 nm之间一度达到了90%以上，表明基于该类染料的电池器件具有良好的光吸收能力以及光电转换能力。
表1 基于实例1制得的光电器件性能数据
Claims (2)
1.一类含有苯氧基长碳链的二噻吩并吡咯功能染料，其特征在于：该类染料具有以下结构通式：
其中，R1为C5-C10的直链烷烃或支链烷烃；R2为C5-C10的直链烷烃或支链烷烃；R4为H、C5-C10的直链烷烃或支链烷烃。
2.根据权利要求1所述的一类含有苯氧基长碳链的二噻吩并吡咯功能染料的应用，其特征在于：所述染料作为光敏剂用于染料敏化太阳能电池中。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010215380.6A CN111253774A (zh) | 2020-03-25 | 2020-03-25 | 一类含有苯氧基长碳链的二噻吩并吡咯功能染料及应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010215380.6A CN111253774A (zh) | 2020-03-25 | 2020-03-25 | 一类含有苯氧基长碳链的二噻吩并吡咯功能染料及应用 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111253774A true CN111253774A (zh) | 2020-06-09 |
Family
ID=70949876
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010215380.6A Pending CN111253774A (zh) | 2020-03-25 | 2020-03-25 | 一类含有苯氧基长碳链的二噻吩并吡咯功能染料及应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111253774A (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114853763A (zh) * | 2022-03-23 | 2022-08-05 | 大连理工大学 | 一类D-π-A化合物及其在钙钛矿太阳能电池中钝化的应用 |
| CN115947735A (zh) * | 2022-12-13 | 2023-04-11 | 南京邮电大学 | 一类有机小分子光学诊疗试剂、纳米粒子及其制备方法和应用 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407574A (zh) * | 2008-12-01 | 2009-04-15 | 中国科学院长春应用化学研究所 | 含二噻吩并吡咯的给体-受体型共轭聚合物及制法和应用 |
| CN102898859A (zh) * | 2012-10-19 | 2013-01-30 | 中国科学院长春应用化学研究所 | 有机染料及在染料敏化太阳电池中的应用 |
| CN109400622A (zh) * | 2018-11-29 | 2019-03-01 | 天津理工大学 | 一种以氮吡咯噻吩为母核的不对称有机空穴传输材料及其合成方法和用途 |
| CN110105375A (zh) * | 2019-05-30 | 2019-08-09 | 西安理工大学 | 以二噻吩并吡咯为分子中心的给-受-给-受-给型齐聚噻吩衍生物及其制备方法 |
-
2020
- 2020-03-25 CN CN202010215380.6A patent/CN111253774A/zh active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407574A (zh) * | 2008-12-01 | 2009-04-15 | 中国科学院长春应用化学研究所 | 含二噻吩并吡咯的给体-受体型共轭聚合物及制法和应用 |
| CN102898859A (zh) * | 2012-10-19 | 2013-01-30 | 中国科学院长春应用化学研究所 | 有机染料及在染料敏化太阳电池中的应用 |
| CN109400622A (zh) * | 2018-11-29 | 2019-03-01 | 天津理工大学 | 一种以氮吡咯噻吩为母核的不对称有机空穴传输材料及其合成方法和用途 |
| CN110105375A (zh) * | 2019-05-30 | 2019-08-09 | 西安理工大学 | 以二噻吩并吡咯为分子中心的给-受-给-受-给型齐聚噻吩衍生物及其制备方法 |
Non-Patent Citations (3)
| Title |
|---|
| HUIXING LI等: "Molecular design of organic sensitizers absorbing over a broadened visible region for dye-sensitized solar cells", 《RSC ADV.》 * |
| KAI MIAO等: "Organic sensitizers featuring thiophene derivative based donors with improved stability and photovoltaic performance", 《PHYS.CHEM.CHEM.PHYS.》 * |
| ZHIHUI WANG等: "New triphenylamine organic dyes containing dithieno[3,2-b:2",3"-d]pyrrole (DTP) units for iodine-free dye-sensitized solar cells", 《ESI FOR CHEMICAL COMMUNICATIONS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114853763A (zh) * | 2022-03-23 | 2022-08-05 | 大连理工大学 | 一类D-π-A化合物及其在钙钛矿太阳能电池中钝化的应用 |
| CN115947735A (zh) * | 2022-12-13 | 2023-04-11 | 南京邮电大学 | 一类有机小分子光学诊疗试剂、纳米粒子及其制备方法和应用 |
| CN115947735B (zh) * | 2022-12-13 | 2024-03-26 | 南京邮电大学 | 一类有机小分子光学诊疗试剂、纳米粒子及其制备方法和应用 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hagberg et al. | Symmetric and unsymmetric donor functionalization. comparing structural and spectral benefits of chromophores for dye-sensitized solar cells | |
| Seo et al. | Novel D-π-A system based on zinc porphyrin dyes for dye-sensitized solar cells: synthesis, electrochemical, and photovoltaic properties | |
| Qu et al. | New diketo-pyrrolo-pyrrole (DPP) sensitizer containing a furan moiety for efficient and stable dye-sensitized solar cells | |
| Kim et al. | A polymer gel electrolyte to achieve≥ 6% power conversion efficiency with a novel organic dye incorporating a low-band-gap chromophore | |
| Srinivas et al. | D-π-A organic dyes with carbazole as donor for dye-sensitized solar cells | |
| Shen et al. | Efficient triphenylamine dyes for solar cells: effects of alkyl-substituents and π-conjugated thiophene unit | |
| CN110183437B (zh) | 一种双D-π-A型柱[5]芳烃染料及其合成方法及其应用 | |
| EP2257601A2 (en) | High molecular extinction coefficient metal dyes | |
| Cheng et al. | Organic dyes incorporating the cyclopentadithiophene moiety for efficient dye-sensitized solar cells | |
| CN102250484B (zh) | 用于染料敏化太阳能电池的咔唑基有机染料的制备方法 | |
| CN103588808A (zh) | 基于poss的固态离子液体及其制备方法和应用 | |
| Chiu et al. | A new series of azobenzene-bridged metal-free organic dyes and application on DSSC | |
| Liu et al. | Tuning band structures of dyes for dye-sensitized solar cells: Effect of different π-bridges on the performance of cells | |
| Liang et al. | New organic photosensitizers incorporating carbazole and dimethylarylamine moieties for dye-sensitized solar cells | |
| CN111253774A (zh) | 一类含有苯氧基长碳链的二噻吩并吡咯功能染料及应用 | |
| CN101899223A (zh) | 三聚茚基三芳胺有机染料及制备和用途 | |
| CN102618066B (zh) | 含杯芳烃衍生物的有机染料、制备方法及其应用 | |
| Guo et al. | Structure-property relationship of different electron donors: new organic sensitizers based on bithiazole moiety for high efficiency dye-sensitized solar cells | |
| Kumar et al. | Synthesis and characterization of simple cost-effective trans-A 2 BC porphyrins with various donor groups for dye-sensitized solar cells | |
| WO2013008951A1 (en) | Organic dye, dye-sensitized metal oxide semiconductor electrode and dye-sensitized solar cell | |
| Houarner et al. | Ruthenium bis-terpyridine complexes connected to an oligothiophene unit for dry dye-sensitised solar cells | |
| Houarner-Rassin et al. | Improved efficiency of a thiophene linked ruthenium polypyridine complex for dry dye-sensitized solar cells | |
| CN101412855B (zh) | 含推S,Se或Te电子基团的联吡啶钌染料及其在染料敏化太阳电池中的应用 | |
| Can et al. | Push-pull type material having spirobifluorene as π-spacer for dye sensitized solar cells | |
| KR101264082B1 (ko) | 벤조씨아졸을 함유하는 염료감응 태양전지용 염료 및 이를 이용한 염료감응 태양전지 |
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 | ||
| AD01 | Patent right deemed abandoned | ||
| AD01 | Patent right deemed abandoned |
Effective date of abandoning: 20211001 |