CN106243328A - 一种含噻吩基苯二胺衍生物合Zn(II)的聚合金属配合物及其制备方法与用途 - Google Patents
一种含噻吩基苯二胺衍生物合Zn(II)的聚合金属配合物及其制备方法与用途 Download PDFInfo
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- CN106243328A CN106243328A CN201610584022.6A CN201610584022A CN106243328A CN 106243328 A CN106243328 A CN 106243328A CN 201610584022 A CN201610584022 A CN 201610584022A CN 106243328 A CN106243328 A CN 106243328A
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- metal complex
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- bqzn
- thiophene
- thienyl
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 125000001544 thienyl group Chemical group 0.000 title claims abstract description 13
- 150000004986 phenylenediamines Chemical class 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 230000001235 sensitizing effect Effects 0.000 claims abstract description 6
- 229930192474 thiophene Natural products 0.000 claims abstract description 6
- 125000005605 benzo group Chemical group 0.000 claims abstract description 5
- 229940049706 benzodiazepine Drugs 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 8
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 8
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 229940052810 complex b Drugs 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229960004756 ethanol Drugs 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- MJFCDPLEATUOPF-UHFFFAOYSA-L dichloronickel;triphenylphosphane Chemical compound Cl[Ni]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 MJFCDPLEATUOPF-UHFFFAOYSA-L 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- HRSADIZPZPRZEI-UHFFFAOYSA-L zinc;diacetate;hydrate Chemical compound O.[Zn+2].CC([O-])=O.CC([O-])=O HRSADIZPZPRZEI-UHFFFAOYSA-L 0.000 claims 1
- 239000000975 dye Substances 0.000 abstract description 15
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 abstract description 3
- -1 thienyl phenylenediamine derivative Chemical class 0.000 abstract description 3
- 238000004873 anchoring Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 230000005611 electricity Effects 0.000 abstract description 2
- JACCFQMSOHCQFN-UHFFFAOYSA-N 2-(2-ethylhexyl)thiophene Chemical compound CCCCC(CC)CC1=CC=CS1 JACCFQMSOHCQFN-UHFFFAOYSA-N 0.000 abstract 1
- 238000007099 Yamamoto allylation reaction Methods 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 abstract 1
- 239000000434 metal complex dye Substances 0.000 abstract 1
- 238000002329 infrared spectrum Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 206010070834 Sensitisation Diseases 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 230000008313 sensitization Effects 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 1
- 229910014568 C—O-M Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- FLPNUCBSFACIHU-UHFFFAOYSA-N benzene-1,2-diamine ethanol Chemical compound C(C)O.NC1=C(C=CC=C1)N FLPNUCBSFACIHU-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- OBISXEJSEGNNKL-UHFFFAOYSA-N dinitrogen-n-sulfide Chemical compound [N-]=[N+]=S OBISXEJSEGNNKL-UHFFFAOYSA-N 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- LGZXYFMMLRYXLK-UHFFFAOYSA-N mercury(2+);sulfide Chemical compound [S-2].[Hg+2] LGZXYFMMLRYXLK-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 229960003540 oxyquinoline Drugs 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000007984 tetrahydrofuranes Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
本发明公开了如式1所示的一种D‑A’‑π‑A型含噻吩基苯二胺衍生物合Zn(II)的聚合金属配合物染料敏化剂及其制备方法与用途。该聚合金属配合物以4,8‑双[5‑(2‑乙基己基)噻吩‑2‑基]苯并[1,2‑B:4,5‑b]二噻吩（BDTT）为电子给体（D）,以噻吩基苯二胺衍生物合Zn(II)配合物为辅助电子受体（A’），Zn(Ⅱ)的辅助配体8‑羟基喹啉衍生物为π桥，氰基（‑CN）和羧基（‑COOH）为主电子受体（A）和锚定基团，通过yamamoto反应将BDTT和Zn(Ⅱ)配合物聚合制备得到聚合金属配合物PBDTT‑BQZn。实验以PBDTT‑BQZn为染料敏化剂的染料敏化太阳能电池,其光伏性能测试表现出较好的效果：光电转化效率（PCE）达到5.87%，热稳定性高，热分解温度达到311℃。
Description
技术领域
本发明涉及用于染料敏化太阳能电池中作染料敏化剂的一种含噻吩基苯二胺衍生物合Zn(II)的聚合金属配合物及其制备方法，属于新材料中的光电材料领域。
背景技术
Grätzel和O’Regan在1991年首次报道染料敏化太阳能电池（DSSCs）后，DSSCs便被认为是未来最有发展潜力的太阳能电池，成为了研发可再生和清洁能源领域的热点。而染料敏化剂在DSSCs中起到将太阳光转变成电子并使电子在分子内转移并注入到电极上TiO2薄膜的关键作用，作为新的光电材料，受到最为广泛、深入的研究和应用开发。在目前大量的研究报道和发明中，染料敏化剂多为D-A和D-π-A型（即电子给体D与受体A通过一个π共轭体系连接）的有机物，而在最近，出现了引入以有机苯并噻二唑（BTH）等拉电子化合物为辅助电子受体（A’）的D-A’-π-A型（即在给体与π共轭体系间再连接一个受体）高性能染料敏化剂分子报道。这种D-A’-π-A型结构的染料相比于D-π-A型染料,因有效减少了电荷复合、增加了染料的电子转移效率和稳定性，从而较大幅度的提高了染料敏化太阳能电池的光电转化效率（PCE）等光伏性能。基于此，本发明研究和开发了以稳定性和吸电子性能优良的过渡金属Zn (Ⅱ)配合物作为辅助电子受体（A’），而发明与制备了一种新的D-A’-π-A聚合金属配合物染料敏化剂。
发明内容
本发明的目的是提供和制备了一种以4,8-双[5-(2-乙基己基)噻吩-2-基]苯并[1,2-B:4,5-b]二噻吩（BDTT）为给体（D），以噻吩基苯二胺衍生物合Zn(II)配合物为辅助受电子体（A’），Zn(Ⅱ)的辅助配体8-羟基喹啉为π桥，氰基（-CN）和羧基（-COOH）为主电子受体（A）和锚定基团的D-A’-π-A型含噻吩基苯二胺衍生物合Zn(II)的聚合金属配合物PBDTT-BQZn。应用于染料敏化太阳能电池中作染料敏化剂，具有较高的光电转化效率和高的热稳定性，其结构式如下：
式1 聚合金属配合物PBDTT-BQZn的结构。
一种含噻吩基苯二胺衍生物合Zn(II)的聚合金属配合物PBDTT-BQZn的合成制备方法：
（1）配体[N-(2,5-二溴噻吩-3-基)亚甲基]苯-1,2-二胺的制备：
将邻苯二胺溶解于烧瓶反应器中的无水乙醇中，在室温和搅拌下将2,5-二溴-3-噻吩甲醛（与邻苯二胺的摩尔比为1.0:1.0）的无水乙醇溶液通过恒压滴液漏斗逐滴加入到烧瓶内，滴完后继续反应2~6 h后过滤，滤渣用冰无水乙醇洗涤数次，真空干燥得到黄绿色固体的配体产物；
（2）Zn(II)配合物BQZn的合成：
按1.0:1.0的摩尔比，取 [N-(2,5-二溴噻吩-3-基)亚甲基]苯-1,2-二胺和2-氰基-3-（8-羟基喹啉-5-基）丙酸于反应器中，加入四氢呋喃搅拌溶解，将二水醋酸锌的甲醇溶液缓慢滴入反应器中后慢慢升高温度，回流反应10~20 h。冷却后过滤，滤渣用无水甲醇进行多次洗涤，干燥得到棕黄色Zn(II)配合物BQZn；
（3）聚合金属配合物PBDTT-BQZn的合成：
将2,6-二溴-4,8-双[5-(2-乙基己基)噻吩-20基]苯并[1,2-B:4,5-b]二噻吩与锌配合物BQZn加入到三颈反应瓶中，然后依次加入三苯基膦、锌粉、双三苯基膦氯化镍和联吡啶，上述依次加料的摩尔比为 1:1:2:5:1:0.1。用精馏DMF溶解，在通氮气保护条件下，反应体系保持80~95℃，反应40~60 h，反应终止并冷却至室温，然后将反应液倒入过量的无水乙醇中，静置过夜后过滤，滤饼用无水乙醇进行多次洗涤，干燥，得到墨绿色固体聚合金属配合物PBDTT-BQZn。
一种含噻吩基苯二胺衍生物合Zn(II)的聚合金属配合物PBDTT-BQZn的用途：在染料敏化太阳能电池中用作吸收太阳光并产生和传输电子的染料敏化剂材料。
本发明积极的技术进步效果在于：（1）发明一种含噻吩基苯二胺衍生物合Zn(II)的聚合金属配合物PBDTT-BQZn是以普通过渡金属Zn(II)的配合物为辅助电子接受体A’的新型聚合物D-A’-π-A型染料敏化剂，具有良好的共轭性，从而加快了电子从给体到受体的传输效率，对染料能隙的调节扩大了其在可见光区域的吸收范围及强度，因此表现出较好的光电转换效率,（2）有较好光稳定性和热稳定性,（3）以Zn代替贵金属钌等，降低了生产成本，且制备方法较简单，无苛刻的高温高压要求。
附图说明
图1 本发明实施例所合成的[N-(2,5-二溴噻吩-3-基)亚甲基]苯-1,2-二胺配体的核磁氢谱（400MHz，CDCl3，TMS）；
图2 本发明实施例所合成的Zn(II)配合物BQZn的红外光谱（IR）（KBr晶体压片，4000~400 cm-1）；
图3本发明实施例所合成的聚合金属配合物PBDTT-BQZn的红外光谱（IR）（KBr晶体压片，4000~400 cm-1）；
图4 本发明实施例合成的聚合金属配合物PBDTT-BQZn的热重分析（TGA）曲线；
图5 本发明实施例合成的聚合金属配合物PBDTT-BQZn的紫外-可见光（UV-vis）吸收光谱；
图6 本发明实施例合成的聚合金属配合物PBDTT-BQZn的染料敏化太阳能电池电流密度-电压(J-V)曲线；
图7 本发明实施例合成的聚合金属配合物PBDTT-BQZn的染料敏化太阳能电池外量子效率（IPCE）曲线。
具体实施方式
本发明的化合物的反应机理为：
下面结合具体实施例对本发明做进一步的说明。
实施例1：
一种含噻吩基苯二胺衍生物合Zn(II)的聚合金属配合物PBDTT-BQZn。
聚合金属配合物PBDTT-BQZn的分子结构式如下：
上述聚合金属配合物PBDTT-BQZn的合成制备方法：
A.[N-(2,5-二溴噻吩-3-基)亚甲基]苯-1,2-二胺配体的制备：取2,5-二溴-3-噻吩甲醛3.5050 g（25 mmol）和邻苯二胺2.7652 g（25 mmol）分别溶解于40 ml的无水乙醇中。室温下，边搅拌边将2,5-二溴-3-噻吩甲醛的无水乙醇溶液通过恒压滴液漏斗逐滴加入到邻苯二胺无水乙醇溶液的烧瓶内，滴完后继续反应4 h。过滤，滤饼用冰的无水乙醇洗涤数次，真空干燥得[(2,5-二溴噻吩-3-基)亚甲基]苯-1,2-二胺配体6.3912 g(产率：71%，其核磁氢谱如图1所示)。FT-IR (KBr): 3408, 3321(-NH2), 3029, 1623(C=N), 1493,1429,836, 737. 1H-NMR (CDCl3, ppm): 8.44 (s, 1H, CH＝N), 7.59 (s, 1H, 噻吩H), 7.12(s, 1H), 7.07-7.09 (m, 1H), 6.76-6.79 (m, 1H), 6.69 (s, 1H) 3.54 (s, 2H).
B. Zn(II)配合物BQZn的合成：取醋酸锌[Zn(CH3COO)2•2H2O] 0.2416 g（1.1 mmol）溶解于20 ml的无水甲醇中备用。称取[(2,5-二溴噻吩-3-基)亚甲基]苯-1,2-二胺0.3607 g（1 mmol）和2-氰基-3-（8-羟基喹啉-5-基）丙酸0.2402 g（1 mmol）置于100 ml的三口瓶中，将25 ml四氢呋喃（THF）加入并搅拌至溶解。缓慢滴加醋酸锌的甲醇溶液，滴完之后，慢慢升高温度到回流之后，反应12 h。冷却过滤后，滤渣用无水甲醇多次洗涤后干燥，得到橘红色产物0.4996g（产率：65%，其红外光谱如图2所示）。FT-IR (KBr): 3436(-OH), 3044(C-H),2220(-CN), 1686(C=O), 1125(C=N-M), 527(N-M). Anal. Calcd for[C26H17Br2SN4O5Zn]: C, 43.21%; H, 2.37%; N, 7.75%, S, 4.44%. Found: C, 43.17%;H, 2.32%; N, 7.81%, S, 4.39%.
C.聚合金属配合物PBDTT-BQZn的合成：分别称取Zn(II)配合物0.3502g（0.4 mmol）、2,6-二溴-4,8-双[5-(2-乙基己基)噻吩-20基]苯并[1,2-B:4,5-b]二噻吩（BDTT）0.2948 g（0.4 mmol），三苯基膦（PPh3）0.2099 g（0.8 mmol），锌粉（Zn）0.1308 g（2 mmol），双三苯基膦氯化镍[Ni2(PPh3)Cl2] 0.2624 g（0.4 mmol）, 联吡啶0.0065 g（0.04 mmol），加入到100ml的单口瓶中，再量取20 ml精制过的DMF，加入上述烧瓶中。反应在氮气氛围中进行，将温度逐渐生至90℃，反应48 h。冷却，然后将反应液倾倒至过量的无水乙醇，静置过夜之后过滤，滤渣用无水乙醇进行多次洗涤，干燥，得到墨绿色固体产物PBDTT-BQZn。（产率：61%，其红外光谱如图3所示）。FT-IR (KBr, cm-1): 3428 (-OH), 3033 (aromatic and vinylicC-H), 2958, 2925 (alkyl C-H), 2206 (-CN), 1658 (C=O), 1564 (C=C), 1525 (C=N),1104 (C-O-M), 494 (N-M). Anal Calcd for [C64H67N4S5O5Zn]: C, 64.17%; H, 5.64%;N, 4.68%; S, 13.38%. Found: C, 64.21%; H, 5.69%; N, 4.63%; S, 13.34%.GPC: =10.5 kg/mol, =22.1 kg/mol, n=9, PDI=2.10。
实施例2：
测定一种含噻吩基苯二胺衍生物合Zn(II)的聚合金属配合物PBDTT-BQZn的热失重曲线(TGA)。方法：Q50热重分析仪，N2保护下以25℃/min的升温速度进行测试，其相关热失重和热分解性能结果如附图4。
实施例3：
以Computer-programmed Keithley 2611 SourceMeter通过电脑控制测量，Solarsimulator (Oriel, 91160-1000 91192, Perccell Technologies) 为光源（500-W Xe，AM1.5 G），电池活性电极有效面积为0.25cm2，测定以聚合金属配合物PBDTT-QBZn为染料敏化剂的染料敏化太阳能电池的性能参数和光电转换效率，电池电流密度-电压(J-V)曲线如图6，其电池外量子效率(IPCE)曲线如图7。表一是它们的光伏性能和光电转换效率测试结果。
表一 聚合物染料敏化剂的光伏性能参数
Claims (3)
1.一种含噻吩基苯二胺衍生物合Zn(II)的聚合金属配合物及其制备方法与用途，其结构式如下：
式1 聚合金属配合物PBDTT-BQZn的结构
2.根据权利要求1所述的一种含噻吩基苯二胺衍生物合Zn(II)的聚合金属配合物的制备方法：
（1）配体[N-(2,5-二溴噻吩-3-基)亚甲基]苯-1,2-二胺的制备：
将邻苯二胺溶解于烧瓶反应器中的无水乙醇中，在室温和搅拌下将2,5-二溴-3-噻吩甲醛（与邻苯二胺的摩尔比为1.0:1.0）的无水乙醇溶液通过恒压滴液漏斗逐滴加入到烧瓶内，滴完后继续反应2~6 h后过滤，滤渣用冰无水乙醇洗涤数次，真空干燥得到黄绿色固体的配体产物；
（2）Zn(II)配合物BQZn的合成：
按1.0:1.0的摩尔比，取 [N-(2,5-二溴噻吩-3-基)亚甲基]苯-1,2-二胺和2-氰基-3-（8-羟基喹啉-5-基）丙酸于反应器中，加入四氢呋喃搅拌溶解，将二水合乙酸锌的甲醇溶液缓慢滴入反应器中后慢慢升高温度，回流反应10~20 h。冷却后过滤，滤渣用无水甲醇进行多次洗涤，干燥得到棕黄色Zn(II)配合物BQZn；
（3）聚合金属配合物PBDTT-BQZn的合成：
将2,6-二溴-4,8-双[5-(2-乙基己基)噻吩-2-基]苯并[1,2-B:4,5-b]二噻吩(BDTT)与锌配合物BQZn加入到三颈反应瓶中，然后依次加入三苯基膦、锌粉、双三苯基膦氯化镍和联吡啶，上述依次加料的摩尔比为 1:1:2:5:1:0.1。用精馏DMF溶解，在通氮气保护条件下，反应体系保持80~95℃，反应40~60 h，反应终止并冷却至室温，然后将反应液倒入过量的无水乙醇中，静置过夜后过滤，滤饼用无水乙醇进行多次洗涤，干燥，得到墨绿色固体聚合金属配合物PBDTT-BQZn。
3.根据权利要求1所述的一种含噻吩基苯二胺衍生物合Zn(II)的聚合金属配合物的用途，在染料敏化太阳能电池中用作染料敏化剂。
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| CN112225883A (zh) * | 2020-10-12 | 2021-01-15 | 湘潭大学 | 四种D-A’-(π-A)2型聚合吡啶衍生物合金属配合物及其制备方法与用途 |
| CN112225883B (zh) * | 2020-10-12 | 2023-05-26 | 湘潭大学 | 四种D-A’-(π-A)2型聚合吡啶衍生物合金属配合物及其制备方法与用途 |
| CN112250843A (zh) * | 2020-10-16 | 2021-01-22 | 湘潭大学 | 四种D-A’-(π-A)2型聚合烷基化水杨醛席夫碱衍生物合金属配合物及其制备方法与用途 |
| CN112250843B (zh) * | 2020-10-16 | 2023-05-30 | 湘潭大学 | 四种D-A’-(π-A)2型聚合烷基化水杨醛席夫碱衍生物合金属配合物及其制备方法与用途 |
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