CN107383003B - 一种含喹吖啶酮的三芳胺类染料敏化剂的合成及应用 - Google Patents
一种含喹吖啶酮的三芳胺类染料敏化剂的合成及应用 Download PDFInfo
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- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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Abstract
本发明公开了一种含喹吖啶酮的三芳胺类化合物及其制备与应用。所述含喹吖啶酮的三芳胺类化合物如式I、式II和式III所示;本发明所述的合成方法为:将式IVa~IVc化合物与式V与有机溶剂混合,在碱性物质的作用下,在氮气保护下,加热回流搅拌反应6~8h,反应完全后,旋干溶剂,残余物用洗脱剂溶剂进行硅胶柱层析,获得式I~III所示的含喹吖啶酮的三芳胺类化合物。本发明所述的含喹吖啶酮的三芳胺类化合物可以作为染料敏化剂应用于染料敏化太阳能电池,为染料敏化剂的筛选增添了新的可应用物质。
Description
(一)技术领域
本发明涉及一种含喹吖啶酮的三芳胺类染料敏化剂的合成及应用。
(二)背景技术
随着能源消耗需求的增加以及化石染料在使用方面的局限性并且在其使用过程中伴随着严重的环境问题,越来越多的研究人员专注于开发新型环境友好、可再生的能源。在众多可再生的能源中,太阳能由于其丰富性、可持续性、无污染性和容易被利用性等优点,被认为是传统化石燃料最有前途的替代品之一。太阳能最常见的利用方式就是把太阳能转化成电能。跟无机太阳能电池相比,有机太阳能电池具有成本低、灵活性好、重量轻和易于制造等特征,因此有着更广阔的应用前景。在此背景下,近年来有机太阳能电池中的染料敏化太阳能电池(DSSCs)由于其易制作、效率高和成本低等优点已受到人们相当大的关注。
大多数有机敏化剂由电子给体、共轭的π桥和电子受体组成,其中三芳胺是有机染料敏化剂常用的电子给体。三芳胺作为电子给体具有以下几个优点:(1)三芳胺是强的给电子基团;(2)三芳胺的非平面结构能够有效抑制电子和氧化的敏化剂之间的电荷重组,同时也有效抑制在TiO2、染料、电解质界面处的电荷重组,减少暗电流的产生,从而增加开路电压值;(3)三芳胺上的C-H键较活泼,氢原子容易被其他富电子基团取代,能够进一步提高三芳胺的给电子能力;(4)三芳胺是良好的耐温和空穴运输材料。强给电子能力的三芳胺部分和受体之间的分子内电荷转移导致三芳胺类敏化剂在光谱吸收时有较强的吸收能力和较宽的吸收范围。喹吖啶酮具有大的共轭结构,能够有效提高敏化剂的给电子能力。喹吖啶酮和它的衍生物作为有机染料时具有优秀的光和热稳定性。本发明以二苯胺-喹吖啶酮的衍生物作为电子给体,分别以苯环、噻吩、呋喃作为π桥,氰基乙酸作为受体,设计合成了3个新型D-D-π-A型的敏化剂。目前,尚无文献报道该结构的太阳能电池应用。
(三)发明内容
本发明的目的在于提供一种含喹吖啶酮的三芳胺类化合物的制备及将其应用于染料敏化太阳能电池。
本发明所述的含喹吖啶酮的三芳胺类化合物的结构式如式I、式II或式III所示:
本发明所述如式I、式II或式III所示的含喹吖啶酮的三芳胺类化合物可按照以下方法制备得到:
向式Iva、Ivb或IVc所示的化合物中加入式V所示的化合物,在有机溶剂中,在碱性物质的作用下,在60~80℃下加热回流搅拌反应6~8h(优选为8h),反应完全后,所得反应混合液经后处理分别得到式I、式II或式III所示的含喹吖啶酮的三芳胺类化合物;所述的式Iva、Ivb或IVc所示的化合物与式V所示的化合物、碱性物质的物质的量之比为:1:1.0~3.0:3.0~5.0;
进一步,所述碱性化合物为哌啶、吡啶或三乙胺。
进一步,所述有机溶剂为氯仿、乙腈或四氢呋喃。
再进一步,所述有机溶剂体积用量以式Iva、Ivb或IVc所示的化合物的物质的量计为30~40mL/mmol,更进一步,优选38mL/mmol。
本发明所述的反应混合液的后处理方法为:反应结束后,所得反应混合液蒸除溶剂后,残余物用洗脱剂溶剂进行硅胶柱层析,所述的洗脱剂溶剂为二氯甲烷和甲醇及醋酸的混合溶剂,收集含目标化合物的洗脱液,浓缩干燥得式I、式II或式III所示的苯并咔唑类化合物。
进一步,优选所述洗脱剂溶剂为体积比为400:4:1的二氯甲烷、甲醇和醋酸的混合溶剂。
本发明所述式IVa~IVc所示的化合物可按照以下方法制备得到:
将式VII所示的化合物、式VIII、IX或X所示的化合物、四三苯基膦钯溶于四氢呋喃(THF)中,加入碳酸钾的水溶液,在N2保护下,于65℃下加热回流10h,反应结束后,向所得反应混合物中加入水,再用二氯甲烷萃取后,有机相干燥后柱层析(VCH2Cl2:VPE=3:1)分别得到式IVa~IVc所示的化合物;所述的式VII所示的化合物与式VIII、IX或X所示的化合物及四三苯基膦钯的物质的量之比为1:1.5:0.1。
进一步,所述的四氢呋喃的加入量以式VII所示的化合物的物质的量计为15ml/mmol。
进一步,所述的碳酸钾水溶液的加入量以式VII所示的化合物的物质的量计为2.5mL/mmol。
再进一步,所述的碳酸钾的水溶液的浓度为2mol/L。
本发明所述的含喹吖啶酮的三芳胺类化合物作为染料敏化剂在染料敏化太阳能电池上的应用。
具体的应用按照如下步骤进行:
将式I、式II或式III所示的含喹吖啶酮的三芳胺类化合物加入CHCl3和CH3OH的混合溶剂中,加入TiO2电极,在黑暗条件下浸泡24h,分别得到负载式I、式II或式III所示的含喹吖啶酮的三芳胺类化合物的TiO2电极,将所述的负载式I、式II或式III所示的含喹吖啶酮的三芳胺类化合物的TiO2电极与铂对电极及含碘电解质组装成染料敏化太阳能电池。将所述的染料敏化太阳能电池于100mW/cm2光强照射下,测定光电压-电流特性曲线。其结果表明此类含喹吖啶酮的三芳胺类化合物的光电转换效率2.91-5.32%。
与现有技术相比,本发明制备的含喹吖啶酮的三芳胺类化合物有益效果主要体现在:
本发明提供了一种新的含喹吖啶酮的三芳胺类化合物,该化合物作为染料敏化剂组装成的染料敏化太阳能电池具有较好的光电转换效率,为染料敏化剂的筛选增添了新的可应用物质。
(四)附图说明
图1为基于式I、式II或式III所示的含吖啶酮的三芳胺类染料敏化剂的太阳能电池的光电流-电压曲线图。
(五)具体实施方式
下面结合具体实施例对本发明进行进一步描述,但本发明的保护范围并不仅限于此:
实施例1
化合物IVa的合成
称取化合物VII(1.56g,2.0mmol),IX(0.45g,3.0mmol),四三苯基膦钯(0.23g,0.2mmol)和碳酸钾溶液(5mL,2mol/L)加入到四氢呋喃(30mL),在氮气保护下,于65℃加热回流10h。待冷却至室温后加水,用二氯甲烷萃取三次,有机层用饱和食盐水洗涤,用无水硫酸钠干燥,旋蒸除去溶剂,粗产物柱层析(VPE:VDCM=1:3)分离得到紫色固体IVa(0.78g,48%)。m.p.109-111℃;1H NMR(500MHz,CDCl3)δ10.05(s,1H),8.82(s,1H),8.76(s,1H),8.61(dd,J=8.1,1.6Hz,1H),8.37(d,J=2.8Hz,1H),7.95(d,J=8.4Hz,2H),7.80(ddd,J=8.7,6.9,1.7Hz,1H),7.75(d,J=8.3Hz,2H),7.66(dd,J=9.2,2.8Hz,1H),7.57-7.52(m,4H),7.35-7.30(m,3H),7.22-7.20(m,4H),7.12(t,J=7.4Hz,1H),4.56-4.51(m,4H),2.08-1.99(m,4H),1.67-1.58(m,4H),1.51-1.45(m,4H),1.40-1.29(m,12H),0.92-0.88(m,6H);HREIMS m/z 808.4468[M+H]+,cacld C55H57N3O3for:807.4400.
化合物I的合成
称取化合物IVa(0.33g,0.4mmol),氰基乙酸V(0.07g,0.84mmol)加入到氯仿溶液中(15mL),然后加入哌啶(0.20mL,2.0mmol),在氮气保护下,于60℃加热回流8h,待冷却至室温后,将反应混合液直接旋干,粗产物经柱层析(以VCH2Cl2:VCH3OH:VHAc=400:4:1为洗脱剂),分离得到黑色固体I(0.23g,67%)。m.p.156-157℃;1H NMR(500MHz,DMSO)δ8.50(s,1H),8.43(s,1H),8.30(d,J=10.7Hz,2H),8.09(d,J=8.4Hz,2H),7.96(d,J=2.7Hz,1H),7.86(d,J=8.4Hz,2H),7.79(d,J=6.6Hz,2H),7.74-7.71(m,3H),7.59(dd,J=9.1,2.5Hz,1H),7.39(t,J=7.8Hz,2H),7.25(t,J=7.3Hz,1H),7.18-7.15(m,3H),7.09(d,J=8.6Hz,2H),4.46-4.34(m,4H),1.87-1.75(m,4H),1.55-1.46(m,4H),1.43-1.35(m,4H),1.32-1.22(m,12H),0.86-0.80(m,6H);HREIMS m/z 875.2354[M+H]+,cacld C58H58N4O4for:874.4458.
实施例2
化合物IVb的合成
称取化合物VII(1.56g,2.0mmol),VIII(0.47g,3.0mmol),四三苯基膦钯(0.23g,0.2mmol)和碳酸钾溶液(5mL,2mol/L)加入到四氢呋喃(30mL),在氮气保护下,于65℃加热回流10h。待冷却至室温后加水用二氯甲烷萃取三次,有机层用饱和食盐水洗涤,用无水硫酸钠干燥,旋蒸除去溶剂,粗产物柱层析(VPE:VDCM=1:3)分离得到紫色固体IVb(0.52g,32%)。m.p.144-145℃;1H NMR(500MHz,CDCl3)δ9.88(s,1H),8.82(s,1H),8.76(s,1H),8.61(dd,J=8.0,1.5Hz,1H),8.35(dd,J=14.1,2.7Hz,1H),7.80(t,J=7.8Hz,1H),7.74(t,J=4.0Hz,1H),7.63(td,J=9.0,2.5Hz,1H),7.58-7.53(m,4H),7.43(d,J=8.8Hz,1H),7.35-7.32(m,3H),7.21(d,J=7.7Hz,1H),7.15-7.12(m,3H),7.07(d,J=8.8Hz,1H),4.56-4.51(m,4H),2.08-1.99(m,4H),1.67-1.62(m,4H),1.52-1.45(m,4H),1.39-1.31(m,12H),0.93-0.88(m,6H);HREIMS m/z 813.5100[M]+,cacld C53H55N3O3S for:813.3964.
化合物II的合成
称取化合物IVb(0.32g,0.4mmol),氰基乙酸V(0.03g,0.4mmol)加入到乙腈溶液中(12mL),然后加入吡啶(0.10mL,1.2mmol),在氮气保护下,于80℃加热回流6h,待冷却至室温后,直接旋干,粗产物柱层析(VCH2Cl2:VCH3OH:VHAc=400:4:1),分离得到黑色固体II(0.31g,88%)。m.p.237-238℃;1H NMR(500MHz,DMSO)δ8.51(bs,2H),8.44(d,J=6.7Hz,2H),8.31(dd,J=8.0,1.7Hz,1H),7.97(t,J=3.8Hz,2H),7.81-7.78(m,2H),7.73(d,J=9.0Hz,1H),7.69(d,J=8.5Hz,2H),7.64-7.60(m,2H),7.40(t,J=7.8Hz,2H),7.27(t,J=7.4Hz,1H),7.20-7.16(m,2H),7.10(d,J=6.6Hz,1H),7.06(d,J=8.4Hz,1H),4.48-4.37(m,4H),1.87-1.78(m,4H),1.56-1.46(m,4H),1.43-1.35(m,4H),1.30-1.21(m,12H),0.87-0.80(m,6H);HREIMS m/z 881.4079[M+H]+,cacld C56H56N4O4S for:880.4022.
实施例3
化合物IVc的合成
称取化合物VII(1.56g,2.0mmol),X(0.42g,3.0mmol),四三苯基膦钯(0.23g,0.2mmol)和碳酸钾(5mL,2mol/L)加入到四氢呋喃(30mL),在氮气保护下,于65℃加热回流10h。待冷却至室温后加水用二氯甲烷萃取三次,有机层用饱和食盐水洗涤,用无水硫酸钠干燥,旋蒸除去溶剂,粗产物柱层析(VPE:VDCM=1:3)分离得到紫色固体IVc(0.64g,40%)。m.p.106-108℃;1H NMR(500MHz,CDCl3)δ9.61(s,1H),8.81(s,1H),8.74(s,1H),8.60(d,J=9.0Hz,1H),8.35(d,J=2.6Hz,1H),7.79(t,J=7.0Hz,1H),7.70(d,J=8.7Hz,2H),7.63(dd,J=9.2,2.6Hz,1H),7.54(t,J=8.0Hz,2H),7.36-7.30(m,4H),7.20(d,J=7.8Hz,2H),7.15-7.12(m,3H),6.73(d,J=3.8Hz,1H),4.59-4.50(m,4H),2.08-1.98(m,4H),1.64-1.58(m,4H),1.51-1.43(m,4H),1.40-1.30(m,12H),0.92-0.88(m,6H);HREIMS m/z 798.4273[M+H]+,cacld C53H55N3O4for:797.4193.
化合物III的合成
称取化合物IVc(0.32g,0.4mmol),氰基乙酸V(0.1g,1.2mmol)加入到四氢呋喃溶液中(16mL),然后加入三乙胺(0.22mL,1.6mmol),在氮气保护下,于65℃加热回流7h,待冷却至室温后,直接旋干,粗产物柱层析(VCH2Cl2:VCH3OH:VHAc=400:4:1),分离得到黑色固体III(0.31g,91%)。m.p.164-165℃;1H NMR(500MHz,DMSO-d6)δ13.56(s,1H),8.46(s,1H),8.38(s,1H),8.28(d,J=7.7Hz,1H),7.99(s,1H),7.96(d,J=2.7Hz,1H),7.80-7.75(m,4H),7.68(d,J=8.7Hz,1H),7.59(dd,J=9.1,2.4Hz,1H),7.51(d,J=3.5Hz,1H),7.40(t,J=7.7Hz,2H),7.25-7.18(m,5H),7.05(d,J=8.7Hz,2H),4.43-4.30(m,4H),1.86-1.75(m,4H),1.55-1.44(m,4H),1.41-1.34(m,4H),1.31-1.23(m,12H),0.86-0.80(m,6H);HREIMSm/z 865.4316[M+H]+,cacld C56H56N4O5for:864.4251.
实施例4
如式I、式II或式III所示的含喹吖啶酮的三芳胺类化合物作为染料敏化剂在染料敏化太阳能电池中的应用。
(1)导电玻璃的切割
开始用欧姆表测试出玻璃的导电面,欧姆表有读数的就是导电面。然后把10×10cm2正方形导电玻璃的非导电面朝上,固定在有刻度标志的桌面上,用玻璃刀切割非导电面,先把它切成10×5cm的两块,然后分别把这两块再四等分,最后切成5×2.5cm2的8块玻璃。
(2)导电玻璃的清洗
将切割好的5×2.5cm2导电玻璃放入到有洗衣粉和清水的大烧杯中,先超声15分钟,然后用清水冲洗干净,然后再加入丙酮超声15分钟后,再加入异丙醇超声15分钟,最后取出处理后的导电玻璃,用吹风机吹干以后,放在培养皿中准备下一步的制备。
(3)涂二氧化钛浆料,制备电池阳极
将处理后的导电玻璃的导电面固定在印刷模板上,用干净的玻璃棒蘸取纳米介孔TiO2浆料涂抹在印刷模板上,用橡胶刮力度均匀地往下刷8次,TiO2浆料能够顺着印刷模板的网均匀地涂到导电玻璃上。涂完以后,把所述的导电玻璃放到温度为125℃的烘箱中烘烧10分钟,然后冷却到室温,再用干净的玻璃棒蘸取纳米介孔TiO2浆料涂抹在印刷模板上,按照上述步骤重复操作得到涂完浆料的导电玻璃。
(4)高温加热
为了让电池阳极更加稳定,提高实验结果的准确性,把涂完浆料的导电玻璃放入马弗炉中高温煅烧,具体的煅烧步骤如下:常温先加热到325℃,这一过程需要10分钟,325℃恒温烧5分钟,花5分钟把温度从325℃加热到375℃,375℃恒温烧5分钟,花5分钟把温度从375℃加热到450℃,450℃恒温烧5分钟,最后花5分钟把温度从450℃加热到500℃,500℃恒温烧5分钟,停止加热,过夜冷却至室温。
(5)电池阳极的制备
分别将式I、式II或式III所示的含喹吖啶酮的三芳胺类化合物加入到溶剂为(VCHCl3:VCH3OH=10:1)的混合溶剂配置成3×10-4mol/L的溶液,分别向所述的溶液中加入TiO2电极,在黑暗条件下浸泡24h,然后取出用吹风机吹干,得到电池阳极备用。
(6)组装太阳能电池
将H2PtCl6×6H2O涂在空白导电玻璃上作为电池阴极,将0.3M 1-甲基-3-丙基碘化咪唑0.03M I2,0.07M LiI,0.1M异硫氰酸胍和0.4M 4-叔丁基吡啶加入到的乙腈溶液中得到含碘0.07mM/L的电解质,将所述的电池阴极、阳极及含碘电解质组装得到染料敏化太阳能电池,对新材料进行光电性能测试。将所述的染料敏化太阳能电池于100mW/cm2光强照射下,测定光电压-电流特性曲线。其结果如图1和表1所示:
表1含喹吖啶酮的三芳胺类染料敏化剂组装得到的DSSC性能参数
由图1和表1可知,所述的式I、式II或染料敏化剂组装得到的染料敏化太阳能电池光电转换效率为2.91-5.32%,其中以呋喃为桥键的式III所示的含喹吖啶酮的三芳胺类染料敏化剂的光电转换效率最好,为5.32%。
Claims (5)
1.一种结构如式I、式II或式III所示的含喹吖啶酮的三芳胺类化合物的制备方法,
其特征在于,所述的制备方法按如下步骤进行:
向式Iva、Ivb或IVc所示的化合物中加入式V所示的化合物,在有机溶剂中,在碱性物质的作用下,在60~80℃下加热回流搅拌反应6~8h,反应完全后,所得反应混合液经后处理分别得到式I、式II或式III所示的含喹吖啶酮的三芳胺类化合物;所述的式Iva、Ivb或IVc所示的化合物与式V所示的化合物、碱性物质的物质的量之比为:1:1.0~3.0:3.0~5.0;
2.如权利要求1所述的制备方法,其特征在于,所述的碱性物质为哌啶、吡啶或三乙胺。
3.如权利要求1所述的制备方法,其特征在于,所述的有机溶剂为氯仿、乙腈或四氢呋喃。
4.如权利要求1所述的制备方法,其特征在于,所述的有机溶剂的体积用量以式Iva、Ivb或IVc所示的化合物的物质的量计为30~40mL/mmol。
5.如权利要求1所述的制备方法,其特征在于,所述的反应混合液的后处理方法为:反应结束后,所得反应混合液蒸除溶剂后,残余物用洗脱剂溶剂进行硅胶柱层析,以二氯甲烷和甲醇及醋酸的混合溶液为洗脱剂,收集含目标化合物的洗脱液,浓缩干燥分别得式I、式II或式III所示的苯并咔唑类化合物。
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