CN105384916B - 含噻吩基单核钌配合物电聚合薄膜的制备方法和光电化学性质 - Google Patents
含噻吩基单核钌配合物电聚合薄膜的制备方法和光电化学性质 Download PDFInfo
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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Abstract
本发明公开了一种含噻吩基单核钌配合物的电聚合薄膜的制备方法及其电化学和光电化学的性质，采用简单的电化学的方法使单核钌配合物在ITO电极上形成聚合物薄膜，对薄膜的电化学的性质测试显示，该聚合物聚合20圈薄膜在水溶液中具有很好的稳定性，对薄膜进行的光电性能测试结果显示，在负偏压部分，所加偏压越负，该薄膜的光电流越大，当偏压为0V时也表现出了相当大的光电流，随着偏压继续增加，光电流的变化幅度明显小于在负偏压时的光电流大小，表现出了很好的整流性质。因此，本发明中的含噻吩基的单核钌配合物电聚合薄膜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，涉及含噻吩基单核钌配合物电聚合薄膜的制备方法及其电化学和光电化学性质。
背景技术
近几年，聚合物薄膜由于其制备方法简单，性能较单体优越，因此引起了研究者们的研究兴趣。在光电器件中，具有高效的光吸收、电荷分离和电荷转移运输功能的材料极为重要[A.Facchetti，π-Conjugated polymers for organic electronics andphotovoltaic cell applications，Chem.Mater.，2011，23，733-758]。然而，一些纯有机聚合物由于其不可逆的还原过程，导致了聚合材料电化学的不稳定性和电荷传输受阻[C.Groves，J.C.Blakesley，N.C.Greenham，Effect of charge trapping on geminaterecombination and polymer solar cell performance，Nano Lett.，2010，10，1063-1069.]。而一些金属具有很好的可逆的氧化还原性质，因此包含这些金属元素的聚合物是一种新型的、有研究价值的功能材料[A.S.Abd-El-Aziz，S.S.Dalgakiran，L.Bichler，Novel synthesis and electropolymerization of metallo-conjugated thiophenederivatives，European Polymer Journal.，2012，48，1901-1913]。而且含有过渡金属的聚合物材料通常具有氧化还原性、磁性、或者催化性能[W.W.Yeung，Luminescentorganometallic poly(aryleneethynylene)s：functional properties towardsimplications in molecular optoelectronics，Dalton Trans.，2007，40，4495-4510.]。
Friebe等用电聚合的方法合成了含有2，6-二喹啉-8-吡啶钌(II)聚噻吩化合物，研究了不同比例的钌(II)-噻吩对其在电化学、导电率及其光学性能方面的影响。研究发现，随着钌(II)比率的增加，聚合物的可逆开关控制的导电率增大，可达到10-5S/cm[C.Friebe，M.Jager，U.S.Schubert，Emitting electrode coatings with redox-switchable conductivity：incorporation of ruthenium(II)-2，6-di(quinolin-8-yl)pyridine complexes into polythiophene by electropolymerization，RSC Adv.，2013，3，11686-11690]。因此，含有噻吩基单核钌配合物的聚合薄膜具有很广泛的应用前景。
发明内容
本发明的目的是在铟-锡氧化物(ITO)导电玻璃上通过电化学的方法制备薄膜，该薄膜的稳定性较好，且形成的薄膜具有较大的光电响应及整流性质。
本发明的技术方案如下：
本发明所提供的含噻吩基单核钌配合物电聚合薄膜，是将钌配合物溶于0.1M四丁基六氟 合磷酸铵的CH2Cl2溶液中，通过电化学的方法将钌配合物沉积到工作电极表面，通过扫描不同的圈数聚合形成具有不同厚度的聚合薄膜，所述单核钌配合物的由阳离子部分和阴离子(抗衡离子)部分组成，其中阳离子部分为[Ru(bpy)2L]2+，阴离子部分为无机盐阴离子ClO4 -，配体L的结构如下式所示：
具体地，单核钌配合物的分子式为[Ru(bpy)2L](ClO4)2，结构如下式所示：
上述单核钌配合物蒸发膜电极的制备方法，包括：将钌配合物溶于0.1M四丁基六氟合磷酸铵的二氯甲烷溶液中，钌配合物的浓度为1mM，以ITO导电玻璃为工作电极，铂电极为对电极，银丝为参比电极，向溶液中通15分钟N2，结束之后，以扫速为50mV/s，分别扫10圈，20圈，30圈，40圈，50圈，即得到聚合不同圈数的薄膜。
本发明还提供上述单核钌配合物聚合薄膜的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：
本发明采用简单的电化学聚合的方法使含有噻吩基的单核钌配合物聚合到ITO片上，形成不同聚合圈数的薄膜，并测定薄膜的电化学性质(电化学稳定性及电子转移速率常数)和光电化学性质(光电流大小及光电转换效率)，在聚合不同圈数的薄膜中发现聚合20圈的薄膜最稳定，聚合薄膜在0.1M硫酸钠水溶液中扫描50圈后，峰电流衰减不到20％。其光电流具有整流的性质。因此，本发明中的钌配合物聚合薄膜在能量转换领域具有广泛的应用前景。
附图说明
图1配合物[Ru(bpy)2L](ClO4)2溶液的电聚合循环伏安图，ITO为工作电极，铂电极为对电极，银丝为参比电极，扫速为50mV/s(1-20圈)。
图2配合物[Ru(bpy)2L](ClO4)2电聚合20圈所得聚合薄膜的扫描50圈后循环伏安图。
图3配合物[Ru(bpy)2L](ClO4)2电聚合20圈所得聚合薄膜的在0.1M的Na2SO4溶液中随扫速变化的循环伏安图，饱和甘汞电极(SCE)为参比电极，铂电极为对电极；内插图为电子转移速率常数的点图。
图4配合物[Ru(bpy)2L](ClO4)2电聚合20圈所得聚合薄膜光电流与电极所加偏压的关系，偏压为-0.3V～+0.1V(a)，+0.2V～+0.9V(b)；光源为100mW/cm2的白光，电极面积为0.28cm2，0.1M的Na2SO4为支持电解质。
图5配合物[Ru(bpy)2L](ClO4)2电聚合20圈所得聚合薄膜在偏压为-0.2V时的单色光光电转化效率-波长(IPCE)曲线。
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的制备
配体L的合成路线如下所示：
化合物1按照文献[Z.H.Peng，A.R.Gharavi，L.P.Yu，Synthesis andcharacterization of photorefractive polymers containing transition metalcomplexes as photosensitizer，J.Am.Chem.Soc.，1997，119(20)，4622-4632.]方法制备。
将化合物1(0.33g，0.72mmol)与噻吩甲醛(0.188g，1.68mmol)溶于10ml四氢呋喃中，在氮气氛围，剧烈搅拌下把10ml的t-BuOK(0.18g)悬浊液缓慢滴加到上述溶液中，此时溶液由浅黄色变为暗红色，上层液面发蓝光。滴加完毕继续室温搅拌12h，体系变成亮黄色。反应完毕，把反应体系倒入300ml的二氯甲烷中，用水洗涤三次，硫酸钠干燥后除去二氯甲烷得粗产物，用二氯甲烷重结晶得亮黄色固体(0.24g，89.6％)。
氢核磁共振谱(δH，ppm，500MHz，CDCl3)：d＝8.77(s，2H；h)，8.52(s，2H；f)，7.98(d，J＝7.8Hz，2H；a)，7.41(d，J＝16.12Hz，2H；d)，7.29(d，J＝5.08Hz，2H；g)，7.17(d，J＝3.4Hz，2H；c)，7.05(t，J＝8.64Hz，2H；b)，6.97(d，J＝16.12Hz，2H；e).
实施例二、钌配合物[Ru(bpy)2L](ClO4)2的制备
钌配合物[Ru(bpy)2L](ClO4)2的合成路线如下所示：
Ru(bpy)2Cl2按照文献[Z.Q.Ji，S.D.Huang，A.R.Guadalupe.，Synthesis，X-raystructures，spectroscopic and electrochemical properties of ruthenium(II)complexes containing2，2’-bipyrimidine.Inorg.Chim.Acta，2000，305，127-134.]方法制备。
将50mg(0.19mmol)配体L溶于6ml DMF中，之后向其中加入10ml乙醇以及88mg(0.23mmol)Ru(bpy)2Cl2，N2保护下加热回流20小时，冷却到室温后，抽滤，除去没有反应的配体，将滤液中的乙醇旋出后，向其中加入高氯酸钠的水溶液，抽滤收集沉淀，将沉淀真空干燥后向其中加入少量的乙腈溶解，之后过氧化铝柱子，展开剂为二氯甲烷∶甲醇＝50∶1，收集浅黄色色谱带，将溶剂旋干后，向其中加入少量乙腈溶解，之后在乙醚中扩散重结晶，抽滤收集沉淀，得到紫红色固体53mg，产率为40.0％。
氢核磁共振谱(δH，ppm，500MHz，DMSO-d6)：8.81(m，6H)，8，46(dd，J＝1.7Hz，7.0Hz，2H)，8.2(m，4H)，7.82(d，J＝5.1Hz，2H)，7.72(m，4H)，7.66(s，1H)，7.61(s，1H)，7.56(m，6H)，7.27(d，J＝3.2Hz，2H)，7.10(dd，J＝3.6Hz，1.4Hz，2H)，6.81(s，1H)，6.77(s，1H)。
快原子轰击质谱(MALDI-TOF MS in CH3CN)：计算值：m/z(100％)＝393.06([(M-2ClO4 -)]2+)，881.5([M-ClO4 -]+)。实验值：m/z(100％)＝392.9([(M-2ClO4 -)]2+)，884.3([M-ClO4 -]+)。
元素分析：C42H32Cl2N6O8RuS2·1.5H2O(F.W＝1011.87)计算值：C：49.85，H：3.49，N：8.31；测量值：C：49.82，H：3.59，N：8.27。
实施例三、钌配合物电聚合薄膜的制备
1.清洗铟-锡氧化物(ITO)导电玻璃。将ITO玻璃切成1.5cm×5cm的小块。依次用洗涤剂，一次水超声清洗各三次，每次超声5分钟，最后用浓氨水∶双氧水∶一次水＝1∶1∶5(v∶v∶v)的混合溶液中70℃下保持半小时。取出后再用一次水超声清洗，最后用洗耳球吹干放入小瓶中，干燥备用。
2.将钌配合物溶于0.1M四丁基六氟合磷酸铵的二氯甲烷溶液中，钌配合物的浓度为1mM，以ITO为工作电极，铂电极为对电极，银丝为参比电极，向溶液中通入N2，通15min，结束之后，以扫速为50mV/s，分别扫描不同的圈数，即得到聚合不同圈数的薄膜，以聚合20圈的薄膜为例(见图1)。
实施例四、电聚合薄膜的电化学及光电化学性质
(一)电化学测试
在CHI-601电化学工作站中进行电化学测试，采用三电极体系，饱和甘汞电极为参比电极，铂丝为对电极，电聚合薄膜为工作电极。支持电解液为0.1M硫酸钠溶液。因为电聚合薄膜为表面控制的氧化还原过程，所以电子转移速率常数ks及转移因子α根据Laviron理论[E.Laviron，General expression of the linear potential sweep voltammogram inthe case of diffusionless electrochemical systems，J.Electroanal.Chem.，1979，101，19.]通过ΔE(ΔE＝Ep-E0′，E0′是氧化或还原峰的峰电位)与扫速(v)的log值作图求得。
根据Laviron理论，ks及α可以由公式1及2求得，
F是法拉第常数，n为氧化还原过程中转移的电子数，va及vc是分别为氧化峰数据及还原峰数据直线拟合后在X轴上的截距，此公式适合用于ΔE＞200mV的数据。
(二)光电化学性质
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-601电化学工作站上测定电聚合薄膜的光电流-诱导时间曲线(I-t曲线)，支持电解液为0.1M硫酸钠溶液，改变所加偏压，测不同偏压下的电聚合薄膜的光电流-诱导时间曲线(I-t曲线)。
单核钌配合物聚合薄膜的单色光转换效率IPCE通过公式3计算得出：
I为光电流密度的大小，Pinc是特定波长下入射光的强度。
通过测定电聚合20圈电聚合薄膜在电解质溶液中扫描50圈的循环伏安曲线(见图2)，可以看出该薄膜在水溶液中比较稳定。
通过测定不同扫速下的电聚合薄膜的循环伏安曲线，可以测定该薄膜的电子转移速率常数(见图3)，通过计算，20圈电聚合薄膜的电子转移速率常数为25s-1。
通过测不同偏压下的电聚合薄膜的光电流-诱导时间曲线(见图4)，发现所加的偏压越负，该电聚合薄膜的光电流越强，当偏压达到0V以上时，随着偏压的增加，薄膜的光电流增加的幅度远远小于在负偏压时的幅度大小，表现出了很好的整流性质。
通过测定在偏压为-0.2时电聚合20圈薄膜在不同波长单色光下的IPCE值(见图5)，求 得光电转换效率为0.12％。
Claims (4)
1.一种含噻吩基单核钌配合物电聚合薄膜，是通过电化学方法将含噻吩基钌配合物聚合到ITO导电玻璃上后得到的聚合薄膜，所述单核钌配合物由阳离子部分和阴离子部分组成，其中，阳离子部分为[Ru(bpy)2L]2+，阴离子部分为无机盐阴离子，配体L的结构如下式所示：
2.如权利要求1所述的单核钌配合物的聚合薄膜，其特征在于，所述单核钌配合物的分子式为[Ru(bpy)2L](ClO4)2，结构如下式所示：
。
3.权利要求1所述的单核钌配合物电聚合薄膜的制备方法是：以ITO为工作电极的三电极的溶有配合物溶液的电化学槽中，循环伏安扫描不同圈数即可得到不同厚度的聚合物薄膜。
4.权利要求1所述的单核钌配合物薄膜在光电转换领域中的应用。
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