CN110400910B - 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 - Google Patents

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 Download PDF

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CN110400910B
CN110400910B CN201810369995.7A CN201810369995A CN110400910B CN 110400910 B CN110400910 B CN 110400910B CN 201810369995 A CN201810369995 A CN 201810369995A CN 110400910 B CN110400910 B CN 110400910B
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高丽华
叶怀尧
王克志
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Abstract

具有良好稳定性以及良好光电转换性能的杂多配合物与钌配位聚合物杂化薄膜，涉及杂多配合物/钌配位聚合物杂化薄膜的制备方法、光电化学活性评价。该薄膜由杂多配合物K5[BW12O40]和含有三苯胺基单核钉配合物通过静电和电聚合双重作用制备而成。在施加偏压‑0.3V(vs SCE)时，用光强为100mW/cm2的白光(730nm＞λ＞325nm)照射该薄膜，能产生的光电流密度可达12.1μA/cm2，表现出良好的光电转换性能以及良好的整流性质，有望在太阳能电池开发方面得到应用。

Description

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
技术领域
本发明属于电化学领域，涉及一种由两个组分形成的杂化薄膜，尤其涉及一种硼钨杂多配合物和含有三苯胺基钌配合物的电聚合薄膜的制备方法及其光电化学性质。
背景技术
随着现代科技的发展，单一性能的材料已不能满足人们的需要。通过两种或多种材料的杂化，可以使杂化材料实现不同性能材料之间的分子级复合以及性能得到互补和优化，因此，杂化材料具有广阔的应用前景而受到人们的广泛关注。
杂多配合物是一类具有结构多样性的金属氧簇合物，由于其结构中含有多个高价氧化态的金属离子，在不同的还原电位下可不同程度的接受电子而发生还原反应，另外，杂多配合物的性质可以通过调整其组成和结构得到调整。因此，杂多配合物在电化学、电分析化学领域得到了广泛应用。钌配合物具有丰富的光物理、光化学性质，激发态反应活性高、寿命长，发光性能良好以及稳定性好等特点，常被用于染料敏化太阳能电池中的光敏剂。我们曾报道一些钌(II)配合物与杂多配合物的静电自组装杂化薄膜，并研究了这些薄膜的光电转换性质(Jian Min Qi，Hui Li Wang，Li Hua Gao，Hao Lin，Ke Zhi Wang.A newinorganic-organic hybrid film based on a terpyridyl ruthenium(II)complex and[BW11Zn(H2O)O39]7-，Materials letters，2015，153，33-35.Honglei Zhang，Jianmin Qi，Lihua Gao，Kezhi Wang，A hybrid electrostatically self-assembled film based ondinuclear ruthenium(II)polypyridyl complex and europium-substitutedtungstoborate，Colloids and Surfaces A：Physicochem.Eng.Aspects 2016，492，119-126.Huaiyao Ye，Jianmin Qi，Rui Sun，Lihua Gao，Kezhi Wang.Photoelectric activehybrid film based on RuII terpyridyl complex and EuIIIsubstituted Kegginpolyoxometalate of [Eu(BW11O39)2]15-，Electrochimica Acta，2017，256，291-298.)。研究结果表明，此类薄膜在白光照射下能产生稳定的阴极光电流，但是组成杂化薄膜的钌配合物以及杂多配合物的组成和结构对薄膜的光电转换性能具有较大的影响。由此可见，通过调整杂化薄膜材料的组成和结构，可以改善材料的光电转换性能。
电化学聚合法是利用前体分子直接在电极表面发生氧化或还原的偶联反应，从而在电极上制备薄膜的方法。该方法成本低，不需要催化剂，可以直接生成稳定交联的聚合物薄膜，薄膜厚度和形貌可通过电化学参数的调节而得到调节。若将具有功能性的分子聚合到电极表面，可获得具有功能性的聚合物薄膜。我们通过大量的实验探索，由含有三苯胺基单核钌配合物和硼钨杂多配合物为组装薄膜的两个组分，通过静电吸引并结合电聚合方法在导电玻璃上制备了一个含有硼钨杂多配合物和钌配位聚合物的杂化薄膜，研究表明：该薄膜材料是一个具有良好光电转换性能的电极材料。目前，该杂化薄膜材料未见报道。
发明内容
本发明的目的是制备一种具有良好光电转换性能的硼钨杂多配合物和钌配位聚合物的杂化薄膜。
本发明的技术方案如下：
首先对基片进行清洁处理，用蒸馏水充分洗净，空气吹干后，将基片浸入到3-氨基丙基-三乙氧基硅烷的乙醇溶液中8小时，取出后用无水乙醇洗净，再浸入到硼钨杂多配合物的酸性水溶液(pH＝2)中1小时，用蒸馏水充分洗去物理吸附的硼钨杂多配合物，空气吹干。此时，电极上通过静电自组装将硼钨杂多配合物固定到电极表面。然后，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，通过电化学聚合方法将单核钌配合物聚合到沉积有一层硼钨杂多配合物的工作电极表面，通过控制扫描速率和扫描圈数使钌配合物聚合，在硼钨杂多配合物层上形成不同厚度的钌配位聚合物薄膜。
本发明采用的单核钌配合物的分子式为[RuL3](ClO4)2，其结构式如下：
Figure BSA0000162752000000021
本发明采用的杂多配合物为K5[BW12O40]，其阴离子为[BW12O40]5-(简写为BW)。
本发明制备的杂多配合物/钌配位聚合物薄膜是首次制备的，该薄膜通过静电和聚合双重作用把杂多配合物阴离子和钌配位聚合物阳离子结合在一起。与现有技术相比，比纯粹的电聚合薄膜具有良好的稳定性，比未聚合的杂多配合物/钌配合物薄膜具有更好的光电转化性能。因此，本发明中的杂多配合物/钌配位聚合物杂化薄膜在能量转换领域具有潜在的应用前景。
附图说明
图1配合物[RuL3](ClO4)2溶液的电聚合循环伏安图，组装一层BW的导电玻璃为工作电极，铂电极为对电极，银丝为参比电极，扫速为25mV/s，聚合1圈。
图2聚合1圈的BW/{RuL3}n电聚合薄膜的紫外可见吸收光谱。
图3聚合1圈的BW/{RuL3}n电聚合薄膜在光照下产生的光电流-时间曲线。光源：100mW/cm2的白光，偏压：-0.3V和0.0V，电极面积：0.28cm2，支持电解质溶液：0.1M的Na2SO4溶液(pH＝1)。
图4聚合1圈的BW/{RuL3}n电聚合薄膜产生的光电流与电极所加偏压的关系，偏压为-0.3V～+0.5V。光源：100mW/cm2的白光，电极面积：0.28cm2，支持电解质溶液：0.1M的Na2SO4溶液(pH＝7)。
具体实施方式
实施例1：BW/{RuL3}n电聚合薄膜的制备
基片的清洗：导电玻璃基片经洗涤剂清洗后，用蒸馏水洗净，吹干。
基片的羟基化：将浓氨水、30％过氧化氢和蒸馏水按1∶1∶5的体积比混合均匀，加热到70℃后，将清洁的基片浸入20分钟，取出后用蒸馏水充分洗净，空气吹干。
基片的硅烷化：配制体积比为5％的3-氨基丙基-三乙氧基硅烷的乙醇溶液，将经过羟基化的基片浸入其中8小时，取出后用无水乙醇洗净，空气吹干。
基片的质子化：将硅烷化的基片浸入pH＝2的盐酸溶液中20分钟，取出后用蒸馏水洗净，空气吹干。
BW/{RuL3}n电聚合薄膜的制备：将单核钌配合物溶于0.1mol/L四丁基六氟合磷酸铵的二氯甲烷溶液中使钌配合物的浓度为0.001mol/L，以组装一层BW的导电玻璃为工作电极，铂电极为对电极，银丝为参比电极，向溶液中通入氮气15分钟后，以0.025V/s扫描速率扫描1圈，即得到BW/{RuL3}n电聚合薄膜，[RuL3](ClO4)2溶液电聚合时的循环伏安图见图1。
薄膜的紫外可见吸收光谱在美国瓦里安公司生产的CARY-50型的紫外-可见分光光度计上进行测定。图2为聚合1圈的BW/{RuL3}n电聚合薄膜的可见吸收光谱，结果表明：薄膜在372和475nm处表现出钌配位聚合物的特征吸收，表明BW/{RuL3}n电聚合薄膜被成功制备。
实施例2：薄膜的光电流测试
光电流的测定在CHI660电化学分析仪上进行(上海辰华仪器有限公司)，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)；测试时模拟太阳光，光强为100mW/cm2白光(730nm＞λ＞325nm)，入射光强度利用标准硅电池校正后的辐照计测定(北京师范大学光学仪器厂)。
室温下，将实施例1制备的BW/{RuL3}n电聚合薄膜做工作电极，铂丝为对电极，饱和甘汞电极为参比电极，置于一定酸度的0.2mol/LNa2SO4的水溶液中，用光强为100mW/cm2的白光(730nm＞λ＞325nm)照射BW/{RuL3}n薄膜工作电极，改变所加偏压和电解质溶液的pH值，测电聚合薄膜的光电流-诱导时间曲线。
在施加偏压分别为-0.3V(vs SCE)和零偏压下，电解质溶液pH值为1，用100mW/cm2的白光照射BW/{RuL3}n薄膜工作电极，产生的光电流-诱导时间曲线如图3所示。结果表明，当光照BW/{RuL3}n薄膜时，在-0.3V(vs SCE)和零偏压下，薄膜均能产生稳定的阴极光电流，多次开关光源，光电流响应是快速的。在施加偏压为-0.3V和零偏压时，薄膜产生的光电流密度可分别达到12.1和9.0μA/cm2。改变外加偏压，测定的电聚合薄膜的光电流-诱导时间曲线示于图4，可见所加的偏压越负，电聚合薄膜产生的光电流越强，且正偏压下光电流很小，也表现出该薄膜具有良好的整流性质。与静电自组装薄膜相比，该电聚合薄膜表现出增强的光电转换性能，有望在太阳能电池的开发方面得到应用。

Claims (1)

1.一种具有增强光电转换性能的、稳定的杂化薄膜，是通过静电和电聚合双重作用将含三苯胺基单核钌配合物聚合到表面沉积有一层Keggin结构硼钨杂多阴离子[BW12O40]5-的导电玻璃上后得到的，其特征在于：该含三苯胺基单核钌配合物通过电聚合形成钌配位聚合物阳离子，该薄膜由该Keggin结构硼钨杂多阴离子[BW12O40]5-和该钌配位聚合物阳离子组成，其中含三苯胺基单核钌配合物的分子式为[RuL3](ClO4)2，其结构式如下：
Figure FSB0000192003830000011
该杂化薄膜用于光电化学电池工作电极。
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