CN109012605B - 一种基于甲基紫精配体的具有光电效应和吸附特性的金属有机杂化材料及应用 - Google Patents
一种基于甲基紫精配体的具有光电效应和吸附特性的金属有机杂化材料及应用 Download PDFInfo
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Abstract
本发明公开了一种基于甲基紫精配体的具有光电效应和吸附特性的金属有机杂化材料及应用，属于光电材料和环境保护领域。本发明通过在黑暗条件下测得的光电流和在375nm波长的激光照射下测得的光电流之间的对比，证明其具有光电效应，这对光伏产业以及环境保护中处理有机染料和降低重金属污染方面将有巨大的潜力。
Description
技术领域
本发明属于光电材料和环境保护领域，尤其是涉及一种新型不含铅的金属有机杂化材料在光伏产业的应用，将在柔性可穿戴和便携式电子设备、光伏建筑一体化和军事等领域具有很强的应用潜力。同时本发明在有机染料以及重金属离子吸附方面的吸附特性，将有望制备成高效的吸附剂，这将在工业污染严重的水质优化方面发挥很大的作用。
背景技术
太阳能作为一种可持续发展的能源，一直以来受到广泛的关注。为了制备高效低价的光伏材料去利用太阳能，有机材料太阳能电池成为了一种潜在的能广泛利用的光伏技术。但是传统金属有机杂化太阳能材料有铅元素，这一有害的元素限制了其应用范围，所以对于环境友好且稳定的钙钛矿材料的研究成为了现在的热点。有机太阳能电池具有质轻、柔性、成本低、弱光响应等优点，是当前太阳能电池技术的前沿热点研究方向。高效率﹑耐弯折和廉价的柔性有机太阳能电池在柔性可穿戴和便携式电子设备、光伏建筑一体化和军事等领域具有很强的应用潜力。
在工业发展中，在通过对一些前期材料的加工处理获得带给人们生活便利的生产成品的同时，因为一些工艺的不成熟或者不可避免的处理环节，往往会产生一些对人的身体有害或者引起环境污染的物质，含有这类物质的工业污水必须经过有效地处理才可以正常排放再由环境自净，因此对于这类物质的处理也将成为工业投入的一部分。选择合适高效的吸附剂将大大的降低工业投入，同时也对环境的保护起到至关重要的作用。
发明内容
本发明的目的在于提供一种基于甲基紫精配体的具有光电效应和吸附特性的金属有机杂化材料的(MV)4[Bi6Cl26]在光电材料和对有机染料以及重金属离子吸附方面的应用；其中的MV指的是甲基紫精双阳离子,它通过4,4’-联吡啶、甲醇、氢碘酸反应后所得，其结构为：
其中所述的光电材料指的是光伏产业、光电器件，例如便携式太阳能电池。所述的吸附有机染料指的是甲基蓝溶液。所述的吸附重金属离子指的是对Cu、Co、Mn、Pb、Ni、Cr的吸附。
本发明中所述(MV)4[Bi6Cl26]材料宏观形貌为黄色棒状晶体，力学性能很差，用很小的力就能使得棒状晶体破碎，在电子显微镜下观察具有类层状结构的特点，这使得它具有了对有机染料和重金属离子吸附的特性。
本发明第一次对获(MV)4[Bi6Cl26]做了TEM测试，并获得了(MV)[BiI3Cl2]晶体的原子像和电子束衍射图像（测试的仪器型号Tecnai G2 F20 TEM）【注，仪器型号G后面的2为上标】，从衍射图像可得知用水热法制备的(MV)[ BiI3Cl2]晶体同时存在单晶和多晶的成分。
本发明更进一步公开了基于甲基紫精配体的具有光电效应和吸附特性的金属有机杂化材料及(MV)4[Bi6Cl26]晶体在用于光伏产业、光电器件方面的应用。本发明通过在黑暗条件下测得的光电流和在375nm波长的激光照射下测得的光电流之间的对比，证明其具有光电效应，其具体实验设计及操作如下：
（1）在不导电的PC板上放置一根(MV)4[Bi6Cl26]晶体，在晶体两端分别用导电银浆镀上电极，在常温下等待银浆干透，并用万用表确认电极已经导电；
（2）将制备好的样品置于电流表探针台，并分别将两个探针与样品两个电极接触，在黑暗条件下测试出50V电压下通过材料的电流曲线；
（3）将375nm的激光照射在样品表面，调节激光功率为70mw，在50V电压下测出通过材料的电流；
（4）将所测未加光和加不同功率的光所测得的电流曲线作图探究其光电特性。
本发明更进一步公开了基于甲基紫精配体的具有光电效应和吸附特性的金属有机杂化材料及(MV)4[Bi6Cl26]晶体在用于吸附有机染料颜色方面的应用。其对有机染料吸附特性的实验设计及详细步骤如下：
（1）首先将只加甲基蓝溶液的比色皿放入紫外可见光吸收仪器里，测出甲基蓝溶液的吸收谱。
（2）准备另外一只比色皿，加入一定量(MV)4[Bi6Cl26]材料，并加入甲基蓝溶液；
（3）每隔 5分钟测一次含有(MV)4[Bi6Cl26]材料的比色皿内溶液的吸收谱，并与甲基蓝的峰值作对比，重复多次直至甲基蓝完全被吸附完。
本发明同时也公开了基于甲基紫精配体的具有光电效应和吸附特性的金属有机杂化材料及(MV)4[Bi6Cl26]晶体在用于吸附有机染料中的重金属离子方面的应用，所述的重金属离子指的是Cu、Co、Mn、Pb、Ni、Cr。其对重金属离子吸附特性的实验设计及详细步骤如下：
（1）首先将一定浓度的有色重金属离子的溶液量取10mL置于试管内，加入一定量的(MV)4[Bi6Cl26]材料；
（2）震荡，使得材料充分吸附，将上清液倒去，用去离子水反复冲洗使得附着在材料表面的重金属离子溶液清洗干净，然后将材料在50℃环境下干燥；
（3）通过红外光谱测试验证是否有重金属离子的吸附，若红外光谱中出现重金属离子化合物的特征峰，则说明材料吸附了重金属离子。同时也可以观察吸附前后溶液颜色的变化，颜色变浅也说明重金属离子被吸附。
本发明的(MV)4[Bi6Cl26]材料由本身不含铅可知，该材料应用于光伏产业将会对环境的毒害性降低，这对于环境友好型能源的开发将是一种不错的选择。同时因为有机配体的存在，像大多数金属有机杂化材料所具有的特性一样，该材料若制备成器件将具有柔性、可穿戴性、便携性等优点。
本发明中所述材料在微观下表现出的类层状特性，这使得该材料在宏观下具有对有机染料、重金属离子等的吸附特性，在实验中，通过紫外可见光吸收、红外光谱等测试手段，证实了该材料在有机染料、重金属离子吸附方面的效果，在经过一段时间的吸附之后，含有有机染料溶液的吸收峰下降，在未摇晃下5分钟内就降低了一半之多，含有有色重金属离子的溶液在经过一段时间的吸附后，颜色变浅，通过红外光谱测试可看出材料的确吸收了重金属离子。
本发明公开了一种基于甲基紫精配体的金属有机杂化材料(MV)4[Bi6Cl26]的应用，重点考察了(MV)4[Bi6Cl26]在光电器件方面，有机染料和重金属离子吸附方面的特性，研究显示(MV)4[Bi6Cl26]具有良好的光电特性和吸附特性，为此先后进行了光电效应的测试和有机染料和重金属离子的吸附实验，基于这些特性，将传统光电器件中无机材料替换为这种材料将会使得器件的柔性提高，提高可穿戴设备（如便携式太阳能电池）的便携性。在吸附方面的优秀性质应用于有害物质的处理将会环境保护领域，这将为这些有害物质的处理提供一种备选材料。
附图说明
图1是(MV)4[Bi6Cl26]材料的粉末XRD衍射图谱；
图2是(MV)4[Bi6Cl26]晶体的SEM照片，从图中可以看出(MV)4[Bi6Cl26]的层状结构；上图为围观下(MV)4[Bi6Cl26]的层状结构 下图为(MV)4[Bi6Cl26]的棒状形貌；
图3是(MV)4[Bi6Cl26]晶体的TEM照片，左图为其晶格条纹，右图为其电子束衍射图片；
图4是黑暗条件和70mw 375nm激光光照下的电流曲线；
图5是(MV)4[Bi6Cl26]吸附甲基蓝时溶液的紫外可见光吸收特征峰变化；
图6是(MV)4[Bi6Cl26]的红外光谱和(MV)4[Bi6Cl26]吸附不同重金属离子之后的红外光谱；a为(MV)4[Bi6Cl26]的红外光谱 b图为(MV)4[Bi6Cl26]材料吸附硫酸钴之后的红外光谱， c图为(MV)4[Bi6Cl26]材料吸附硫酸锰之后的红外光谱， d图为(MV)4[Bi6Cl26]材料吸附硝酸铜之后的红外光谱。
具体实施方式
为了更清楚地说明本发明，下面结合实施例和附图对本发明做进一步的说明。需要说明的是本发明并不局限于以下具体实施例，凡在本申请技术方案基础上做的等同变换均落入本发明的保护范围。下述实施例中的实验方法，如无特殊说明，均为常规方法。下述实施例中所用的试验材料均为商品，如无特殊说明，均默认试剂为商店购买得到。其中4,4’-联吡啶搅拌购买于上海笛柏。
实施例1
(MV)4[Bi6Cl26]晶体的制备，该晶体其形貌为黄色棒状晶体，该黄色棒状晶体在微观下具有类层状结构的特性，其空间群为P-1，其晶胞参数为a=9.409(3)Å；b=12.656(4)Å;c=19.857(6)Å；α=72.213(6)°；β=76.551(6)°；γ=72.277(6)°，按以下步骤进行：
1）将0.1mL氢碘酸57%（w/w）、4mL甲醇混合反应30分钟，再加入0.0624g 4,4’-联吡啶搅拌，称取0.1261g氯化铋并加入1.7mL35%盐酸（w/w），将两次反应的液体混合转移至23mL反应釜内，再加入6mL甲醇；
2）用3小时从25℃升至165℃，在165℃保温16小时，最后用11小时从165℃降温至室温25℃；
3）样品分离方法：将实验中反应釜内的样品转移至20mL小烧杯，用胶头滴管吸取适量甲醇加入烧杯内，用另一支胶头滴管搅拌，并将上面液体及黄色的(MV)4[Bi6Cl26]晶体同时吸取出来，重复多次，使得所得(MV)4[Bi6Cl26]晶体尽可能多的分离出来，将所得的(MV)4[Bi6Cl26]晶体及其溶液静止一段时间，待晶体沉淀后将上清液倒去，在自然条件下让其干燥，并收集到样品瓶里。详见图1是(MV)4[Bi6Cl26]材料的粉末XRD衍射图谱；图2是(MV)4[Bi6Cl26]晶体的SEM照片，从图中可以看出(MV)4[Bi6Cl26]的层状结构；图3是(MV)4[Bi6Cl26]晶体的TEM照片，左图为其晶格条纹，右图为其电子束衍射图片。
实施例2
(MV)4[Bi6Cl26]制备光伏器件时制备薄膜的方法：
（1）分离出纯净的(MV)4[Bi6Cl26]材料，干燥箱中用80℃温度环境进行干燥；
（2）用长宽之比为7：3刚玉坩埚，将(MV)4[Bi6Cl26]材料放在坩埚一头，将Nb-SrTiO3基片（购买于合肥科晶）放在坩埚另一头；
（3）将坩埚放入管式炉玻璃管中，使得放(MV)4[Bi6Cl26]材料的坩埚一头位于加热丝正中央；
（4）管式炉的操作以及温度参数设置为以下：
（a）打开氮气瓶通氮气3分钟，使得玻璃管内空气排干净，
（b）温度参数为从室温升高至300℃，用时10分钟，在300℃保温30分钟，然后关闭仪器；
（c）取出Nb-SrTiO3基片，其表面即可生长出一层(MV)4[Bi6Cl26]薄膜。采用该方法制备(MV)4[Bi6Cl26]薄膜将具有易操作，制备时间短的优点。
实施例3
为了更好的了解本发明具有的应用于光伏产业、光电器件方面的潜力，以下是对材料进行的光电流测试：
实验设计及操作如下：
（1）在不导电的PC板上放置一根(MV)4[Bi6Cl26]晶体，在晶体两端分别用导电银浆镀上电极，在常温下等待银浆干透，并用万用表确认电极已经导电；
（2）将制备好的样品置于电流表探针台，并分别将两个探针与样品两个电极接触，在黑暗条件下测试出50V电压下通过材料的电流曲线，黑暗条件下电流曲线如图4中平滑曲线所示；
（3）将375nm的激光照射在样品表面，调节激光功率为70mw，在50V电压下测出通过材料的电流，70mw功率375nm激光照射下材料的电流曲线如图4中线和圆圈组合的线所示；
（4）相比黑暗条件下的电流，加光照之后通过材料的电流明显增加，这说明光照条件下材料中出现了光电流。
（5）在光照条件下该材料表现出了光电效应，这有望应用于光伏产业和光电器件，同时这种金属有机杂化材料中具有的有机成分使得应用该材料的器件具有柔性可弯曲的特性，同时相比于传统硅基无机材料具有的原料昂贵、工艺复杂、对环境有害等特点，这种材料制备的原料获取容易、价格低廉，制备也相对容易，同时材料中不含对环境和人体有害的铅、呻等元素，应用于光电领域将会表现出很大的优势。
实施案4
为了更好的了解本发明具有的应用于有机染料吸附剂的潜力，以下是对材料进行有机染料的吸附试验：
(MV)4[Bi6Cl26]吸附有机染料的实验操作以及现象结果：
（1）首先将只加甲基蓝溶液的比色皿放入紫外可见光吸收仪器里，测出甲基蓝溶液的吸收谱；
（2）准备另外一只比色皿，加入一定量(MV)4[Bi6Cl26]材料，并加入甲基蓝溶液
（3）在黑暗条件下使材料静置吸附5分钟，测出含有(MV)4[Bi6Cl26]材料的比色皿内溶液的吸收峰；
（4）在黑暗条件下使材料继续吸附10分钟，此时发现溶液谱峰并没有下降；
（5）将比色皿摇晃振动半分钟，静置，继续黑暗条件吸附10分钟测出溶液吸收峰；
（6）继续静置吸附10分钟，测出吸收峰，发现和谱峰基本上没有下降；
（7）将比色皿摇晃振动半分钟，静置，继续黑暗条件吸附10分钟测出溶液吸收峰；
（8）重复（7）两次测出吸收峰。
本发明的上述实施例中甲基蓝溶液紫外可见光吸收图如图5所示；从结果可以看出在加入(MV)4[Bi6Cl26]材料后，在静置条件下材料进行5分钟的吸附就可以使得甲基蓝溶液谱峰下降很多，这说明了(MV)4[Bi6Cl26]材料对有机染料的吸附效果很好，将这种材料应用于工业污水处理中来处理有机染料的污染将会取得很好地效果。
实施例5
为了更好的了解本发明具有的应用于重金属离子潜力，以下是对材料进行重金属离子的吸附试验：
(MV)4[Bi6Cl26]吸附重金属离子的实验方案设计：
（1）首先将一定浓度的有色重金属离子的溶液量取5mL置于试管内，加入一定量的(MV)4[Bi6Cl26]材料；
（2）震荡，使得材料充分吸附，将上清液倒去，用去离子水反复冲洗使得附着在材料表面的重金属离子溶液清洗干净，然后将材料在50℃环境下干燥；
（3）通过红外光谱测试验证重金属离子的吸附，通过图6中(MV)4[Bi6Cl26]材料吸附重金属离子后的红外光谱和纯净的(MV)4[Bi6Cl26]材料的红外光谱对比，可以通过吸附之后的谱图中1100cm-1附近处硫酸根和1380cm-1附近硝酸根离子的特征峰可知(MV)4[Bi6Cl26]材料对重金属离子（Cu、Co、Mn、Pb、Ni、Cr）的确具有吸附效果；
附图6中（a）图为(MV)4[Bi6Cl26]材料的红外光谱，（b）图为(MV)4[Bi6Cl26]材料吸附硫酸钴之后的红外光谱，（c）图为(MV)4[Bi6Cl26]材料吸附硫酸锰之后的红外光谱，（d）图为(MV)4[Bi6Cl26]材料吸附硝酸铜之后的红外光谱。本发明中通过重金属盐中具有的酸根离子红外特征峰确定对重金属离子的吸附效果。 本发明中(MV)4[Bi6Cl26]具有的对重金属离子的吸附效果用于工业废水的处理，将对降低因重金属污染带来的环境和健康问题产生显著地效果。
实施例6
应用实例
某颜料化工厂工业废水，出厂水质检测铅离子含量1.25×103mg / L，Cr含量为114mg / L，这一含量显然超出了人体安全浓度，同时也对环境中的生物也具有伤害性，经(MV)4[Bi6Cl26]处理后水质监测均下降至铅离子含量0.16mg / LCr含量0.16mg / L。因此(MV)4[Bi6Cl26]对重金属离子的吸附效果显著，能够被用来制作有害物质吸附剂以保护环境。
本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定，对于该材料具有的吸附重金属离子的性质，在上述说明的基础上还可以做出其它不同形式的变化或变动，这里无法对所有的实施方式予以穷举，凡是属于本发说明书明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之列。
Claims (2)
1.一种基于甲基紫精配体的具有吸附特性的金属有机杂化材料(MV)4[Bi6Cl26] 晶体在对有机染料以及重金属离子吸附方面的应用。
2.权利要求1所述的应用，其中所述的吸附有机染料指的是甲基蓝溶液。
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