CN110010367B - 一种二维金属有机框架半导体材料及制备方法及应用 - Google Patents
一种二维金属有机框架半导体材料及制备方法及应用 Download PDFInfo
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Abstract
本发明公开了一种二维金属有机框架半导体材料及制备方法及应用，制备方法为：在惰性气氛保护下，将2,3,6,7,10,11,14,15‑八羟基四苯并萘(I)与二价金属离子放入溶剂中，在室温‑85℃条件下，反应12‑72h，得到一种二维金属有机框架半导体材料(II)；反应式为：
本发明的二维金属有机框架半导体材料合成步骤简单，所需条件温和。获得的是具有菱形孔道的二维片层结构，具有高电导率，高稳定性，高度可逆的氧化还原性等优势。用本发明的方法获得的二维金属有机框架半导体材料制备的电容器装置操作简便，且具有大的电容量，良好的稳定性和优异的循环性能。
Description
技术领域
本发明属于金属有机框架材料及电化学能量存储领域，特别是涉及一种具有菱形孔道的二维金属有机框架半导体材料及制备方法及应用。
背景技术
超级电容器，是混合动力汽车和便携式电子设备中高功率电子器件的重要组成部分，具有高能量密度、快速充放电能力和良好的循环稳定性等优点。通常，根据储能机理的不同，超级电容器可分为双电层电容器和贋电容器两种。它们分别要求材料具有高的电导率，大的比表面积和高度可逆的氧化还原特性。多孔碳材料，导电聚合物和过渡金属氧化物是超级电容器的三类重要的电极材料。与传统的超级电容器材料相比，金属有机框架(MOFs)材料具有比表面积大、孔隙率高、结构可调等优异的特性。其大的比表面积赋予了MOFs材料吸附电解质中的离子的能力，这对产生大的双层电容是有益的。另外，MOFs材料中的金属离子或金属簇以及多样化的有机连接体为框架结构提供了多种氧化还原位点，利于产生大的贋电容能量。然而，传统的MOFs材料由于导电性较差，一般为绝缘体材料(σ<10-10Scm-1)要将该类材料应用于能量存储领域，通常需要使用碳纳米管或石墨烯作为导电添加剂形成复合组分，或者将其作为热解合成碳的前驱体。这些方法在很大程度上会破坏材料本身的多孔结构，并且阻碍了对有机配体固有的氧化还原性的利用，从而导致低电容量和低功率密度。
最近，具有扩展π-共轭层和类石墨烯孔道结构的二维MOFs受到了科学家的广泛关注，主要是由于其良好的导电性能(σ>10-3S cm-1)和独特的物理化学特性。这类材料通常利用有机连接体上的-OH，-NH2，-SH与过渡金属Cu，Co，Ni等构成平面几何配位，并形成亚纳米孔道。其中，基于-OH的有机连接体，由于可以在酚式、半醌式和醌式之间进行可逆的结构互变，因此具有高度可逆的氧化还原特性，从而在能量存储领域具有很大的应用潜力。最近报道的部分二维MOFs，例如Ni3(HITP)2(HITP＝2、3、6、7、10、11-六氨基苯并菲)，Cu3(HHTP)2(HHTP＝2、3、6、7、10、11-六羟基苯并菲)，均表现出良好的导电性和明显的双电层电容器性能，然而它们只有较低的质量电容和面积电容。这是由于它们没有充分利用MOF中有机连接体和金属离子的氧化还原特性，从而缺乏贋电容的贡献。因此，制备具有高电容量并且兼具双层电容和贋电容两种机制的新型二维导电MOF电极材料成为了一个新的挑战。
发明内容
本发明的目的是克服现有技术的不足，提供一种二维金属有机框架半导体材料。
本发明的第二个目的是提供一种二维金属有机框架半导体材料的制备方法。
本发明的第三个目的是提供一种二维金属有机框架半导体材料的应用。
本发明的技术方案概述如下：
一种二维金属有机框架半导体材料的制备方法，包括如下步骤：
在惰性气氛保护下，将2,3,6,7,10,11,14,15-八羟基四苯并萘(I)与二价金属离子放入溶剂中，在室温-85℃条件下，反应12-72h，得到一种二维金属有机框架半导体材料(II)；
反应式为：
二价金属离子为Cu，Co，Ni，Mn或Fe离子。
溶剂由体积比1：(1-4)的N，N-二甲基甲酰胺和水组成。
上述方法制备的一种二维金属有机框架半导体材料。
上述一种二维金属有机框架半导体材料制备超级电容器的应用。
本发明的优点：
本发明的二维金属有机框架半导体材料合成步骤简单，所需条件温和。获得的是具有菱形孔道的二维片层结构，具有高电导率，高稳定性，高度可逆的氧化还原性等优势。用本发明的方法获得的二维金属有机框架半导体材料制备的电容器装置操作简便，且具有大的电容量，良好的稳定性和优异的循环性能。
附图说明
图1为实施例1制备的二维金属有机框架半导体材料的扫描电镜和高分辨透射电镜照片。其中，图1A为实施例1制备的二维金属有机框架半导体材料的扫描电镜照片，图1B为实施例1制备的二维金属有机框架半导体材料的透射电镜照片，图1C为实施例1制备的二维金属有机框架半导体材料的选取电子衍射图，图1D为实施例1制备的二维金属有机框架半导体材料的高分辨透射电镜照片。
图2为实施例1制备的二维金属有机框架半导体材料的粉末XRD谱图。
图3为实施例1制备的二维金属有机框架半导体材料的红外谱图。
图4为实施例1制备的二维金属有机框架半导体材料的变温电导率曲线。
图5为实施例3制备的对称性电容器的变扫速循环伏安曲线，图中循环伏安曲线由内向外扫描速度依次减小。
图6为实施例3制备的对称性电容器的恒流充放电曲线，图中倍率曲线从左到右电流密度依次减小。
图7为实施例3制备的对称性电容器的稳定性测试曲线。
具体实施方式
下面结合具体实施例对本发明作进一步的说明。
2,3,6,7,10,11,14,15-八羟基四苯并萘的制备：
根据文献Varshney，S.K.，et al.，Liquid Crystals，2009，36，1409-1415中的合成方法制备。
实施例1
一种二维金属有机框架半导体材料的制备方法，包括如下步骤：
在氩气保护下，将8.6毫克的2,3,6,7,10,11,14,15-八羟基四苯并萘I与5.5毫克的一水合醋酸铜溶于500微升脱气的N，N-二甲基甲酰胺和2毫升脱气的纯净水中，超声10min，在85℃条件下，反应72h，降至常温，离心，固体水洗三次，丙酮洗三次。室温真空干燥一天，得黑色粉末，即得到一种二维金属有机框架半导体材料II-1；
反应式如下：
图1实施例1制备的二维金属有机框架半导体材料的扫描电镜和高分辨透射电镜照片。证明实施例1制备的二维金属有机框架半导体材料为杆状微晶，长度在500nm左右。二维金属有机框架半导体材料具有菱形孔道的AA堆积的二维片层结构。高分辨透射电镜照片中可以看到规则的菱形孔道，大小与模拟的孔道尺寸一致，基本没有缺陷。
图2为实施例1制备的二维金属有机框架半导体材料的粉末XRD谱图，证明二维金属有机框架半导体材料具有良好的结晶性和相纯度。
图3为实施例1制备的二维金属有机框架半导体材料的红外谱图，羟基的振动峰在二维金属有机框架半导体材料的谱图中完全消失，证明了配体与铜离子之间的成功配位。
图4为实施例1制备的二维金属有机框架半导体材料在不同温度下(273K-313K)的变温电导率曲线，产物的电导率与周围环境温度程正相关。
实验证明，用四水合醋酸钴，四水合醋酸镍，四水合醋酸锰和四水合氯化亚铁分别替代本实施例的一水合醋酸铜，其它同本实施例，分别获得不同的二维金属有机框架半导体材料。
实施例2
自支撑二维金属有机框架半导体材料薄膜的制备方法，步骤如下：
将实施例1制备的10毫克二维金属有机框架半导体材料粉末和2毫克导电炭黑，置于玛瑙研钵中研磨均匀，加入2毫克60％的聚四氟乙烯(胶黏剂)和2滴无水乙醇，持续研磨使混合均匀，研磨过程中不断加入少量无水乙醇防止混合物干燥。待混合物变成类似面糊状时，使用小钢勺不断搅拌，直至溶剂完全挥发，得到有延展性的面团状混合物。使用对辊机反复碾压样品制成厚度为40微米的薄膜。在70℃下真空干燥12小时，得到干燥的自支撑二维金属有机框架半导体材料薄膜。将上述薄膜裁剪成若干个边长为0.3厘米的正方形膜用于测试。
实施例3
对称型固态超级电容器电池装置制备及电化学电容器测试，包括如下步骤：
使用两片实施例2获得的正方形膜，中间用NKK-MPF30AC-100做分隔膜，30微升1M氯化钠水溶液作为电解质，封装在一个电池中。静置过夜后，依次测试该装置的循环伏安曲线、恒流充放电曲线和循环稳定性能。首先，工作电位窗口确定为0-1.0V，在此期间电池为纯电容响应。随后，分别测试5mV s-1-100mV s-1不同扫速下的循环伏安曲线(如图5所示)。曲线呈现近似矩形的轨迹，有两个明显的氧化还原峰，说明二维金属有机框架半导体材料的电容由双层电容和贋电容两种机理共同支配。另外，给定不同的电流密度0.2A g-1-10Ag-1，测试充电放电曲线并根据放电曲线计算电容量(如图6所示)，电流密度为0.2A g-1时，单电极的质量电容是396F g-1。当电流密度从0.2A g-1增加50倍时，仍有将近60％的电容保留，表现出良好的倍率性能。最后，在5A g-1的电流密度下测试电容器装置的循环稳定性(如图7所示)，在循环测试2000个充放电周期后其电容仍可保持80％，表现出良好的稳定性。
两电极对称型电池装置的电容计算方程如下：
Claims (5)
1.一种二维金属有机框架半导体材料的制备方法，其特征在于包括如下步骤：
在惰性气氛保护下，将2,3,6,7,10,11,14,15-八羟基四苯并萘(I)与二价金属离子放入溶剂中，在室温-85℃条件下，反应12-72h，得到一种二维金属有机框架半导体材料(II)；
反应式为：
2.根据权利要求1所述的制备方法，其特征在于所述二价金属离子为Cu，Co，Ni，Mn或Fe离子。
3.根据权利要求1所述的制备方法，其特征在于所述溶剂由体积比1：(1-4)的N，N-二甲基甲酰胺和水组成。
4.权利要求1-3之一的方法制备的一种二维金属有机框架半导体材料。
5.权利要求4的一种二维金属有机框架半导体材料制备超级电容器电极材料的应用。
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