CN114479110A - 以三苯基锑为骨架的共价有机框架及其制备方法和应用 - Google Patents
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Abstract
以三苯基锑为骨架的共价有机框架及其制备方法和应用,涉及共价有机框架(COFs)材料领域。所述材料通过含有三苯基锑的三醛化合物与芳香二胺单体缩合而成,包括以下步骤:1)三(4‑甲酰基苯基)锑和芳香二胺分别加入到有机溶剂中,超声分散后加入醋酸溶液,得到悬浊液;2)上述所得悬浊液通过液氮冷冻‑抽真空‑脱气处理,密封后加热72小时得到粗产物;3)所得到的粗产物经过N,N‑二甲基甲酰胺(DMF)抽滤洗涤,然后用四氢呋喃(THF)进行索氏提取、真空干燥得到以三苯基锑为骨架的共价有机框架。本发明涉及的共价有机框架材料首次以具有氧化还原活性的三苯基锑结构单元为骨架,以其为活性材料的电极表现出出色的超级电容器性能。
Description
技术领域
本发明涉及共价有机框架(COFs)材料领域,具体涉及一类以三苯基锑为骨架的新型COF材料及其制备方法和超级电容器应用。
背景技术
超级电容器是一种脉冲电流系统,能够在小于1分钟的时间里释放高电流以及非常大的功率,目前最典型的应用就是满足启动和制动所需要的瞬时能量的提供。电极材料比表面积,孔结构,电导率,物理化学稳定性等参数对于其超级电容器性能至关重要。具有较大比表面积,均匀的孔径结构以及良好物理化学稳定性的COFs材料成为了新的候选材料。2020年公开了以三苯基膦为骨架的COF材料(Phos-COF),并进一步探索了其作为超级电容器电极材料的潜能,结果表明Phos-COF电导率不够高,以其为正极活性材料的超级电容器性能不佳。之后,通过引入导电成分氧化还原石墨烯制备复合材料,可以很好的解决电导率低的问题。但导电成分的引入同时也带来了1)孔结构的堵塞,从而使孔道表面不能得到有效的利用;2)COF材料晶性会得到破坏,从而使原本具有的高效离子传输通道被破坏。
发明内容
本发明的目的是提供一种本征电导率较高且具有氧化还原活性单元,即提供赝电容的COF材料,提出以三苯基锑为骨架构建COFs材料,该材料表现出比Phos-COF更高的电导率和超级电容器性能。
以三苯基锑为骨架的共价有机框架,其结构通式为:
所述的以三苯基锑为骨架的共价有机框架的制备方法,其特征在于该方法是由三(4-甲酰基苯基)锑单体和芳香二胺单体在相应的溶剂体系下,在加热条件下合成,具体步骤如下:
S1:将三(4-甲酰基苯基)锑单体和相应的芳香二胺单体溶解在溶剂中,超声分散,加入醋酸溶液,继续超声分散形成悬浊液;其中,
三(4-甲酰基苯基)锑与芳香二胺单体的摩尔比为2:3;
三(4-甲酰基苯基)锑在混合溶剂中的反应浓度为0.1-0.5mol/L;
醋酸溶液的浓度为3-15mol/L;
所述溶剂为均三甲苯和1,4-二氧六环的混合溶剂,均三甲苯和1,4-二氧六环体积比为1:1-3:1;
S2:将所述悬浊液依次经过液氮冷冻、抽真空、解冻处理,最后抽真空密封并在110-130℃下静置至少72小时,得粗产物;其中,液氮冷冻、抽真空、脱气处理的次数至少为3次;
S3:将所述粗产物用N,N-二甲基甲酰胺抽滤洗涤,然后用四氢呋喃索氏提取后真空干燥,即得到以三苯基锑为骨架的共价有机框架。
所述芳香二胺为对苯二胺、对联苯二胺和对联三苯二胺。
采用本发明的方法可制备出以三苯基锑为骨架的共价有机框架。所得材料结晶性好,稳定性高,实现了三苯基锑结构单元在COFs骨架中的均匀有序分布。本发明通过自下而上的合成策略,在COFs骨架中引入氧化还原活性位点,赋予COFs材料良好的赝电容性能。这些氧化还原活性位点可以快速有效地吸收和释放电荷,为超级电容器电极材料提供有效和快速的充放电特性。
附图说明
图1为Sb-COF-1的合成路线及结构通式。
图2为Sb-COF-1样品的测试结果图,其中:
a为XRD图谱,出现COF材料AA堆叠的特征峰;b为红外光谱,可以看出S-COF-1中有明显的C=N双键特征峰(1616cm-1),而单体三苯基锑三醛的醛基特征峰则基本没有,表明COF材料成功被合成;c为BET表面积分析;d为孔径分布曲线;c和d表明获得的Sb-COF-1具有很好的比表面积和孔结构;e为2D结构表征图。
图3为本发明制备的Sb-COF-1材料的电镜照片,其中:
a-c是SEM的表征图像,显示了纳米棒的整体尺寸是均匀的,长度大约在200纳米,揭示了通过这种溶剂热合成法能够获得均匀的纳米棒状结构;d-f是TEM表征图像图,显示了Sb-COF-1呈现一种聚集的纳米棒状形态,平均直径为100±20纳米;相比于微米或更大尺度的结构,纳米结构能提供更多的电子传输通道,同时有利于双层电容和赝电容的贡献。
图4为三电极模式下Sb-COF-1在1M KOH电解液中的电化学测试曲线,其中:
a为不同扫描速率下的CV曲线;b为在不同电流密度下的GCD曲线;c为比电容以及库伦效率曲线;d为循环稳定性曲线。
图5为Sb-COF-1材料组成的双电极体系电化学测试曲线,其中:
a为Sb-COF-1//rGO ASC器件在不同扫描速率下的CV曲线;b为不同电流密度下的GCD曲线;c为器件的比电容以及相应的库伦效率;d表示的是在9Ag-1时的循环稳定性。上述结果表明由Sb-COF-1和rGO分别作为正负极的电容具有很好的超级电容器性能。
图6为Sb-COF-2的合成路线及结构式。
图7为Sb-COF-2样品的XRD图谱。
图8为Sb-COF-3的合成路线及结构式。
图9为Sb-POP的XRD图谱。
图10为三电极模式下Sb-POP在1M KOH电解液中的电化学测试曲线,其中:
a为不同扫描速率下的CV曲线;
b为在不同电流密度下的GCD曲线;
c为比电容;
d为奈奎斯特图。
具体实施方式
下面结合附图和具体实施例进一步说明本发明。以下实施例将有助于本领域的技术人员进一步理解本发明但不以任何形式限制本发明,应当指出的是,对本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。
实施例1:三苯基锑为骨架的共价有机框架,其结构式如图1所示。由三(4-甲酰基苯基)锑单体和对苯二胺在相应的溶剂体系下溶热过程合成,具体步骤如下:
S1:将40mg,0.092mmol三(4-甲酰基苯基)锑和14.8mg,0.137mmol对苯二胺溶解在含有混合溶剂的玻璃管中,超声分散,然后向该体系继续添加0.18毫升6M醋酸,继续超声分散形成悬浊液A;
所述的混合溶剂为0.28ml,由均三甲苯和1,4-二氧六环按体积比为3:1混合而成。
S2:将所述悬浊液A依次经过液氮冷冻、抽真空、解冻处理,最后抽真空密封并在120℃下静置72小时以上,得到粗产物;
S3:将粗产物用N,N-二甲基甲酰胺抽滤洗涤,然后用四氢呋喃索氏提取后真空干燥,即得到以三苯基锑为骨架的共价有机框架产物Sb-COF-1。
Sb-COF-1的相关测试结果如图2所示。其中:
图2a是X射线衍射图,表明Sb-COF-1具有较高结晶性,图中3.91,6.41,7.93,12.92和21.96度是材料AA堆叠的特征峰;
图2b是FT-IR图,光谱显示在1616cm-1处有强烈的C=N特征吸收峰,表明亚胺键的成功生成;
图2c是氮气吸脱附曲线和孔径分布图,可以看出吸附曲线归类为典型的Ⅰ型等温线,表明材料是微孔结构,由此得出材料比表面积为969m2/g,孔径主要分布在1.19和1.29nm。
图3是电镜照片,揭示了材料的微观结构,呈现出一种棒状的堆积形式,其平均直径为100±20纳米,长度大约在200纳米。
将Sb-COF-1应用于超级电容器领域。
在三电极系统测试中,工作电极的制备是将Sb-COF(70wt%)、碳黑(20wt%)和溶解在N-甲基吡咯烷酮(NMP)中的PVDF(10wt%)混合成浆液,涂在1*2cm2的镍泡沫上;然后放在60摄氏度的烘箱中干燥,形成以Sb-COF-1为正极的电极片。
经测试,在三电极情况下Sb-COF-1的CV和GCD如图4a,b所示:
图4a可以看出,具有特征氧化还原峰的非矩形CV曲线即使在200mV s-1的高扫描速率下也能保持其形状不变,表明其具有优异的氧化还原性能和电化学稳定性;
图4b可以看出,其比电容达到了179F g-1,随着循环过程中(10万次)的不断活化,比电容可进一步提高到380F g-1。
在Sb-COF-1//rGO的双电极应用中,以Sb-COF-1为正极,rGO为负极,电解液是1MKOH,以不同的扫描速率以及电流密度来进行测试。结果如图5所示,表明由Sb-COF-1和rGO分别作为正负极的电容具有很好的超级电容器性能。
循环过程中所得到的具体参数如表一所示。能量密度最高可达到69Wh Kg-1(功率密度为3024W Kg-1),这也是目前报道的纯COFs超级电容器电极材料最高的能量密度和功率密度之一。
实施例2:本实施例提供一种三苯基锑为骨架的共价有机框架制备方法,本实施例中所选用的二胺单体为25.2mg,0.137mmol对联苯二胺,其它技术内容同实施例1,所得产物为Sb-COF-2。
实施例3:本实施例提供一种三苯基锑为骨架的共价有机框架制备方法,本实施例中所选用的二胺单体为35.6mg,0.137mmol对联三苯二胺,其它技术内容同实施例1,所得产物为Sb-COF-3。
实施例4:本实施例提供一种三苯基锑为骨架的共价有机框架制备方法,本实施例中所选用的醋酸为9M,其它技术内容同实施例1,所得产物为Sb-COF-1,其XRD与实施例1所得材料相同。
实施例5:本实施例提供一种三苯基锑为骨架的共价有机框架制备方法,本实施例中所选用的均三甲苯和1,4-二氧六环按体积比为2:1混合而成,其它技术内容同实施例1,所得产物为Sb-COF-1,其XRD与实施例1所得材料相同。
实施例6:本实施例提供一种三苯基锑为骨架的多孔有机聚合物的制备方法,本实施例中所选用的混合溶剂体积为2.8ml,由均三甲苯和1,4-二氧六环按体积比为3:1混合而成,其它技术内容同实施例1,所得产物为无定型的Sb-POP。
实施例7:本实施例提供一种三苯基锑为骨架的多孔有机聚合物的制备方法,本实施例中所选用的三(4-甲酰基苯基)锑与芳香二胺单体的摩尔比为1:3,其它技术内容同实施例1,所得产物为无定型的Sb-POP。
实施例6和7所得的Sb-POP的XRD检测结果相同,如图9所示,在小角度范围内(1-10°)没有衍射峰,表明所得材料为无定型材料。从图10c可以看出,实施例6所得Sb-POP电极的比电容仅为16Fg-1,远小于Sb-COF的179Fg-1。
以上对本发明的具体实施例进行了描述。应该理解的是,上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对实施方式的限定,本领域技术人员可以在权利要求的范围内做出各种变形或修改,这并不影响本发明的实质内容。例如使用不同的方法比例来进行COFs材料的制备。这里无需也无法对所有的实施方式予以穷举,而由此所引申出的显而易见的变化或变动仍处于本申请型的保护范围之中。
Claims (4)
2.以三苯基锑为骨架的共价有机框架的制备方法,其特征在于该方法是由三(4-甲酰基苯基)锑单体和芳香二胺单体在相应的溶剂体系下,在加热条件下合成,具体步骤如下:
S1:将三(4-甲酰基苯基)锑单体和相应的芳香二胺单体溶解在溶剂中,超声分散,加入醋酸溶液,继续超声分散形成悬浊液;其中,
三(4-甲酰基苯基)锑与芳香二胺单体的摩尔比为2:3;
三(4-甲酰基苯基)锑在混合溶剂中的反应浓度为0.1-0.5mol/L;
醋酸溶液的浓度为3-15mol/L;
所述溶剂为均三甲苯和1,4-二氧六环的混合溶剂,均三甲苯和1,4-二氧六环体积比为1:1-3:1;
S2:将所述悬浊液依次经过液氮冷冻、抽真空、解冻处理,最后抽真空密封并在110-130℃下静置至少72小时,得粗产物;其中,液氮冷冻、抽真空、脱气处理的次数至少为3次;
S3:将所述粗产物用N,N-二甲基甲酰胺抽滤洗涤,然后用四氢呋喃索氏提取后真空干燥,即得到以三苯基锑为骨架的共价有机框架。
3.如权利要求1所述的以三苯基锑为骨架的共价有机框架,其特征在于所述的芳香二胺为对苯二胺、对联苯二胺、对联三苯二胺。
4.如权利要求2所述的以三苯基锑为骨架的共价有机框架,其特征在于以三苯基锑为骨架构建的COFs材料作为正极材料应用于超级电容器领域。
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