CN115894912B - 一种基于三维共价有机框架的高铼酸根吸附方法 - Google Patents
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Abstract
本发明公开了一种基于三维共价有机框架的高铼酸根吸附方法,属于环境保护技术领域。本发明将四(4‑氨基苯基)甲烷和1,1'‑双(2,4‑二硝基苯基)‑4,4'‑二氯化联吡啶通过微波反应制备三维共价有机框架,该三维共价有机框架具有三倍互穿金刚石网络和三维疏水通道,耐酸碱性、结晶度以及重复使用性好,对高铼酸根的捕获速度快、效率高且选择性好,有良好应用前景。
Description
技术领域
本发明属于环境保护技术领域,具体涉及一种基于三维共价有机框架的高铼酸根吸附方法。
背景技术
随着核能工业的发展,在核燃料循环中高效处置和回收核废料具有重要的生态意义。235U或239Pu核裂变过程中产生的99Tc是一种长寿命(t1/2=2.13×105年)放射性同位素,在有氧条件下主要以+7氧化态的高锝酸根离子(TcO4 -)存在(Alberto,R.;Bergamaschi,G.;Braband,H.;Fox,T.;Amendola,V.99TcO4 -:Selective recognition and trapping inaqueous solution,Angewandte Chemie International Edition,2012,51(39),9772-9776)。TcO4 -的非络合性质和高水溶性使其在环境中具有高度的流动性。从水溶液中有效和选择性地去除TcO4 -是一项重大的科学难题和技术挑战。由于99Tc具有放射性,不能在普通实验室中处理,因此高铼酸根离子(ReO4 -)通常用作TcO4 -的化学模拟物进行研究(Xie,K.;Dong,Z.;Zhao,L.Radiation synthesis of ionic liquid-functionalized silica-based adsorbents:a preliminary investigation on its application for removalof ReO4 -as an analog for TcO4 -,Environmental Science and Pollution Research,2021,28(14),17752-17762)。
离子交换具有易于实施且对目标阴离子回收率高的特点,研究者开发了阴离子交换材料用于从核废料溶液中去除ReO4 -/TcO4 -(Wilmarth,W.R.;Lumetta,G.J.;Johnson,M.E.;Poirier,M.R.;Thompson,M.C.;Suggs,P.C.;Machara,N.P.Review:waste-pretreatment technologies for remediation of legacy defense nuclear wastes,Solvent Extraction and Ion Exchange,2011,29(1),1-48)。传统的商业聚合物交换树脂可以有效地去除ReO4 -/TcO4 -,但其在极端条件下的耐辐射性和化学稳定性较差。无机阳离子材料(如,层状双氢氧化物、硫凝胶、钍基材料等)可以用作阴离子交换材料,然而,它们大多吸附容量低、吸附动力学慢以及对ReO4 -/TcO4 -的选择性差。近年来,金属有机框架(MOF)在去除ReO4 -/TcO4 -方面表现出良好的性能,然而,相对较低的稳定性阻碍了MOF在复杂水体系中的应用。因此,迫切需要开发吸附动力学快速、吸附容量高以及化学稳定性好的新型ReO4 -/TcO4 -吸附材料。
共价有机框架(COF)是一类新兴的结晶多孔聚合物,具有周期性分子序和固有孔隙率。与金属有机框架和聚合物树脂相比,具有强共价键的刚性有机单元赋予了COF更高的化学稳定性。COF的疏水多孔通道有利于加速阴离子交换过程,使其成为去除阴离子污染物的新兴候选材料。迄今为止,用于捕获ReO4 -/TcO4 -的COF主要是基于二维构造单元。与二维COF相比,三维COF具有明显的优势,包括高表面积、低密度、开放通道和丰富的可用活性位点等(Wang,S.;Li,X.-X.;Da,L.;Wang,Y.;Xiang,Z.;Wang,W.;Zhang,Y.-B.;Cao,D.Athree-dimensional sp2 carbon-conjugated covalent organic framework,Journalof the American Chemical Society,2021,143(38),15562-15566)。这些特性使三维COF成为捕获ReO4 -/TcO4 -的理想候选者,但由于建筑单元和反应类型的限制,三维COF的合成具有极大的挑战性。迄今为止,尚未见三维COF用于捕获ReO4 -/TcO4 -的报道。
发明内容
针对目前高铼酸根/高锝酸根捕获材料的吸附容量低、吸附动力学慢、稳定性较差以及现有二维COF只具有一维通道等问题,本发明提供了一种三维共价有机框架的合成方法及其对高铼酸根的吸附应用。本发明将四(4-氨基苯基)甲烷和1,1'-双(2,4-二硝基苯基)-4,4'-二氯化联吡啶通过Zincke反应制备三维共价有机框架。本发明采用阳离子型1,1'-双(2,4-二硝基苯基)-4,4'-二氯化联吡啶构建具有高电荷密度的阳离子型三维共价有机框架,提高了对高铼酸根离子的吸附容量;该三维共价有机框架具有3倍互穿金刚石网络结构,该结构极稳定的低密度刚性骨架,增强了三维共价有机框架的耐酸碱性;此外,由于高铼酸根离子比其他典型无机阴离子的疏水性强,该共价有机框架具有的开放三维疏水通道,其疏水表面有利于高铼酸根离子在孔隙内的扩散,使其对高铼酸根的捕获速度快且选择性好,可高效去除模拟汉福德废液中的高铼酸根离子。因此,本发明制备的三维共价有机框架制备方法简便、结晶度高、稳定性好、电荷密度高,在捕获高铼酸根中具有超快的速度、高的吸附率、优越的选择性以及可重复使用性等优越性,是一种高铼酸根的高效捕获材料,有良好的应用前景。
本发明通过如下技术方案实现:
本发明提供了一种三维共价有机框架的合成方法,包括以下步骤:
1)以四(4-氨基苯基)甲烷和1,1'-双(2,4-二硝基苯基)-4,4'-二氯化联吡啶为反应原料,向其中加入无水乙醇和水混合均匀;
2)将步骤1)所得混合液加热并搅拌,反应结束后冷却过滤,沉淀经洗涤干燥得到三维共价有机框架。
作为优选,步骤1)所述四(4-氨基苯基)甲烷与1,1'-双(2,4-二硝基苯基)-4,4'-二氯化联吡啶的摩尔比为1:(1-3)。
作为优选,步骤1)所述无水乙醇和水的体积比为(1-6):1。
作为优选,步骤2)所述混合液加热采用微波辐射加热,温度为80-100℃,搅拌反应2h。
本发明还提供了上述合成方法获得的三维共价有机框架在吸附高铼酸根中的应用。
作为优选,所述三维共价有机框架能够在竞争性阴离子共存条件下选择性吸附去除高铼酸根;所述竞争性阴离子包括NO3 -、SO4 2-、PO4 3-、CO3 2-。
作为优选,所述三维共价有机框架经过4个吸附/脱附循环后,对高铼酸根的去除率仍超过99%。
与现有技术相比,本发明的有益效果是:
(1)本发明将四(4-氨基苯基)甲烷和1,1'-双(2,4-二硝基苯基)-4,4'-二氯化联吡啶通过Zincke反应制备三维共价有机框架,方法简便且产物的结晶度高。
(2)本发明制备的三维共价有机框架具有3倍互穿金刚石(dia)网络结构,该结构具有稳定的低密度刚性骨架,增强了三维共价有机框架的耐酸碱性。
(3)本发明制备的三维共价有机框架具有开放的三维疏水通道,疏水表面有利于高铼酸根离子在孔隙内的扩散,对高铼酸根的捕获速度快且选择性好。
(4)本发明采用阳离子型单体1,1'-双(2,4-二硝基苯基)-4,4'-二氯化联吡啶可直接构建具有高电荷密度的阳离子型三维共价有机框架,从而提高对高铼酸根离子的吸附容量。
(5)本发明制备的三维共价有机框架的稳定性好,对高铼酸根的吸附速度快、吸收容量高以及可重复使用性好,可有效去除模拟废液中的高铼酸根离子,有良好的应用前景。
附图说明
图1是TFAM-BDNP的合成路线示意图。
图2中(a)是实验测得的TFAM-BDNP的PXRD图,(b)是模拟3倍互穿金刚石(dia)网络结构的TFAM-BDNP的PXRD图。
图3是TFAM、BDNP和TFAM-BDNP的红外光谱图。
图4是TFAM-BDNP在经不同条件处理后的红外光谱图。
图5是TFAM-BDNP对ReO4 -的吸附等温线图。
图6是TFAM-BDNP对ReO4 -的吸附动力学图。
图7是TFAM-BDNP对ReO4 -的吸附选择性图。
图8是TFAM-BDNP在不同浓度NO3 -存在条件下对ReO4 -的吸附选择性图。
图9是TFAM-BDNP在不同浓度SO4 2-存在条件下对ReO4 -的吸附选择性图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚,下面将结合实施例对本发明的技术方案进行清楚、完整地描述。实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。
除非另有定义,本文所使用的所有技术和科学术语与本发明技术领域的技术人员通常理解的含义相同。在本发明的说明书所使用的术语只是为了描述具体实施例的目的,并非用于限制本发明。本文所使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。
实施例1:三维共价有机框架的制备与表征
将28.2mg的四(4-氨基苯基)甲烷(TFAM)和83.3mg的1,1'-双(2,4-二硝基苯基)-4,4'-二氯化联吡啶(BDNP)置于微波反应管中,再加入12.5mL无水乙醇(EtOH)和3.1mL水,混合均匀后置于微波反应器中,在微波辐射下于90℃搅拌反应2h,冷却至室温并过滤,用无水乙醇和水洗涤沉淀,将沉淀在45℃下真空干燥,得到三维共价有机框架(TFAM-BDNP)。
图1是TFAM-BDNP的合成路线示意图。
采用X射线粉末衍射(PXRD)表征三维共价有机框架TFAM-BDNP的结晶度。图2是实验测得的TFAM-BDNP的PXRD图(a)和模拟3倍互穿金刚石(dia)网络结构的TFAM-BDNP的PXRD图(b)。由图2a可见,实验测得的TFAM-BDNP的2θ角在3.29°出现一个强衍射峰,在5.62°、6.00°、6.77°、7.56°、8.60°和9.77°有六个弱衍射峰,分别对应于(111),(202),(230),(003),(203),(133)和(214)晶面。实验测得的TFAM-BDNP的PXRD图(图2a)与模拟3倍互穿金刚石(dia)网络结构的PXRD图(图2b)相匹配,表明采用本发明方法合成的三维共价有机框架TFAM-BDNP的结晶度好。
图3为TFAM、BDNP和TFAM-BDNP的红外光谱图。由图3可见,与单体TFAM和BDNP的红外光谱相比,TFAM-BDNP的红外光谱中1346cm-1和1543cm-1处的硝基特征峰消失,表明TFAM和BDNP发生Zincke反应合成了TFAM-BDNP。
为了研究TFAM-BDNP的化学稳定性,分别将TFAM-BDNP置于3M NaOH、3M HCl和200kGyγ-射线辐照的不同条件下处理24小时,测试处理前后TFAM-BDNP的红外光谱。图4是TFAM-BDNP在经不同条件处理后的红外光谱图。由图4可见,TFAM-BDNP经3M NaOH、3M HCl或200kGyγ-射线辐照24小时后其红外光谱无明显变化,表明TFAM-BDNP具有良好的耐酸碱以及耐辐照稳定性。这是由于本发明方法制备的三维共价有机框架TFAM-BDNP具有3倍互穿金刚石网络结构,该结构具有极稳定的低密度刚性骨架,从而增强了TFAM-BDNP的稳定性。
实施例2:TFAM-BDNP对ReO4 -的吸附
(1)pH优化
将10mg的TFAM-BDNP加入到20mL含有400ppm ReO4 -的溶液中,用NaOH和HNO3调节溶液pH值为2-12,室温下在摇床上振荡24h,用0.22μm微孔滤膜过滤,通过电感耦合等离子体质谱检测滤液中残留的ReO4 -浓度,计算TFAM-BDNP对ReO4 -的吸附量。结果表明,TFAM-BDNP在pH值2-12的宽pH范围内对ReO4 -均有良好的吸附性能,选择最佳pH值为7。
(2)TFAM-BDNP对ReO4 -的吸附容量和吸附动力学行为
将高铼酸钠溶解在超纯水中配制成不同浓度(0-1000mg/L)的ReO4 -溶液,用HNO3或NaOH调节溶液pH值为7,向20mL的ReO4 -溶液中加入10mg的TFAM-BDNP,室温下在摇床上振荡24h,用0.22μm微孔滤膜过滤,通过电感耦合等离子体质谱检测滤液中残留的ReO4 -浓度,计算TFAM-BDNP对ReO4 -的吸附容量。图5是TFAM-BDNP对ReO4 -的吸附等温线图。由图5可见,TFAM-BDNP对ReO4 -的最大吸附容量为998.3mg/g。TFAM-BDNP对ReO4 -的高吸附性能可能是由于本发明采用阳离子型1,1'-双(2,4-二硝基苯基)-4,4'-二氯化联吡啶构建了具有高电荷密度的阳离子型三维共价有机框架,在静电相互作用中提供了更多的作用位点,从而提高了对ReO4 -离子的吸附容量。
将10mg的TFAM-BDNP加入到20mL pH为7含有28mg/L的ReO4 -的溶液中,室温下在摇床上振荡,分别在不同时间间隔内取1mL混合液用0.22μm膜过滤器过滤,通过电感耦合等离子体质谱法检测滤液中的ReO4 -浓度,计算TFAM-BDNP对ReO4 -的去除率。图6是TFAM-BDNP对ReO4 -的吸附动力学图。由图6可见,TFAM-BDNP对ReO4 -的吸附容量随着吸附时间的延长而增大,当吸附时间为60s时,TFAM-BDNP对ReO4 -的吸附即达到饱和,速度非常快。这是由于ReO4 -离子比其他典型无机阴离子的疏水性强,而本发明制备的TFAM-BDNP具有开放的三维疏水通道,其疏水表面有利于ReO4 -离子在孔隙内的扩散,从而大大提升了对ReO4 -的吸附速度。
(3)TFAM-BDNP对ReO4 -吸附的选择性
将10mg三维共价有机框架TFAM-BDNP加入到20mL含有0.1mM(25ppm)的ReO4 -和相同浓度竞争性阴离子(NO3 -、SO4 2-、PO4 3-、CO3 2-)的溶液中,室温下在摇床上振荡24h,用0.22μm微孔滤膜过滤,通过电感耦合等离子体质谱检测滤液中残留的ReO4 -浓度,考察TFAM-BDNP对ReO4 -吸附的选择性。图7是TFAM-BDNP对ReO4 -的吸附选择性图。由图7可见,TFAM-BDNP对ReO4 -的去除率近100%,而NO3 -、SO4 2-、PO4 3-或CO3 2-等阴离子几乎不影响TFAM-BDNP对ReO4 -的去除,表明TFAM-BDNP对ReO4 -的吸附选择性好。
研究了TFAM-BDNP在不同浓度NO3 -和SO4 2-存在条件下对ReO4 -的吸附选择性。将10mg的TFAM-BDNP加入到20mL含有0.1mM的ReO4 -和不同浓度NaNO3(0.1mM,1mM,5mM,10mM,50mM)或Na2SO4(0.1mM,1mM,10mM,100mM,600mM)的溶液中,室温下在摇床上振荡24h,用0.22μm微孔滤膜过滤,通过电感耦合等离子体质谱检测滤液中的ReO4 -浓度。图8是TFAM-BDNP在不同浓度NO3 -存在条件下对ReO4 -的吸附选择性图。由图8可见,当NO3 -是ReO4 -浓度的100倍和500倍时,TFAM-BDNP对ReO4 -的去除率仍分别达到74.6%和51.7%。图9是TFAM-BDNP在不同浓度SO4 2-存在条件下对ReO4 -的吸附选择性图。由图9可见,当SO4 2-是ReO4 -浓度的6000倍时,TFAM-BDNP对ReO4 -的去除率仍可达73%。以上结果表明,本发明制备的三维共价有机框架TFAM-BDNP对ReO4 -具有优异的吸附选择性,这可能是因为TFAM-BDNP的三维疏水骨架更有利于选择性吸附电荷密度相对较低的ReO4 -。
(4)TFAM-BDNP的循环使用性
将100mg的TFAM-BDNP加入到200mL pH为7含有28mg/L的ReO4 -的溶液中,室温下在摇床上振荡24h,取1mL混合液用0.22μm膜过滤器过滤,通过电感耦合等离子体质谱法检测滤液中的ReO4 -浓度,计算TFAM-BDNP对ReO4 -的去除率。吸附后的混合液经抽滤,用无水乙醇和水洗涤沉淀并在45℃真空干燥过夜,分散到1M NaCl溶液中,室温下搅拌12h,再用无水乙醇和水洗涤并在45℃下真空干燥过夜,得到再生的TFAM-BDNP。经过4个吸附/脱附循环后,TFAM-BDNP对ReO4 -的去除率仍可达99%以上,表明本发明制备的TFAM-BDNP有良好的循环使用性能。
实施例3:TFAM-BDNP对样品中ReO4 -的去除
将50mg的TFAM-BDNP加入到10mL模拟的汉福德废液中,室温下在摇床上振荡24h,用0.22μm微孔滤膜过滤,通过电感耦合等离子体质谱检测滤液中的ReO4 -浓度。结果表明,TFAM-BDNP可捕获模拟的汉福德废液中81.9%的ReO4 -。
可见,本发明方法制备的三维共价有机框架制备方法简便、结晶度高、稳定性好以及电荷密度高,具有3倍互穿金刚石网络结构以及开放的三维疏水通道,对ReO4 -具有吸附速度快、吸附容量大、选择性好以及可重复使用等优越性,可高效去除模拟汉福德废液中的ReO4 -,有良好应用前景。
以上所描述的实施例仅表达了本发明的几种优选实施例,其描述较为具体和详细,但并不用于限制本发明。应当指出,对于本领域的技术人员来说,本发明还可以有各种变化和更改,凡在本发明的构思和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (6)
1.一种三维共价有机框架的合成方法,其特征在于,包括以下步骤:
1)以四(4-氨基苯基)甲烷和1,1'-双(2,4-二硝基苯基)-4,4'-二氯化联吡啶为反应原料,向其中加入无水乙醇和水混合均匀;
2)将步骤1)所得混合液加热并搅拌,反应结束后冷却过滤,沉淀经洗涤干燥得到三维共价有机框架;所述混合液加热采用微波辐射加热;微波辐射加热温度为80-100℃,搅拌反应2 h。
2.根据权利要求1所述一种三维共价有机框架的合成方法,其特征在于,步骤1)所述四(4-氨基苯基)甲烷与1,1'-双(2,4-二硝基苯基)-4,4'-二氯化联吡啶的摩尔比为1:(1-3)。
3.根据权利要求1所述一种三维共价有机框架的合成方法,其特征在于,步骤1)所述无水乙醇和水的体积比为(1-6):1。
4.权利要求1-3任一项所述合成方法获得的三维共价有机框架在吸附高铼酸根中的应用。
5.根据权利要求4所述三维共价有机框架在吸附高铼酸根中的应用,其特征在于,所述三维共价有机框架能够在竞争性阴离子共存条件下选择性吸附去除高铼酸根;所述竞争性阴离子包括NO3 -、SO4 2-、PO4 3-、CO3 2-。
6.根据权利要求4所述三维共价有机框架在吸附高铼酸根中的应用,其特征在于,所述三维共价有机框架经过4个吸附/脱附循环后,对高铼酸根的去除率仍超过99%。
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