CN116059974B - 一种噻吩-2-羧酸改性硅胶复合材料及其制备方法和应用 - Google Patents
一种噻吩-2-羧酸改性硅胶复合材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明提供了一种噻吩‑2‑羧酸改性硅胶复合材料及其制备方法和应用,该方法将噻吩‑2‑羧酸与纳米硅胶在催化条件下进行酯化反应,利用噻吩‑2‑羧酸上的羧基与纳米硅胶上的羟基发生酯化作用合成结构稳定的复合材料,一定程度的键合,使复合材料对不同物质由于吸附机理的不同表现出不同的吸附能力,以达到材料对不同物质选择性吸附富集的优异性能,实现有效的吸附分离。吸附结果表明,本发明提供的噻吩‑2‑羧酸改性硅胶复合材料仅对对硝基酚具有明显的吸附效果,而对另外三种酚几乎没有吸附能力,因此本发明的复合材料可以应用到从小分子有机酚类中分离对硝基酚。
Description
技术领域
本发明涉及复合材料技术领域,特别涉及一种噻吩-2-羧酸改性硅胶复合材料及其制备方法和应用。
背景技术
酚类化合物具有高毒性,在低浓度时便可使细胞变性。例如对硝基苯酚,其污染具有持久性、生物蓄积性,甚至具有剧毒。在非常低的浓度下,频繁接触对硝基苯酚会导致高铁血红蛋白形成、贫血、肝肾损伤、眼睛和皮肤刺激、肿瘤、癌症和全身中毒。因此,对如何快速高效地分离去除水溶液中酚类污染物的研究受到广泛重视。
常用的分离回收方法包括吸附分离法、膜分离技术和萃取法等。在这些技术中,吸附分离法因其设计简单、操作方便、效率高而被公认为最适用的技术。在吸附过程中,硅胶因其具有稳定的化学性质、较好的耐热性、很强的力学强度,在压力下不变形、不破碎等优点,被广泛作为吸附分离材料。但是,基于硅胶表面的多羟基,硅胶本身是没有办法应用到水溶液中吸附或者分离的,且容易结块或成糊状。
氧化石墨烯已被广泛应用于水溶液中无机金属离子及有机污染物的吸附分离,氧化石墨烯的改性主要应用于从稀土离子中分离重金属和有机污染物。氧化石墨烯的改性对有机污染物的吸附具有较高效率,但是改性氧化石墨烯无法从不同的有机酚中选择性吸附对硝基酚。
因此,本发明设计了一种噻吩-2-羧酸改性硅胶复合材料及其制备方法和应用。
发明内容
本发明提供了一种噻吩-2-羧酸改性硅胶复合材料及其制备方法和应用,其目的是为了解决背景技术存在的上述问题。
为了达到上述目的,本发明的实施例提供了一种噻吩-2-羧酸改性硅胶复合材料及其制备方法和应用。
本发明实施例的一方面,提供了一种噻吩-2-羧酸改性硅胶复合材料的制备方法,包括如下步骤:
(1)以硅胶、噻吩-2-羧酸为原料,备用;
(2)以无水N,N-二甲基甲酰胺为溶剂,将所述硅胶和噻吩-2-羧酸混合,超声分散均匀,在无水条件下进行催化反应,经洗涤、干燥得到噻吩-2-羧酸改性硅胶复合材料。
进一步地,步骤(1)所述硅胶为纳米硅胶,平均晶粒为5~100nm。
进一步地,步骤(2)中将1.0~50.0g硅胶、20.0~1000.0mL无水N,N-二甲基甲酰胺、1.0~50.0g噻吩-2-羧酸超声分散混合均匀。
进一步地,步骤(2)中催化剂采用0.04~1.0g N,N’-二环己基碳二亚胺与0.04~1g 4-二甲氨基吡啶联用,与反应物超声搅拌至混合均匀。
进一步地,步骤(2)中催化反应采用防潮回流装置,在110~160℃下加热回流反应24~60h。
进一步地,步骤(2)中无水条件下进行催化反应具体表现为:始终在搅拌下进行,反应完成后将反应液自然冷却至室温,将所得产物离心洗涤,沉淀物用20-500mL乙醇反复洗涤5次及以上、用去离子水反复洗涤5次及以上,收集离心后的沉淀物,并用少量乙醚洗涤,经干燥得到噻吩-2-羧酸改性硅胶复合材料。
基于一个发明总的构思,本发明还提供了上述的制备方法获得的噻吩-2-羧酸改性硅胶复合材料。
本发明实施例的另一方面,一种上述的制备方法获得的噻吩-2-羧酸改性硅胶复合材料在有机酚类污染物中的应用,所述噻吩-2-羧酸改性硅胶复合材料用于水溶液中选择性吸附分离有机酚类污染物。
进一步地,所述有机酚类污染物包括苯酚、对苯二酚、间硝基酚、对硝基酚。
进一步地,所述水溶液中有机酚类污染物浓度为10~100mg/L。
本发明的上述方案有如下的有益效果:
(1)本发明的噻吩-2-羧酸与纳米硅胶在催化条件下进行酯化反应,利用噻吩-2-羧酸上的羧基与纳米硅胶上的羟基发生酯化作用合成结构稳定的复合材料,一定程度的键合,使复合材料对不同物质由于吸附机理的不同表现出不同的吸附能力,以达到材料对不同物质选择性吸附富集的优异性能,实现有效的吸附分离。此外,吸附结果表明,本发明提供的噻吩-2-羧酸改性硅胶复合材料仅对对硝基酚具有明显的吸附效果,而对另外三种酚几乎没有吸附能力,因此本发明的复合材料可以应用到从小分子有机酚类中分离对硝基酚。
(2)本发明的复合材料表现出良好的疏水性能,有利于复合材料吸附后的再回收。
(3)相较于未改性的硅胶,基于硅胶表面的多羟基,没有办法应用到水溶液中吸附或者分离,且容易结块或成糊状,本发明的硅胶改性后,可以使用大极性溶剂(水)作为溶剂,应用于水溶液中有机污染物的吸附分离。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1是本发明实施例纳米硅胶对有机酚(对苯二酚、间硝基酚、对硝基酚、苯酚)的吸附能力对比图;
图2是本发明实施例噻吩-2-羧酸改性硅胶复合材料对有机酚(对苯二酚、间硝基酚、对硝基酚、苯酚)的吸附能力对比图;
图3是本发明实施例噻吩-2-羧酸、纳米硅胶、硅胶-噻吩-2-羧酸复合材料以及硅胶-噻吩-2-羧酸-对硝基酚复合材料的傅里叶变换红外光谱图;
图4是本发明实施例纳米硅胶的10微米扫描电子显微镜图;
图5是本发明实施例纳米硅胶的1微米扫描电子显微镜图;
图6是本发明实施例硅胶-噻吩-2-羧酸复合材料的20微米扫描电子显微镜图;
图7是本发明实施例硅胶-噻吩-2-羧酸复合材料的1微米扫描电子显微镜图;
图8是本发明实施例硅胶-噻吩-2-羧酸复合材料的C元素映射图像;
图9是本发明实施例硅胶-噻吩-2-羧酸复合材料的O元素映射图;
图10是本发明实施例硅胶-噻吩-2-羧酸复合材料的Si元素映射图;
图11是本发明实施例硅胶-噻吩-2-羧酸复合材料的S元素映射图;
图12是本发明实施例硅胶-噻吩-2-羧酸复合材料C、O、Si、S元素映射分析图。
具体实施方式
为使本发明要解决的技术问题、技术方案和优点更加清楚,下面将结合附图及具体实施例进行详细描述。
除非另有定义,下文中所使用的所有专业术语与本领域技术人员通常理解含义相同。本文中所使用的专业术语只是为了描述具体实施例的目的,并不是旨在限制本发明的保护范围。
除非另有特别说明,本发明中用到的各种原材料、试剂、仪器和设备等均可通过市场购买得到或者可通过现有方法制备得到。
本发明针对现有的问题,提供了一种噻吩-2-羧酸改性硅胶复合材料及其制备方法和应用。
实施例1
一种噻吩-2-羧酸改性硅胶复合材料的制备方法,步骤如下:
量取50mL用分子筛处理过的无水N,N-二甲基甲酰胺于150mL圆底烧瓶中并加入2.5g纳米硅胶SG,超声15min,适量搅拌,使其充分溶解,做好封口处理待用。
依次称取2.5g噻吩-2-羧酸、0.1g N,N’-二环己基碳二亚胺与0.1g 4-二甲氨基吡啶于上述圆底烧瓶中,封口,超声15分钟并搅拌混合均匀得混合反应液。
将反应液在一个防潮回流装置中,持续磁力搅拌下在120℃温度下加热回流反应36h。
反应完成后使反应液自然冷却至室温,将所得产物离心洗涤,沉淀物用30mL乙醇反复洗涤5次、用去离子水反复洗涤5次,收集离心后的沉淀物,用少量乙醚冲洗,再经干燥得到噻吩-2-羧酸改性硅胶复合材料SG-TCA。
实施例2
一种噻吩-2-羧酸改性硅胶复合材料的制备方法,步骤如下:
量取100mL用分子筛处理过的无水N,N-二甲基甲酰胺于250mL圆底烧瓶中并加入5g纳米硅胶SG,超声15min,适量搅拌,使其充分溶解,做好封口处理待用。
依次称取5g噻吩-2-羧酸、0.2g N,N’-二环己基碳二亚胺与0.2g 4-二甲氨基吡啶于上述圆底烧瓶中,封口,超声15分钟并搅拌混合均匀得混合反应液。
将反应液在一个防潮回流装置中,持续磁力搅拌下在140℃温度下加热回流反应48h。
反应完成后使反应液自然冷却至室温,将所得产物离心洗涤,沉淀物用40mL乙醇反复洗涤5次、用去离子水反复洗涤5次,收集离心后的沉淀物,用少量乙醚冲洗,再经干燥得到噻吩-2-羧酸改性硅胶复合材料SG-TCA。
实施例3
一种噻吩-2-羧酸改性硅胶复合材料的制备方法,步骤如下:
量取150mL用分子筛处理过的无水N,N-二甲基甲酰胺于250mL圆底烧瓶中并加入8.5g纳米硅胶SG,超声15min,适量搅拌,使其充分溶解,做好封口处理待用。
依次称取8.5g噻吩-2-羧酸、0.3g N,N’-二环己基碳二亚胺与0.3g 4-二甲氨基吡啶于上述圆底烧瓶中,封口,超声15分钟并搅拌混合均匀得混合反应液。
将反应液在一个防潮回流装置中,持续磁力搅拌下在140℃温度下加热回流反应50h。
反应完成后使反应液自然冷却至室温,将所得产物离心洗涤,沉淀物用60mL乙醇反复洗涤6次、用去离子水反复洗涤6次,收集离心后的沉淀物,用少量乙醚冲洗,再经干燥得到噻吩-2-羧酸改性硅胶复合材料SG-TCA。
实施例4
一种噻吩-2-羧酸改性硅胶复合材料的制备方法,步骤如下:
量取200mL用分子筛处理过的无水N,N-二甲基甲酰胺于500mL圆底烧瓶中并加入10g纳米硅胶SG,超声15min,适量搅拌,使其充分溶解,做好封口处理待用。
依次称取10g噻吩-2-羧酸、0.4g N,N’-二环己基碳二亚胺与0.4g 4-二甲氨基吡啶于上述圆底烧瓶中,封口,超声15分钟并搅拌混合均匀得混合反应液。
将反应液在一个防潮回流装置中,持续磁力搅拌下在140℃温度下加热回流反应52h。
反应完成后使反应液自然冷却至室温,将所得产物离心洗涤,沉淀物用80mL乙醇反复洗涤7次、用去离子水反复洗涤7次,收集离心后的沉淀物,用少量乙醚冲洗,再经干燥得到噻吩-2-羧酸改性硅胶复合材料SG-TCA。
实施例5
一种噻吩-2-羧酸改性硅胶复合材料的制备方法,步骤如下:
量取300mL用分子筛处理过的无水N,N-二甲基甲酰胺于1000mL圆底烧瓶中并加入20g纳米硅胶SG,超声15min,适量搅拌,使其充分溶解,做好封口处理待用。
依次称取20g噻吩-2-羧酸、0.6g N,N’-二环己基碳二亚胺与0.6g 4-二甲氨基吡啶于上述圆底烧瓶中,封口,超声15分钟并搅拌混合均匀得混合反应液。
将反应液在一个防潮回流装置中,持续磁力搅拌下在150℃温度下加热回流反应56h。
反应完成后使反应液自然冷却至室温,将所得产物离心洗涤,沉淀物用120mL乙醇反复洗涤9次、用去离子水反复洗涤9次,收集离心后的沉淀物,用少量乙醚冲洗,再经干燥得到噻吩-2-羧酸改性硅胶复合材料SG-TCA。
应用例
将实施例1所制备的噻吩-2-羧酸改性硅胶复合材料作为吸附剂吸附水溶液中小分子有机酚类污染物(对苯二酚HQ、间硝基酚MNP、对硝基酚PNP、苯酚PH进行吸附实验)。采用傅里叶红外光谱对材料化学组成进行分析,通过SEM观察材料形貌变化,材料吸附结果及材料表征如下:
从图1可以看出改性前的纳米硅胶对四种酚均有吸附能力,而从图2可以看出噻吩-2-羧酸改性硅胶复合材料仅对对硝基酚具有明显的吸附效果,而对另外三种酚几乎没有吸附能力,因此可以应用到从水溶液中有机酚类混合物中分离对硝基酚。
从图3可以看出噻吩-2-羧酸复合材料的合成是成功的,由于噻吩-2-羧酸分子和纳米硅胶官能团之间存在酯化作用,与单纯的纳米硅胶的特征吸收峰相比有明显的C=O(1651cm-1)和噻吩环特征吸收峰(1385cm-1)出现。同时硅胶-噻吩-2-羧酸复合材料在吸附对硝基酚后C=O和噻吩环的特征峰出现偏移,这是因为复合材料对对硝基酚的吸附机理主要是π-π作用,复合材料吸附对硝基酚后由于硝基中的N原子具有吸电子效应,导致噻吩环的特征峰和C=O(1385cm-1、1651cm-1)分别向1394cm-1和1657cm-1高波数移动,表明复合材料对对硝基酚有较好的吸附。
从图4至图12可以进一步看出噻吩-2-羧酸改性硅胶复合材料的合成是成功的。通过扫描电子显微镜(SEM)观察了纳米硅胶及噻吩-2-羧酸改性硅胶复合材料(图4至7)的形貌。可以看出纳米硅胶是颗粒状的,粒径小,形状不规则较分散,纳米硅胶的表面粗糙,存在孔隙结构(图4和5),噻吩-2-羧酸改性硅胶复合材料粒径增大,形状不规则但与纳米硅胶相比较不分散,放大可看到复合材料依旧是表面粗糙的多孔结构(图6和7)。用能量色散X射线光谱仪(EDS)测定了噻吩-2-羧酸改性硅胶复合材料的元素映射图像。可以看出噻吩-2-羧酸改性硅胶中除含有Si、O两种元素外还含有S和C元素,说明硅胶-噻吩-2-羧酸复合材料复合成功(图8至11),且复合材料中只含有C、O、Si和S元素,说明制备的硅胶-噻吩-2-羧酸复合材料纯度较高,没有杂质。硅胶-噻吩-2-羧酸复合材料中的元素含量如图12所示。
本发明制备的噻吩-2-羧酸改性硅胶复合材料结构稳定,对有机酚有较好的吸附选择性,可实现水溶液中对硝基酚的吸附及对有机酚类混合物的有效分离。
以上所述是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明所述原理的前提下,还可以作出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.一种噻吩-2-羧酸改性硅胶复合材料的制备方法,其特征在于,包括如下步骤:
(1)以硅胶、噻吩-2-羧酸为原料,备用;
(2)以无水N,N-二甲基甲酰胺为溶剂,将所述硅胶和噻吩-2-羧酸混合,超声分散均匀,在无水条件下进行催化反应,经洗涤、干燥得到噻吩-2-羧酸改性硅胶复合材料;
所述噻吩-2-羧酸改性硅胶复合材料可以应用到从小分子有机酚类中分离对硝基酚。
2.根据权利要求1所述的噻吩-2-羧酸改性硅胶复合材料的制备方法,其特征在于,步骤(1)所述硅胶为纳米硅胶,平均晶粒为5~100nm。
3.根据权利要求1所述的噻吩-2-羧酸改性硅胶复合材料的制备方法,其特征在于,步骤(2)中将1.0~50.0g硅胶、20.0~1000.0mL无水N,N-二甲基甲酰胺、1.0~50.0g噻吩-2-羧酸超声分散混合均匀。
4.根据权利要求1所述的噻吩-2-羧酸改性硅胶复合材料的制备方法,其特征在于,步骤(2)中催化剂采用0.04~1.0g N,N’-二环己基碳二亚胺与0.04~1g 4-二甲氨基吡啶联用,与反应物超声搅拌至混合均匀。
5.根据权利要求1所述的噻吩-2-羧酸改性硅胶复合材料的制备方法,其特征在于,步骤(2)中催化反应采用防潮回流装置,在110~160℃下加热回流反应24~60h。
6.根据权利要求1所述的噻吩-2-羧酸改性硅胶复合材料的制备方法,其特征在于,步骤(2)中无水条件下进行催化反应具体表现为:始终在搅拌下进行,反应完成后将反应液自然冷却至室温,将所得产物离心洗涤,沉淀物用20-500mL乙醇反复洗涤5次及以上、用去离子水反复洗涤5次及以上,收集离心后的沉淀物,并用少量乙醚洗涤,经干燥得到噻吩-2-羧酸改性硅胶复合材料。
7.如权利要求1~6任一项所述的制备方法获得的噻吩-2-羧酸改性硅胶复合材料。
8.一种如权利要求1~6任一项所述的制备方法获得的噻吩-2-羧酸改性硅胶复合材料在有机酚类污染物中的应用,其特征在于,所述噻吩-2-羧酸改性硅胶复合材料用于水溶液中选择性吸附分离对硝基酚。
9.根据权利要求8所述的应用,其特征在于,所述有机酚类污染物包括苯酚、对苯二酚、间硝基酚、对硝基酚。
10.根据权利要求8所述的应用,其特征在于,所述水溶液中有机酚类污染物浓度为10~100mg/L。
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