CN113620302A - 一种磺酸基改性二氧化硅气凝胶及其制备方法和应用 - Google Patents
一种磺酸基改性二氧化硅气凝胶及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种磺酸基改性二氧化硅气凝胶及其制备方法和应用,本发明以四烷氧基硅烷和巯基硅烷为共前驱体硅源,通过溶胶‑凝胶共缩聚法制备巯基改性二氧化硅凝胶,在无水乙醇溶液中进行老化,湿凝胶分别在氧化剂溶液和酸溶液中进行氧化和酸化,最后通过常压干燥制得磺酸基改性二氧化硅气凝胶。本发明所述的制备方法简单,易操作,过程易控制,可连续化生产。获得的磺酸基改性二氧化硅气凝胶具有优异的物理化学特性,不仅具有高比表面积和高孔隙率,同时气凝胶表面含有丰富的磺酸基官能团。本发明所述的磺酸基改性二氧化硅气凝胶可用于空气中碱性气体的吸附,水体中有机污染物和重金属离子的吸附,还可作为一种良好的固体酸催化剂。
Description
技术领域
本发明涉及环境污染治理技术领域,具体涉及一种磺酸基改性二氧化硅气凝胶及其制备方法,并作为环境净化材料应用。
背景技术
二氧化硅气凝胶是一种以空气为介质的纳米多孔材料,具有低密度(0.003~0.35g/cm3)、高比表面积(600~1500m2/g)、高孔隙率(80~99.9%)和孔隙结构可调的优异物理特性,在化学、热学、声学、光学、电学等领域具有广阔的应用前景,近年来,二氧化硅气凝胶被认为是一种潜在优异的环境净化功能材料,在吸附、催化和分离等方向展现出优异的性能。
二氧化硅气凝胶作为高效环境净化材料应用,不仅需要保持其优异多孔特性,同时还需调控其表面官能团特性。传统的二氧化硅气凝胶的骨架表面主要是硅羟基,硅羟基可通过氢键作用吸附空气中的水蒸汽,从而达到空气中除湿的目的。然而,传统二氧化硅气凝胶对环境中的其他污染物去除效果往往较差,这是由于其表面的硅羟基与污染物的作用力弱、选择性差。因此,对于二氧化硅气凝胶需要对其表面官能团修饰或者复合,提高对目标污染物的吸附选择性和结合能。如专利授权公告号为CN107188188B的专利中公开了一种胺基改性二氧化硅气凝胶的制备方法,将胺基官能团嫁接于二氧化硅气凝胶骨架表面,显著提高了气凝胶对污染物的吸附性能,该胺基改性二氧化硅气凝胶可用于空气中二氧化碳的捕集、硫氧化物的净化以及水中有机污染物的吸附。专利申请公告号为CN 111253615A的专利公开了一种超疏水有机硅气凝胶及其常温常压干燥制备方法,通过对硅基气凝胶进行表面超疏水修饰,所获得的有机硅基气凝胶具有超疏水亲油特性,可以在油水分离中展现出良好的应用。专利申请公告号为CN109133071A的专利公开了一种有机杂化二氧化硅气凝胶的制备方法,通过氯丙基三甲氧基硅烷和氨丙基三甲氧基硅烷反应制备的复合硅烷偶联剂改性二氧化硅气凝胶骨架表面,获得的有机杂化二氧化硅气凝胶具有较高的萃取性能,在环境检测、食品检测和药物分析领域具有一定的应用潜力。
虽然目前公开了各种二氧化硅气凝胶的改性制备方法,但是目前二氧化硅气凝胶的改性主要集中于疏水改性和胺基改性方面,对于其他官能团的改性制备方法和工艺仍缺少研究。
发明内容
本发明的目的在于提供一种工艺简单、过程易控制、可连续化生产的磺酸基改性二氧化硅气凝胶的方法,所述磺酸基改性二氧化硅气凝胶具有高比表面积和高孔隙率,同时含有丰富的磺酸基官能团。本发明的另一个目的是提供了所述磺酸基改性二氧化硅气凝胶作为环境净化材料的应用。
本发明所述的磺酸基改性二氧化硅气凝胶块体的制备方法包括以下步骤:
(1)将巯基硅烷、四烷氧基硅烷、乙醇、水按一定比例混合,搅拌均匀并使硅源水解形成硅溶胶。
在步骤(1)中,按原料体积比,四烷氧基硅烷:巯基硅烷∶无水乙醇∶水= 5:(0.5-3):(10-30):(0.9-3.6),硅源水解时所述的搅拌时间控制在16-24小时之间。
(2)向步骤(1)得到的水解的硅溶胶中加入氨水,搅拌至混合均匀,静置凝胶化,老化后得到巯基改性二氧化硅湿凝胶。
在步骤(2)中,加入氨水后的搅拌时间5-30 分钟,静置时间1-5小时。
在步骤(2)中,所述湿凝胶的老化温度可为25-60℃,时间可为20-36小时。
(3)将步骤(2)得到的巯基改性湿凝胶依次浸没于氧化剂和酸溶液中,将湿凝胶表面的巯基进行氧化和酸化获得磺酸基,再通过水洗和乙醇溶剂交换,最后通过常压干燥制得磺酸基改性二氧化硅气凝胶。
在步骤(3)中,所述湿凝胶浸没于氧化剂的时间为6-24小时。
在步骤(3)中,所述酸溶液的浓度为0.1-1 mol/L。
在步骤(3)中,所述常压干燥的温度为80-120℃,干燥时间为4-8小时。
本发明所述的磺酸基改性二氧化硅气凝胶的制备方法中,在溶胶-凝胶阶段通过共缩聚的方法,加入巯基硅烷和硅源一起反应,可形成二氧化硅凝胶骨架的均匀体改性,最后氧化酸化、常压干燥制备得到带有磺酸基功能化基团的二氧化硅气凝胶。制备的磺酸基改性二氧化硅气凝胶为纳米多孔结构,孔径分布相对集中在1-10 nm,孔体积为0.1-1 cm3g-1。比表面积为100-1000 m2g-1。
本发明制备磺酸基改性二氧化硅气凝胶具有丰富的纳米多孔结构,同时表面含有丰富的磺酸基官能团。所述磺酸基改性二氧化硅气凝胶可作为高效气体吸附材料,通过酸-碱吸附作用选择性吸附去除空气中的碱性气体,如氨气、三甲基胺、三乙基胺等;也可以作为水体吸附材料,通过质子交换、酸碱吸附和络合等作用吸附水体中的有机污染物或重金属离子;此外,二氧化硅气凝胶表面丰富的磺酸基还可以提供酸性催化位点,从而作为固体酸催化剂。所述磺酸基改性二氧化硅气凝胶制备条件温和、工艺简单,有望作为环境净化材料应用。
与现有技术比较,本发明具有如下突出优点:
本发明采用共缩聚、后氧化以及常压干燥工艺制备磺酸基改性二氧化硅气凝胶,既保持了二氧化硅气凝胶比表面积大、孔径小和孔隙率高的优点,同时气凝胶表面磺酸基的分布均匀含量高且可控。本发明所采用的制备工艺简单、易控,成本低,避免后嫁接法对二氧化硅凝胶的孔洞堵塞,同时改性反应慢、改性基团分布不均匀和含量难以控制的缺点。在制备过程中采用常压干燥,从而避免了超临界温度及压力较高带来的设备高要求与操作危险的问题。并且制备得到的磺酸基改性二氧化硅气凝胶作为环境净化材料应用时展现出优异的性能。
附图说明
图1为本发明实施例1制备的磺酸基改性二氧化硅气凝胶的照片。
图2为本发明实施例1制备的磺酸基改性二氧化硅气凝胶的扫描电镜照片。
图3为本发明实施例1制备的磺酸基改性二氧化硅气凝胶的氮气吸附脱附曲线以及孔径分布图。
图4 为本发明实施例1制备的磺酸基改性二氧化硅气凝胶对NH3的静态吸附等温线曲线。
具体实施方式
下面通过实施例结合附图对本发明作进一步说明。
实施例1
原料体积比:正硅酸四乙酯:(3-巯基丙基)三甲氧基硅烷:乙醇:水=5:2:20:3,将5ml的正硅酸四乙酯、2ml的(3-巯基丙基)三甲氧基硅烷与20ml的无水乙醇混合搅拌,再加入3ml的水,持续搅拌以促进硅源的水解,16小时后将向溶胶中加入催化剂氨水,搅拌10分钟,然后将得到的二氧化硅凝胶静置2小时。再将湿凝胶置于无水乙醇溶液中进行老化,老化温度为60℃,老化时间为12小时。老化后将湿凝胶加入双氧水的溶液中浸泡24小时使其巯基氧化,再加入0.1mol/L的硫酸中酸化,酸化后用凝胶水洗和乙醇替换,最后再次常压干燥,干燥温度为80℃,干燥4小时,即得到的磺酸基改性二氧化硅气凝胶。
实施例2
原料体积比:正硅酸四乙酯:(3-巯丙基)三乙氧基硅烷:乙醇:水=5:1:15:3.6,将5ml的正硅酸四乙酯、1ml的(3-巯丙基)三乙氧基硅烷与15ml的无水乙醇混合搅拌,再加入3.6ml的水,持续搅拌以促进硅源的水解,20小时后将向溶胶中加入催化剂氨水,搅拌20分钟,然后将得到的二氧化硅凝胶静置5小时。再将湿凝胶置于无水乙醇溶液中进行老化,老化温度为60℃,老化时间为24小时。老化后将湿凝胶加入次氯酸钠的溶液中浸泡24小时使其巯基氧化,再加入1mol/L的盐酸中酸化,酸化后用凝胶水洗和乙醇替换,最后再次常压干燥,干燥温度为80℃,干燥4小时,即得到的磺酸基改性二氧化硅气凝胶。
实施例3
原料体积比:正硅酸四乙酯:巯丙基甲基二甲氧基硅烷:乙醇:水=5:2:30:1.8,将5ml的正硅酸四乙酯、2ml的巯丙基甲基二甲氧基硅烷与30ml的无水乙醇混合搅拌,再加入1.8ml的水,持续搅拌以促进硅源的水解,24小时后将向溶胶中加入催化剂氨水,搅拌10分钟,然后将得到的二氧化硅凝胶静置1小时。再将湿凝胶置于无水乙醇溶液中进行老化,老化温度为50℃,老化时间为36小时。老化后将湿凝胶加入双氧水的溶液中浸泡24小时使其巯基氧化,再加入0.1mol/L的硫酸中酸化,酸化后用凝胶水洗和乙醇替换,最后再次常压干燥,干燥温度为120℃,干燥6小时,即得到的磺酸基改性二氧化硅气凝胶。
实施例4
原料体积比:正硅酸四乙酯:(3-巯基丙基)三甲氧基硅烷:乙醇:水=5:3:10:2.7,将5ml的正硅酸四乙酯、3ml的(3-巯基丙基)三甲氧基硅烷与10ml的无水乙醇混合搅拌,再加入2.7ml的水,持续搅拌以促进硅源的水解,24小时后将向溶胶中加入催化剂氨水,搅拌30分钟,然后将得到的二氧化硅凝胶静置5小时。再将湿凝胶置于无水乙醇溶液中进行老化,老化温度为35℃,老化时间为36小时。老化后将湿凝胶加入次氯酸钠的溶液中浸泡6小时使其巯基氧化,再加入0.5mol/L的硫酸中酸化,酸化后用凝胶水洗和乙醇替换,最后再次常压干燥,干燥温度为100℃,干燥8小时,即得到的磺酸基改性二氧化硅气凝胶。
实施例5
原料体积比:正硅酸四甲酯:(3-巯丙基)三乙氧基硅烷:乙醇:水=5:1:25:0.9,将5ml的正硅酸四甲酯、1ml的(3-巯丙基)三乙氧基硅烷与25ml的无水乙醇混合搅拌,再加入0.9ml的水,持续搅拌以促进硅源的水解,20小时后将向溶胶中加入催化剂氨水,搅拌10分钟,然后将得到的二氧化硅凝胶静置4小时。再将湿凝胶置于无水乙醇溶液中进行老化,老化温度为55℃,老化时间为24小时。老化后将湿凝胶加入双氧水的溶液中浸泡24小时使其巯基氧化,再加入1mol/L的硫酸中酸化,酸化后用凝胶水洗和乙醇替换,最后再次常压干燥,干燥温度为80℃,干燥8小时,即得到的磺酸基改性二氧化硅气凝胶。
Claims (9)
1.一种磺酸基改性的二氧化硅气凝胶的制备方法,其特征在于由以下具体步骤制备:
(1)将巯基硅烷、四烷氧基硅烷、乙醇、水按一定比例混合,搅拌均匀并使硅源水解形成硅溶胶;
(2)向步骤(1)得到的水解的硅溶胶中加入氨水,搅拌至混合均匀,静置凝胶化,老化后得到巯基改性二氧化硅湿凝胶;
(3)将步骤(2)得到的巯基改性湿凝胶依次浸没于氧化剂和酸溶液中,将湿凝胶表面的巯基进行氧化和酸化获得磺酸基,再通过水洗和乙醇溶剂交换,最后通过常压干燥制得磺酸基改性二氧化硅气凝胶。
2.如权利要求1所述一种磺酸基改性二氧化硅气凝胶的制备方法,所述溶胶按原料体积比,优选范围为四烷氧基硅烷:巯基硅烷:乙醇:水=5:(0.5-3):(10-30):(0.9-3.6)。
3.如权利要求1所述一种磺酸基改性二氧化硅气凝胶的制备方法,其特征在于所述巯基硅烷的种类包括(3-巯基丙基)三甲氧基硅烷、(3-巯丙基)三乙氧基硅烷或者巯丙基甲基二甲氧基硅烷的中一种或者多种。
4.如权利要求1所述一种磺酸基改性二氧化硅气凝胶的制备方法,其特征在于所述四烷氧基硅烷的种类为正硅酸四乙酯或者正硅酸四甲酯。
5.如权利要求1所述一种磺酸基改性二氧化硅气凝胶的制备方法,其特征在于所述老化温度应控制在25-60℃,老化的时间为20-36小时,常压干燥温度为80-120℃。
6.如权利要求1所述一种磺酸基改性二氧化硅气凝胶的制备方法,其特征在于所述氧化剂为双氧水、次氯酸钠或者高锰酸钾中的一种或者多种。
7.如权利要求1所述一种磺酸基改性二氧化硅气凝胶的制备方法,其特征在于所述酸化剂为硫酸、盐酸或者硝酸中的一种或者多种。
8.如权利要求 1~7中所述一种磺酸基改性二氧化硅气凝胶的制备方法制备的磺酸基改性二氧化硅气凝胶,磺酸基改性二氧化硅气凝胶的比表面积为100-1000 m2g-1,孔径为1-10 nm,孔体积0.1-1 cm3g-1。
9.如权利要求 1~7 中所述一种磺酸基改性二氧化硅气凝胶的制备方法制备的磺酸基改性二氧化硅气凝胶,磺酸基改性二氧化硅气凝胶可作为环境净化材料应用,包括用于空气中碱性气体的吸附,水体中有机污染物和重金属离子的吸附,还可作为一种良好的固体酸催化剂。
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