CN111659349B - 一种自组装蜂巢活性炭-纳米粒子模块及其制备方法 - Google Patents

一种自组装蜂巢活性炭-纳米粒子模块及其制备方法 Download PDF

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CN111659349B
CN111659349B CN202010547932.3A CN202010547932A CN111659349B CN 111659349 B CN111659349 B CN 111659349B CN 202010547932 A CN202010547932 A CN 202010547932A CN 111659349 B CN111659349 B CN 111659349B
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吴宁安
杜川
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Tianjin Tsingke Environmental Protection Technology Co ltd
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Abstract

本发明提供了一种自组装蜂巢活性炭‑纳米粒子模块及其制备方法,所述自组装蜂巢活性炭‑纳米粒子模块包括载体、吸附剂、固化剂和纳米粒子,所述载体、吸附剂、固化剂和纳米粒子层叠组装,所述纳米粒子覆盖于载体表面上。本发明所述的自组装蜂巢活性炭‑纳米粒子模块,制备方法简单,蜂巢活性炭提供了极高的比表面积,纳米粒子均匀自组装在蜂巢活性炭的表面,达到了彻底吸附分解空气中甲醛、乙醛、苯、甲苯、二甲苯、VOCs等有害化学物质的目的。

Description

一种自组装蜂巢活性炭-纳米粒子模块及其制备方法
技术领域
本发明属于空气净化领域,尤其是涉及一种自组装蜂巢活性炭-纳米粒子模块及其制备方法。
背景技术
随着社会的发展与进步,室内、车内化学污染问题越来越引起人们的重视。甲醛、苯系物、氨、挥发性有机物(VOCs)等污染性气体是造成室内、车内污染的主要化学物质,严重威胁着人类的身体健康。
目前治理室内、车内化学污染问题的常用方法主要是物理法、化学法以及物理化学结合的方法。物理法是指采用活性炭、分子筛等多孔材料吸附空气中的甲醛、苯系物、氨、VOCs等化学物质,这种方法在短时间内具有较好的吸附效果,然而长时间使用容易存在吸附饱和后的解吸问题,使得甲醛、苯系物、氨、VOCs等化学物质重新挥发到空气中;化学法是指采用化学分解的方法达到清除空气中的甲醛、苯系物、氨、VOCs等化学物质的目的,然而容易存在作用效率低下的问题;物理化学结合方法是指通过两者的复合,主动吸附空气中的甲醛、苯系物、氨、VOCs等化学物质,然后进一步进行分解清除,如活性炭-二氧化钛材料,然而,这种材料多存在二氧化钛在活性炭上负载不牢固的问题,这严重影响了其实际生产应用。
因此,通过使用一种与空气中的污染性化学物质具有较高接触面积的自组装蜂巢活性炭-纳米粒子模块,主动吸附空气中的甲醛、苯系物、氨、VOCs等化学物质,然后进一步对其进行彻底分解,有效提高其降解效率,对于创造人类美好的家居环境具有重要意义。
发明内容
有鉴于此,本发明旨在提出一种自组装蜂巢活性炭-纳米粒子模块及其制备方法,该模块具有较大的表面积,纳米粒子均匀牢固负载,彻底吸附分解空气中的甲醛、乙醛、苯、甲苯、二甲苯、VOCs等有害化学物质,有效提高上述有害化学物质的降解效率。
为达到上述目的,本发明的技术方案是这样实现的:
一种自组装蜂巢活性炭-纳米粒子模块,包括载体、吸附剂、固化剂和纳米粒子,所述吸附剂负载于载体上,所述固化剂和纳米粒子负载于吸附剂上。
进一步的,所述载体为蜂巢活性炭,所述吸附剂为聚电解质和无机盐。
本发明还提供了上述的自组装蜂巢活性炭-纳米粒子模块的制备方法,包括以下步骤:
S1、向水中加入聚电解质和无机盐制备混合液a,所述混合液a包含1-50g/L的聚电解质和0.01-0.05mol/L的无机盐;
S2、向水中加入纳米粒子和固化剂制备混合液b,所述混合液b包含质量分数为1%-10%的纳米粒子和质量分数为0.01%-0.5%的固化剂,并将混合液b超声震荡均匀;
S3、将步骤S1得到的所述混合液a负载于蜂巢活性炭的表面;
S4、将步骤S2得到的所述混合液b负载于步骤S3得到的蜂巢活性炭的表面;
S5、将步骤S4得到的蜂巢活性炭放入烘箱中,40-70℃干燥5-10小时;
S6、将0.2-0.7mol/L的NaOH溶液负载于步骤S5得到的蜂巢活性炭的表面;
S7、将步骤S6得到的蜂巢活性炭放入烘箱中,40-70℃干燥5-10小时,得到自组装蜂巢活性炭-纳米粒子模块。
进一步的,所述步骤S1中,所述聚电解质为阴离子聚电解质或阳离子聚电解质,优选地,所述阴离子聚电解质为聚丙烯酸、聚甲基丙烯酸、聚苯乙烯磺酸、聚乙烯磺酸和聚乙烯磷酸中的一种或两种以上,所述阳离子聚电解质为聚烯丙胺盐酸盐、聚乙烯亚胺、聚乙烯胺、聚二烯丙基二甲基氯化铵、聚乙烯吡啶、聚磷酸盐和聚硅酸盐中的一种或两种以上。
进一步的,所述步骤S1中,所述无机盐为氯化钠、氯化钾、氯化铵、硫酸钠、硫酸钾、硝酸钠、硝酸钾中的一种或两种以上。
进一步的,所述步骤S2中,所述纳米粒子的粒径为3-800nm,所述纳米粒子为纳米二氧化钛、纳米氧化锌、纳米氧化钨、纳米硫化镉、纳米硫化锌、纳米负离子电气石中的一种或两种以上。
进一步的,所述步骤S2中,所述固化剂为聚乙烯醇、聚乙烯吡咯烷酮、聚乙二醇、聚环氧乙烯中的一种或两种以上。
进一步的,所述步骤S3中,通过浸渍或者喷洒的方式使混合液a负载于蜂巢活性炭的表面,浸渍或喷洒时间为5-10min,混合液a与蜂巢活性炭的质量之比为1:1-1:2。
进一步的,所述步骤S4中,通过浸渍或者喷洒的方式使混合液b负载于步骤S3得到的蜂巢活性炭的表面,浸渍或喷洒时间为5-10min,混合液b与步骤S3得到的蜂巢活性炭的质量之比为1:1-1:2。
进一步的,所述步骤S6中,通过浸渍或者喷洒的方式使NaOH溶液负载于步骤S5得到的蜂巢活性炭的表面,NaOH溶液与步骤S5得到的蜂巢活性炭的质量之比为1:1-1:2。
混合液a中阴离子聚电解质或阳离子聚电解质的选择是与蜂巢活性炭表面及纳米粒子的荷电性有关,其基本原则是与蜂巢活性炭表面以及纳米粒子的荷电性相反,其目的是通过静电自组装于蜂巢活性炭表面形成自组装吸附层。具体来说,首先确保阴离子聚电解质或阳离子聚电解质需与蜂巢活性炭电荷相反,这样利于蜂巢活性炭与聚电解质的静电自组装从而形成吸附层;其次阴离子聚电解质或阳离子聚电解质也需与纳米粒子的电荷性相反,从而利于聚电解质与纳米粒子之间的静电自组装。
混合液b中的固化剂起到固化的作用。
本发明得到的自组装蜂巢活性炭-纳米粒子模块,添加NaOH的目的在于给自组装模块提供碱性中心,进一步提升自组装材料的降解效率。
相对于现有技术,本发明所述的自组装蜂巢活性炭-纳米粒子模块及其制备方法具有以下优势:
本发明所述的自组装蜂巢活性炭-纳米粒子模块,蜂巢活性炭提供了极高的比表面积,纳米粒子均匀自组装在蜂巢活性炭的表面,负载牢固,不易脱落,循环性能好,达到了彻底吸附分解空气中甲醛、乙醛、苯、甲苯、二甲苯、VOCs等有害化学物质的目的。
附图说明
构成本发明的一部分的附图用来提供对本发明的进一步理解,本发明的示意性实施例及其说明用于解释本发明,并不构成对本发明的不当限定。在附图中:
图1为本发明实施例1所述的自组装蜂巢活性炭-纳米粒子模块的扫描电镜图;
图2为本发明实施例1所述的自组装蜂巢活性炭-纳米粒子模块的循环除醛性能图;
图3为本发明实施例1所述的自组装蜂巢活性炭-纳米粒子模块的除醛性能图;
图4为本发明实施例1所述的自组装蜂巢活性炭-纳米粒子模块的除氨气性能图;
图5为本发明对比例所述的单纯的蜂巢活性炭浸渍纳米二氧化钛的除醛性能图。
具体实施方式
除有定义外,以下实施例中所用的技术术语具有与本发明所属领域技术人员普遍理解的相同含义。以下实施例中所用的试验试剂,如无特殊说明,均为常规生化试剂;所述实验方法,如无特殊说明,均为常规方法。
下面结合实施例及附图来详细说明本发明。
实施例1
一种自组装蜂巢活性炭-纳米粒子模块的制备方法,具体包括以下步骤:
1.制备混合液a,使其包含10g/L的阳离子聚电解质聚烯丙胺盐酸盐、0.01mol/L的NaCl溶液;
2.制备混合液b,使其包含质量分数为5%的纳米二氧化钛(粒径为5nm)和0.05%的固化剂聚乙烯醇,并超声震荡均匀;
3.将所述混合液a通过浸渍法负载于蜂巢活性炭的表面,浸渍时间为5min,混合液a与蜂巢活性炭的质量之比为1:2;
4.将所述混合液b通过喷洒法负载于步骤3得到的蜂巢活性炭的表面,喷洒时间为5min,混合液b与步骤3得到的蜂巢活性炭的质量之比为1:1.5;
5.将步骤4得到的蜂巢活性炭放入烘箱中,70℃干燥7小时;
6.将0.5mol/L的NaOH溶液通过浸渍法负载于步骤5得到的蜂巢活性炭的表面,NaOH溶液与步骤5得到的蜂巢活性炭的质量之比为1:1.5;
7.将步骤6得到的产物放入烘箱中,70℃干燥8小时,得到自组装蜂巢活性炭-纳米粒子模块。
对制备得到的自组装蜂巢活性炭-纳米粒子模块在电镜下进行扫描,扫描结果见图1,从图1可以看出纳米二氧化钛粒子均匀负载在蜂巢活性炭的表面。
对制备得到的自组装蜂巢活性炭-纳米粒子模块进行紫外光光催化循环除醛性能测试,测试结果如图2所示,从图2中可以看出本发明所述的自组装蜂巢活性炭-纳米粒子模块除醛性能好,能在60min的时间内将甲醛浓度从0.9pp降低至0.1ppm,而且还具有稳定的除醛活性,经过4次循环使用后,其除醛效率仍可达到90%以上。
对制备得到的自组装蜂巢活性炭-纳米粒子模块进行紫外光光催化除醛性能测试,测试结果如图3所示,从图3中可以看出本发明所述的自组装蜂巢活性炭-纳米粒子模块除醛性能好,能在30min的时间内将甲醛浓度从0.6pp降低至0.1ppm,而且还具有稳定的除醛活性,在三十天的时间内经过6次循环使用后,其仍能将甲醛浓度从0.6pp降低至0.1ppm。
对制备得到的自组装蜂巢活性炭-纳米粒子模块进行除氨气性能测试,测试结果如图4所示,从图4中可以看出本发明所述的自组装蜂巢活性炭-纳米粒子模块在经过2次循环使用后,仍然表现出较好的除氨气性能。
实施例2
一种自组装蜂巢活性炭-纳米粒子模块的制备方法,具体包括以下步骤:
1.制备混合液a,使其包含10g/L的阳离子聚电解质聚乙烯胺、0.01mol/L的NaCl溶液;
2.制备混合液b,使其包含质量分数为5%的纳米电气石负离子(粒径为400-500nm)和0.05%的固化剂聚环氧乙烯,并超声震荡均匀;
3.将所述混合液a通过浸渍法负载于蜂巢活性炭的表面,浸渍时间为5min,混合液a与蜂巢活性炭的质量之比为1:2;
4.将所述混合液b通过喷洒法负载于步骤3得到的蜂巢活性炭的表面,喷洒时间为6min,混合液b与步骤3得到的蜂巢活性炭的质量之比为1:1.5;
5.将步骤4得到的蜂巢活性炭放入烘箱中,70℃干燥8小时;
6.将0.5mol/L的NaOH溶液通过喷洒法负载于所述步骤5得到的蜂巢活性炭的表面,NaOH溶液与步骤5得到的蜂巢活性炭的质量之比为1:1.5;
7.将步骤6得到的产物放入烘箱中,70℃干燥9小时,得到自组装蜂巢活性炭-纳米粒子模块。
实施例3
一种自组装蜂巢活性炭-纳米粒子模块的制备方法,具体包括以下步骤:
1.制备混合液a,使其包含10g/L的阳离子聚电解质(聚烯丙胺盐酸盐和聚乙烯胺按体积比3:1组成的混合液)、0.01mol/L的NaCl溶液;
2.制备混合液b,使其包含质量分数为5%的纳米粒子(纳米二氧化钛与电气石负离子的质量比为2:1,纳米二氧化钛粒径为5nm,纳米电气石负离子粒径为400-500nm)和0.05%的固化剂聚环氧乙烯,并超声震荡均匀;
3.将所述混合液a通过浸渍法负载于蜂巢活性炭的表面,浸渍时间为6min,混合液a与蜂巢活性炭的质量之比为1:2;
4.将所述混合液b通过喷洒法负载于步骤3得到的蜂巢活性炭的表面,喷洒时间为5min,混合液b与步骤3得到的蜂巢活性炭的质量之比为1:1.5;
5.将步骤4得到的蜂巢活性炭放入烘箱中,70℃干燥8小时;
6.将0.5mol/L的NaOH溶液负载于步骤5得到的蜂巢活性炭的表面,NaOH溶液与步骤5得到的蜂巢活性炭的质量之比为1:1.5;
7.将步骤6得到的产物放入烘箱中,70℃干燥9小时,得到自组装蜂巢活性炭-纳米粒子模块。
对比例
单纯的蜂巢活性炭浸渍纳米二氧化钛,与实施例1的制备过程不同之处在于,省略步骤1和4,且制备时未加入固化剂。测试制备得到的单纯的蜂巢活性炭浸渍纳米二氧化钛的光催化除醛性能测试,测试结果见图5,从图5可以看出,其除醛性能与实施例1相差较大,仅能在30min的时间内将甲醛浓度从0.6pp降低至0.3ppm左右;而实施例1制备得到的自组装蜂巢活性炭-纳米粒子模块能在30min的时间内将甲醛浓度从0.6pp降低至0.1ppm,而且还具有稳定的除醛活性,在三十天的时间内经过6次循环使用后,其仍能将甲醛浓度从0.6pp降低至0.1ppm。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。

Claims (9)

1.一种自组装蜂巢活性炭-纳米粒子模块,其特征在于:包括载体、吸附剂、固化剂和纳米粒子,所述吸附剂负载于载体上,所述固化剂和纳米粒子负载于吸附剂上;
所述载体为蜂巢活性炭,所述吸附剂为聚电解质和无机盐;
所述纳米粒子为纳米二氧化钛、纳米氧化锌、纳米氧化钨、纳米硫化镉、纳米硫化锌、纳米负离子电气石中的一种或两种以上;
所述自组装蜂巢活性炭-纳米粒子模块的制备方法,包括以下步骤:
S1、向水中加入聚电解质和无机盐制备混合液a,所述混合液a包含1-50g/L的聚电解质和0.01-0.05mol/L的无机盐;
S2、向水中加入纳米粒子和固化剂制备混合液b,所述混合液b包含质量分数为1%-10%的纳米粒子和质量分数为0.01%-0.5%的固化剂,并将混合液b超声震荡均匀;
S3、将步骤S1得到的所述混合液a负载于蜂巢活性炭的表面;
S4、将步骤S2得到的所述混合液b负载于步骤S3得到的蜂巢活性炭的表面;
S5、将步骤S4得到的蜂巢活性炭放入烘箱中,40-70℃干燥5-10小时;
S6、将0.2-0.7mol/L的NaOH溶液负载于步骤S5得到的蜂巢活性炭的表面;
S7、将步骤S6得到的蜂巢活性炭放入烘箱中,40-70℃干燥5-10小时,得到自组装蜂巢活性炭-纳米粒子模块。
2.根据权利要求1所述的自组装蜂巢活性炭-纳米粒子模块,其特征在于:所述步骤S1中,所述聚电解质为阴离子聚电解质或阳离子聚电解质。
3.根据权利要求2所述的自组装蜂巢活性炭-纳米粒子模块,其特征在于:所述阴离子聚电解质为聚丙烯酸、聚甲基丙烯酸、聚苯乙烯磺酸、聚乙烯磺酸和聚乙烯磷酸中的一种或两种以上,所述阳离子聚电解质为聚烯丙胺盐酸盐、聚乙烯亚胺、聚乙烯胺、聚二烯丙基二甲基氯化铵、聚乙烯吡啶、聚磷酸盐和聚硅酸盐中的一种或两种以上。
4.根据权利要求1所述的自组装蜂巢活性炭-纳米粒子模块,其特征在于:所述步骤S1中,所述无机盐为氯化钠、氯化钾、氯化铵、硫酸钠、硫酸钾、硝酸钠、硝酸钾中的一种或两种以上。
5.根据权利要求1所述的自组装蜂巢活性炭-纳米粒子模块,其特征在于:所述步骤S2中,所述纳米粒子的粒径为3-800nm。
6.根据权利要求1所述的自组装蜂巢活性炭-纳米粒子模块,其特征在于:所述步骤S2中,所述固化剂为聚乙烯醇、聚乙烯吡咯烷酮、聚乙二醇、聚环氧乙烯中的一种或两种以上。
7.根据权利要求1所述的自组装蜂巢活性炭-纳米粒子模块,其特征在于:所述步骤S3中,通过浸渍或者喷洒的方式使混合液a负载于蜂巢活性炭的表面,浸渍或喷洒时间为5-10min,混合液a与蜂巢活性炭的质量之比为1:1-1:2。
8.根据权利要求1所述的自组装蜂巢活性炭-纳米粒子模块,其特征在于:所述步骤S4中,通过浸渍或者喷洒的方式使混合液b负载于步骤S3得到的蜂巢活性炭的表面,浸渍或喷洒时间为5-10min,混合液b与步骤S3得到的蜂巢活性炭的质量之比为1:1-1:2。
9.根据权利要求1所述的自组装蜂巢活性炭-纳米粒子模块,其特征在于:所述步骤S6中,通过浸渍或者喷洒的方式使NaOH溶液负载于步骤S5得到的蜂巢活性炭的表面,NaOH溶液与步骤S5得到的蜂巢活性炭的质量之比为1:1-1:2。
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