CN111167513B - 一种用于去除水中硝酸盐的柔性电催化膜及其制备方法和应用 - Google Patents
一种用于去除水中硝酸盐的柔性电催化膜及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种用于去除水中硝酸盐的柔性电催化膜及其制备方法和应用,属于电催化膜技术领域。本发明方法首先将芳纶纤维溶液滴加至水离子水中制得芳纶纳米纤维溶胶,然后将含有3,4‑乙烯二氧噻吩和硝酸铁的乙醇溶液与芳纶纳米纤维溶胶反应制得导电芳纶纳米纤维溶胶,最后将经四甲基氢氧化铵溶液超声预处理后的MXene纳米片滴加至导电芳纶纳米纤维溶胶中制得柔性电催化膜,制备出的柔性电催化膜具备良好的机械强度和柔性,在电催化还原硝酸盐过程中不仅能高效去除硝酸盐,而且可以解决电催化材料因表面污染而失效的问题,使用寿命长。
Description
技术领域
本发明具体涉及一种用于去除水中硝酸盐的柔性电催化膜及其制备方法和应用,属于电催化膜技术领域。
背景技术
地下水硝酸盐超标、城市污水厂碳源不足导致尾水硝酸盐偏高等问题成为水和污水处理的挑战。微生物反硝化法处理该类水体的过程中需要外加碳源,难以实际应用。同时,利用离子交换、电渗析、反渗透等技术处理该类水和污水,投资及维护费用高,寻求高效的硝酸盐去除方法是目前关注和研发的热点。
电催化还原法可在恒定电势的作用下使硝酸盐还原成氮气的过程自发进行。相较于上述处理技术,电催化还原法具备操作简单、能耗低、处理效率高等优点。然而,实际污水中存在颗粒和胶体物质,这些物质中富含金属离子、有机物、微生物,在电催化材料长期运行过程中,水中的胶体容易附着在其表面进而造成电催化材料功能的丧失。因此研发出一种既能够解决电催化还原硝酸盐过程中所面临的电催化材料因表面污染而失效的问题,又能高效去除硝酸盐的电催化材料是目前电催化还原法水处理技术中亟需解决的问题。
发明内容
针对现有技术中的问题,本发明提供一种用于去除水中硝酸盐的柔性电催化膜及其制备方法和应用,本发明方法操作简单,采用该方法制得的柔性电催化膜在电催化还原硝酸盐过程中不仅能高效去除硝酸盐,而且可以解决电催化材料因表面污染而失效的问题,使用寿命长。
为实现以上技术目的,本发明的技术方案是:
一种用于去除水中硝酸盐的柔性电催化膜的制备方法,包括如下步骤:
(4)芳纶纳米纤维溶胶的制备:
将芳纶纺织线破碎后加入到二甲基亚砜中,搅拌,然后加入氢氧化钾,继续搅拌至芳纶纤维完全溶解得到芳纶纤维溶液,将得到的芳纶纤维溶液滴加至去离子水中,搅拌一段时间后离心,取上层清液得到芳纶纳米纤维溶胶;
(5)导电芳纶纳米纤维溶胶的制备:
将3,4-乙烯二氧噻吩和硝酸铁溶解在乙醇中,搅拌均匀得混合溶液;将得到的混合溶液加入步骤(1)中制得的芳纶纳米纤维溶胶中,40~50℃反应1~3h,得到导电芳纶纳米纤维溶胶;
(6)柔性电催化膜的制备:
将MXene纳米片加入到四甲基氢氧化铵溶液中,冰浴超声处理1~2h,然后将超声处理后的MXene纳米片溶液滴加至步骤(2)中制得的导电芳纶纳米纤维溶胶中,搅拌1~2h后抽滤,得到柔性电催化膜。
优选地,步骤(1)中所述芳纶、二甲基亚砜、去离子水的用量比为1g:(300~800)mL:(2000~3000)mL。
优选地,步骤(1)中所述芳纶与氢氧化钾的质量比为1:(0.8~2)。
优选地,步骤(2)中所述3,4-乙烯二氧噻吩与硝酸铁的质量比为1:(1.5~3),所述的混合溶液与芳纶纳米纤维溶胶的体积比为1:(3~5)。
优选地,步骤(3)中所述MXene纳米片与导电芳纶纳米纤维溶胶的用量比为1g:(0.5~2)L。
采用上述任一方法制得的柔性电催化膜。
上述制得的柔性电催化膜在对硝酸盐电催化还原上的应用,步骤为:将柔性电催化膜作为阴极放置于第一容器中并将阴极与直流电源的负极相连,将石墨棒作为阳极放置于第二容器中并将阳极与直流电源的正极相连,第一容器的顶部和底部分别设有进水口和出水口,第一容器和第二容器通过连通管连通,连通管上设有质子交换膜,第一容器和第二容器中初始盛放有浓度相同的硝酸盐溶液。
优选地,所述硝酸盐溶液的pH值为6~9,浓度为1~10mg/L,所述直流电源的电压为0.6~1.0V,所述柔性电催化膜的水通量为50~150L/(m2 h bar)。
从以上描述可以看出,本发明具备以下优点:
1.本发明首先将芳纶纤维溶液滴加至水离子水中制得芳纶纳米纤维溶胶,然后将含有3,4-乙烯二氧噻吩和硝酸铁的乙醇溶液与芳纶纳米纤维溶胶反应制得导电芳纶纳米纤维溶胶,最后将经四甲基氢氧化铵溶液超声预处理后的MXene纳米片滴加至导电芳纶纳米纤维溶胶中制得柔性电催化膜,本发明制备方法简单,制备出的柔性电催化膜具备良好的机械强度和柔性,对硝酸盐的电催化还原效果显著,可适用于硝酸盐超标水和废水的快速处理。
2.现有普通电催化材料的还原活性位点均局限于材料表面,当实际污水中存在的颗粒和胶体物质附着在电催化材料表面时容易造成电催化材料的失效(如图2中a、b、c所示),相比于现有普通电催化材料,本发明制备的电催化膜对污水中的污染物具有优异的截留性能且富含发达的层间纳米水通道,其还原活性位点不仅分布于膜表面而且还分布在膜的多层水通道中,即使被截留至水中的污染物附着在电催化膜表面也不会造成电催化膜的失效(如图2中d所示),可以大大延长电催化膜的使用寿命。
附图说明
图1是实施例1制得的柔性电催化膜实物;
图2是实施例1制得的柔性电催化膜的断面扫描电镜图片;
图3是实施例1中电催化膜在应用时的膜催化系统的结构示意图;
图4是在表面附着有污染物颗粒后本发明制得的柔性电催化膜(d)与常用电催化材料(a/b/c)中还原活性位点的分布情况;
具体实施方式
下面通过实施例子,进一步阐述本发明的特点,但不对本发明的权利要求做任何限定。
实施例1:
一种用于去除水中硝酸盐的柔性电催化膜的制备方法,包括如下步骤:
(1)芳纶纳米纤维溶胶的制备:
将1g芳纶纺织线破碎后加入到300mL二甲基亚砜中,搅拌,然后加入0.8g氢氧化钾,继续搅拌至芳纶纤维完全溶解得到芳纶纤维溶液,将得到的芳纶纤维溶液滴加至2000mL去离子水中,搅拌2h后在2500rpm转速下离心,取上层清液得到芳纶纳米纤维溶胶;
(2)导电芳纶纳米纤维溶胶的制备:
将0.1g 3,4-乙烯二氧噻吩和0.15g硝酸铁溶解在50mL乙醇中,搅拌3h得混合溶液;将得到的混合溶液加入150mL步骤(1)中制得的芳纶纳米纤维溶胶中,40℃反应3h,得到导电芳纶纳米纤维溶胶;
(3)柔性电催化膜的制备:
将1g MXene纳米片(购于泰州北科纳米材料有限公司,该MXene纳米片具有超过两层的多层结构)加入到0.5g/L的四甲基氢氧化铵溶液中,冰浴超声处理1.5h,然后将超声处理后的MXene纳米片溶液滴加至500mL步骤(2)中制得的导电芳纶纳米纤维溶胶中,搅拌1.5h后抽滤,得到柔性电催化膜。该柔性电催化膜的电导率为1340S/cm。
如图3所示,柔性电催化膜在应用时的膜催化系统包括第一容器10、第二容器2、直流电源3、柔性电催化膜4和石墨棒5,其中,第一容器的顶部和底部分别设有进水口11和出水口12,第一容器10和第二容器2中初始均盛放有相同的硝酸盐溶液,第一容器10和第二容器2通过连通管6连通,连通管6上设有质子交换膜7,以防止电解过程中第二容器溶液中产生的氧化性物质由连通管进入第一容器中,柔性电催化膜4作为阴极放置于第一容器10中并将阴极与直流电源3的负极相连,石墨棒5作为阳极放置于第二容器2中并将阳极与直流电源3的正极相连。
取本实施例柔性电催化膜,在直流电源电压为0.8V、柔性电催化膜的水通量为100L/(m2 h bar)的条件下运行上述膜催化系统,柔性电催化膜在1h内对pH值中性、浓度为10mg/L(以N计)的硝酸盐溶液的氮气选择还原性可达76.7%。
实施例2:
一种用于去除水中硝酸盐的柔性电催化膜的制备方法,包括如下步骤:
(1)芳纶纳米纤维溶胶的制备:
将1g芳纶纺织线破碎后加入到500mL二甲基亚砜中,搅拌,然后加入1.5g氢氧化钾,继续搅拌至芳纶纤维完全溶解得到芳纶纤维溶液,将得到的芳纶纤维溶液滴加至2500mL去离子水中,搅拌2h后在2500rpm转速下离心,取上层清液得到芳纶纳米纤维溶胶;
(2)导电芳纶纳米纤维溶胶的制备:
将0.1g 3,4-乙烯二氧噻吩和0.20g硝酸铁溶解在100mL乙醇中,搅拌3h得混合溶液;将得到的混合溶液加入400mL步骤(1)中制得的芳纶纳米纤维溶胶中,45℃反应2h,得到导电芳纶纳米纤维溶胶;
(3)柔性电催化膜的制备:
将1g MXene纳米片(购于泰州北科纳米材料有限公司,该MXene纳米片具有超过两层的多层结构)加入到0.5g/L的四甲基氢氧化铵溶液中,冰浴超声处理1.5h,然后将超声处理后的MXene纳米片溶液滴加至1L步骤(2)中制得的导电芳纶纳米纤维溶胶中,搅拌1.5h后抽滤,得到柔性电催化膜。该柔性电催化膜的电导率890S/cm。
取本实施例柔性电催化膜,在直流电源电压为0.6V、柔性电催化膜的水通量为100L/(m2 h bar)的条件下运行与实施例1相同的膜催化系统,柔性电催化膜在1h内对pH值中性、浓度为10mg/L(以N计)的硝酸盐溶液的氮气选择还原性可达68.2%。
实施例3:
一种用于去除水中硝酸盐的柔性电催化膜的制备方法,包括如下步骤:
(1)芳纶纳米纤维溶胶的制备:
将1g芳纶纺织线破碎后加入到800mL二甲基亚砜中,搅拌,然后加入2g氢氧化钾,继续搅拌至芳纶纤维完全溶解得到芳纶纤维溶液,将得到的芳纶纤维溶液滴加至3000mL去离子水中,搅拌2h后在2500rpm转速下离心,取上层清液得到芳纶纳米纤维溶胶;
(2)导电芳纶纳米纤维溶胶的制备:
将0.1g 3,4-乙烯二氧噻吩和0.30g硝酸铁溶解在100mL乙醇中,搅拌3h得混合溶液;将得到的混合溶液加入500mL步骤(1)中制得的芳纶纳米纤维溶胶中,50℃反应1h,得到导电芳纶纳米纤维溶胶;
(3)柔性电催化膜的制备:
将1g MXene纳米片(购于泰州北科纳米材料有限公司,该MXene纳米片具有超过两层的多层结构)加入到0.5g/L的四甲基氢氧化铵溶液中,冰浴超声处理1.5h,然后将超声处理后的MXene纳米片溶液滴加至2L步骤(2)
中制得的导电芳纶纳米纤维溶胶中,搅拌1.5h后抽滤,得到柔性电催化膜。
该柔性电催化膜的电导率为570S/cm。
取本实施例柔性电催化膜,在直流电源电压为1.0V、柔性电催化膜的水通量为100L/(m2 h bar)的条件下运行与实施例1相同的膜催化系统,柔性电催化膜在1h内对pH值中性、浓度为10mg/L(以N计)的硝酸盐溶液的氮气选择还原性可达59.4%。
可以理解的是,以上关于本发明的具体描述,仅用于说明本发明而并非受限于本发明实施例所描述的技术方案。本领域的普通技术人员应当理解,仍然可以对本发明进行修改或等同替换,以达到相同的技术效果;只要满足使用需要,都在本发明的保护范围之内。
Claims (8)
1.一种用于去除水中硝酸盐的柔性电催化膜的制备方法,其特征在于,包括如下步骤:
(1)芳纶纳米纤维溶胶的制备:
将芳纶纺织线破碎后加入到二甲基亚砜中,搅拌,然后加入氢氧化钾,继续搅拌至芳纶纤维完全溶解得到芳纶纤维溶液,将得到的芳纶纤维溶液滴加至去离子水中,搅拌一段时间后离心,取上层清液得到芳纶纳米纤维溶胶;
(2)导电芳纶纳米纤维溶胶的制备:
将3,4-乙烯二氧噻吩和硝酸铁溶解在乙醇中,搅拌均匀得混合溶液;将得到的混合溶液加入步骤(1)中制得的芳纶纳米纤维溶胶中,40~50℃反应1~3h,得到导电芳纶纳米纤维溶胶;
(3)柔性电催化膜的制备:
将MXene纳米片加入到四甲基氢氧化铵溶液中,冰浴超声处理1~2h,然后将超声处理后的MXene纳米片溶液滴加至步骤(2)中制得的导电芳纶纳米纤维溶胶中,搅拌1~2h后抽滤,得到柔性电催化膜。
2.如权利要求1所述的柔性电催化膜的制备方法,其特征在于,步骤(1)中所述芳纶、二甲基亚砜、去离子水的用量比为1g:(300~800)mL:(2000~3000)mL。
3.如权利要求1所述的柔性电催化膜的制备方法,其特征在于,步骤(1)中所述芳纶与氢氧化钾的质量比为1:(0.8~2)。
4.如权利要求1所述的柔性电催化膜的制备方法,其特征在于,步骤(2)中所述3,4-乙烯二氧噻吩与硝酸铁的质量比为1:(1.5~3),所述的混合溶液与芳纶纳米纤维溶胶的体积比为1:(3~5)。
5.如权利要求1所述的柔性电催化膜的制备方法,其特征在于,步骤(3)中所述MXene纳米片与导电芳纶纳米纤维溶胶的用量比为1g:(0.5~2)L。
6.采用权利要求1~5任一所述的方法制得的柔性电催化膜。
7.如权利要求6所述的柔性电催化膜在对硝酸盐电催化还原上的应用,其特征在于,步骤为:将柔性电催化膜作为阴极放置于第一容器中并将阴极与直流电源的负极相连,将石墨棒作为阳极放置于第二容器中并将阳极与直流电源的正极相连,第一容器的顶部和底部分别设有进水口和出水口,第一容器和第二容器通过连通管连通,连通管上设有质子交换膜,第一容器和第二容器中初始盛放有浓度相同的硝酸盐溶液。
8.如权利要求7所述的应用,其特征在于,所述硝酸盐溶液的pH值为6~9,浓度为1~10mg/L,所述直流电源的电压为0.6~1.0V,所述柔性电催化膜的水通量为50~150L/(m2.h.bar)。
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