CN108190855B - 用于水中离子脱除的掺杂三维多孔碳及其制备方法 - Google Patents
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Abstract
本发明涉及一种用于水中离子脱除的掺杂三维多孔碳及其制备方法,本发明以聚苯乙烯微球为硬模板,以石墨烯为增强导电性的助剂,以壳聚糖及植酸为氮、磷元素掺杂源并起到阻碍石墨烯重新堆叠的作用。可应用于海水淡化、水中重金属离子的脱除以及超级电容器、锂离子电池的电极材料,本发明的优点在于增加了碳材料的润湿性和导电性,工艺简单、成本低。
Description
技术领域
本发明涉及一种用于水中离子脱除的掺杂三维多孔碳及其制备方法,可用于水中盐分或重金属离子的脱除。
背景技术
淡水资源是全球部分地区的匮乏资源,海水淡化技术的进步为沿海的缺水地区带来了利好。电容器脱盐法是一种新兴的高效、低成本的海水淡化法。电容器脱盐方法是一种利用电化学双电层原理,通过高比表面积、孔道丰富的电极材料对水中含有的离子进行吸附和储存的方法。通过在平行板电容器电极之间施加一定强度的电场,填充在电极之间的水中的离子会在电场作用下向电性相反的电极方向移动,并且最终吸附在电极材料的外表面及孔道表面上,达到去除离子的效果。
对电容器脱盐来说最重要的脱盐电极材料,对脱盐电极材料的要求是对水的润湿性好、导电性好、化学稳定性好、脱盐比容量高。Caudle等人最早将活性炭用于电容器脱盐,为电容器脱盐奠定了基础;Hae-Hyun Junga等人采用溶剂交换法制备了间苯二酚/甲醛凝胶,然后煅烧制得碳气凝胶脱盐电极;Rudra Kumar等人利用溶胶-凝胶法制备了有机/无机前驱体,并进一步煅烧制备了碳气凝胶脱盐电极。还有许多研究人员也尝试制备了很多新型脱盐电极材料,但是对于脱盐电极材料的润湿性差、比容量低的缺点仍未很好的解决,同时还存在脱盐电极材料成本高的缺点。
发明内容
本发明的目的之一在于提供了一种用于水中离子脱除的掺杂三维多孔碳。
本发明的目的之二在于提供该掺杂三维多孔碳的制备方法,该方法通过氮、磷元素共掺杂提高了电极材料的亲水性和导电性,并且脱盐比容量高,制备成本低。氮、磷元素掺杂到碳的晶格中,导致碳的晶格出现缺陷,电子云分布不再均匀,因而增加了碳的导电性;同时碳与杂原子形成的化学键是极性键,与同样具有极性的水分子亲和力强,因而增强了碳材料对水的润湿性。本发明中,植酸含有磷元素,作为磷源;壳聚糖含有氮元素,作为氮源,并且壳聚糖可以阻碍氧化石墨烯层的堆叠,有利于获得高比表面积材料。
为达到上述目的,本发明采用如下技术方案:
一种用于水中离子脱除的掺杂三维多孔碳,其特征在于该掺杂三维多孔碳是由直径为100~400 nm的中空碳球及不完整的中空碳球构成,各碳球之间有薄层碳相连,氮与磷元素掺杂在碳球球壳与薄层碳中,其中氮、磷和碳的质量比为:0.5~3:2~6:85~95。
一种制备上述的用于水中离子脱除的掺杂三维多孔碳的方法,其特征在于该方法的具体步骤为:
a. 将粒径为100~300 nm聚苯乙烯微球的分散液加入浓度为2.5~7.5 mg/ml五倍子酸水溶液,然后混合均匀,然后边搅拌边向其中加入浓度为10~20 mg/ml的三价铁离子盐水溶液,搅拌20~40 min,然后向其中加入浓度为1~4 mg/ml的氧化石墨烯水溶液,然后将含有0.5~2 ml乙酸的浓度为5~15 mg/ml的壳聚糖水溶液加入上述溶液并搅拌均匀,然后再加入质量分数为40%~60%的植酸溶液并搅拌,最终得到混合物;所述聚苯乙烯微球分散液含有的苯乙烯微球质量、五倍子酸水溶液含有的五倍子酸质量、三价铁离子盐水溶液所含有的三价铁离子质量、壳聚糖水溶液含有的壳聚糖质量、氧化石墨烯水溶液含有的氧化石墨烯质量与植酸溶液含有的植酸的质量比例分别在0.5~1:1~2:0.1~0.3:1~2 :0.08~0.3:0.2~0.4
b. 将步骤a所得到的混合物进行离心分离,将所得沉淀物冷冻干燥,得到干燥产物;
c. 将步骤b所得的干燥产物在惰性气氛中,700℃~900℃下煅烧1.5~4小时,然后将煅烧产物在1~3 mol/L的盐酸、硫酸或硝酸中浸渍刻蚀,然后边过滤边加水洗涤,直至滤液pH在6~8,然后将所得的固体烘干,即得到用于水中离子脱除的掺杂三维多孔碳。
上述的含有三价铁离子的溶液是三氯化铁、硫酸铁、硝酸铁、乙酸铁中的一种的水溶液。
本发明提供的一种三维多孔碳的制备方法具有工艺简单、成本低、脱盐量高的特征,具有突出的实质性特点和显著的进步。本发明制备的用于水中离子脱除的掺杂三维多孔碳可应用于海水淡化、水中重金属离子的脱除以及超级电容器、锂离子电池的电极材料,。
附图说明
图1是实施例1的透射电子显微镜照片;
图2中的曲线都是电压在1.2V、流速为40ml/min、氯化钠溶液浓度为500ppm条件下的电容器脱盐的测试结果,曲线a是实施例一的脱盐测试结果,曲线b是实施例二的脱盐测试结果,曲线c是实施例三的脱盐测试结果,曲线d是实施例四的测试结果。
具体实施方式
为了更清楚地说明本发明,列举以下实施例,但本发明可实施的情况并不仅限于实施例的范围。
实施例一:
将1g五倍子酸一水合物溶于200ml去离子水,通过磁力搅拌搅成均一溶液,再加入浓度为50mg/ml的聚苯乙烯微球水分散液10ml,搅拌均匀,然后用注射泵以30ml/h的速率向上述混合物中逐滴滴加12.5mg/ml的乙酸铁水溶液40ml,然后向其中加入2mg/ml的氧化石墨烯溶液40ml,然后以400rpm转速下搅拌30min。然后将含有1.5ml质量分数为36%的乙酸和1g壳聚糖的水溶液100ml加入上述混合物,在400rpm转速下搅拌1h,然后向其中加入0.2g植酸溶液并继续搅拌30min,然后将所得混合物在6000rpm下离心5min,将沉淀物以冷冻干燥使其充分干燥,将干燥后的产物在氩气中、800℃下煅烧2h,升温速率为5℃/min。然后将煅烧后产物浸入2mol/L的盐酸溶液中,并搅拌24h,然后将其稀释后抽滤,并用去离子水洗涤至中性,然后将所得固体在60℃下烘干,即可得到三维多孔碳材料。
将烘干后的粉末与导电炭黑super p、PTFE 5wt%乙醇溶液一起混合均匀,均匀地涂覆于石墨纸上,厚度不大于200μm,然后在120℃下烘干。测试脱盐量是在1.2V电压、流速为40ml/min、NaCl浓度为500ppm条件下进行的。
实施例二:
将1g五倍子酸一水合物溶于200ml去离子水,通过磁力搅拌搅成均一溶液,再加入浓度为50mg/ml的聚苯乙烯微球水分散液10ml,搅拌均匀,然后用注射泵以30ml/h的速率向上述混合物中逐滴滴加12.5mg/ml的硫酸铁水溶液40ml,然后向其中加入2mg/ml的氧化石墨烯溶液40ml,然后以400rpm转速下搅拌30min。然后将含有1.5ml质量分数为36%的乙酸和1g壳聚糖的水溶液100ml加入上述混合物,在400rpm转速下搅拌1h,然后向其中加入0.2g植酸溶液并继续搅拌30min,然后将所得混合物在6000rpm下离心5min,将沉淀物以冷冻干燥使其充分干燥,将干燥后的产物在氩气中、800℃下煅烧2h,升温速率为5℃/min。然后将煅烧后产物浸入2mol/L的盐酸溶液中,并搅拌24h,然后将其稀释后抽滤,并用去离子水洗涤至中性,然后将所得固体在60℃下烘干,即可得到三维多孔碳材料。
将烘干后的粉末与导电炭黑super p、PTFE 5wt%乙醇溶液一起混合均匀,均匀地涂覆于石墨纸上,厚度不大于200μm,然后在120℃下烘干。测试脱盐量是在1.2V电压、流速为40ml/min、NaCl浓度为500ppm条件下进行的。
实施例三:
将1g五倍子酸一水合物溶于200ml去离子水,通过磁力搅拌搅成均一溶液,再加入浓度为50mg/ml的聚苯乙烯微球水分散液10ml,搅拌均匀,然后用注射泵以30ml/h的速率向上述混合物中逐滴滴加12.5mg/ml的六水合氯化铁水溶液40ml,然后向其中加入2mg/ml的氧化石墨烯溶液40ml,然后以400rpm转速下搅拌30min。然后将含有1.5ml质量分数为36%的乙酸和1g壳聚糖的水溶液100ml加入上述混合物,在400rpm转速下搅拌1h,然后向其中加入0.2g植酸溶液并继续搅拌30min,然后将所得混合物在6000rpm下离心5min,将沉淀物以冷冻干燥使其充分干燥,将干燥后的产物在氩气中、800℃下煅烧2h,升温速率为5℃/min。然后将煅烧后产物浸入2mol/L的盐酸溶液中,并搅拌24h,然后将其稀释后抽滤,并用去离子水洗涤至中性,然后将所得固体在60℃下烘干,即可得到三维多孔碳材料。
将烘干后的粉末与导电炭黑super p、PTFE 5wt%乙醇溶液一起混合均匀,均匀地涂覆于石墨纸上,厚度不大于200μm,然后在120℃下烘干。测试脱盐量是在1.2V电压、流速为40ml/min、NaCl浓度为500ppm条件下进行的。
实施例四:
将1g五倍子酸一水合物溶于200ml去离子水,通过磁力搅拌搅成均一溶液,再加入浓度为50mg/ml的聚苯乙烯微球水分散液10ml,搅拌均匀,然后用注射泵以30ml/h的速率向上述混合物中逐滴滴加12.5mg/ml的九水合硝酸铁铁水溶液40ml,然后向其中加入2mg/ml的氧化石墨烯溶液40ml,然后以400rpm转速下搅拌30min。然后将含有1.5ml质量分数为36%的乙酸和1g壳聚糖的水溶液100ml加入上述混合物,在400rpm转速下搅拌1h,然后向其中加入0.2g植酸溶液并继续搅拌30min,然后将所得混合物在6000rpm下离心5min,将沉淀物以冷冻干燥使其充分干燥,将干燥后的产物在氩气中、800℃下煅烧2h,升温速率为5℃/min。然后将煅烧后产物浸入2mol/L的盐酸溶液中,并搅拌24h,然后将其稀释后抽滤,并用去离子水洗涤至中性,然后将所得固体在60℃下烘干,即可得到三维多孔碳材料。
将烘干后的粉末与导电炭黑super p、PTFE 5wt%乙醇溶液一起混合均匀,均匀地涂覆于石墨纸上,厚度不大于200μm,然后在120℃下烘干。测试脱盐量是在1.2V电压、流速为40ml/min、NaCl浓度为500ppm条件下进行的。
根据图2所示的测试结果,实施例一的所述方案是最优方案。
上述对于示例性实施例进行说明,不应理解为对本发明进行限制。虽然已经公开了多个示例性实施例,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。因此,采用与本发明上述实施例相同或近似的步骤及结构,而得到的其他的三维多孔碳的制备方法,均在本发明的保护范围之内。
Claims (2)
1.一种用于水中离子脱除的掺杂三维多孔碳,其特征在于该掺杂三维多孔碳是由直径为100~400nm的中空碳球及不完整的中空碳球构成,各碳球之间有薄层碳相连,氮与磷元素掺杂在碳球球壳与薄层碳中,其中氮、磷和碳的质量比为:0.5~3:2~6:85~95;采用如下方法制备而成:该方法的具体步骤为:
a.将粒径为100~300nm聚苯乙烯微球的分散液加入浓度为2.5~7.5mg/ml五倍子酸水溶液,然后混合均匀,然后边搅拌边向其中加入浓度为10~20mg/ml的三价铁离子盐水溶液,搅拌20~40min,然后向其中加入浓度为1~4mg/ml的氧化石墨烯水溶液,然后将含有0.5~2ml乙酸的浓度为5~15mg/ml的壳聚糖水溶液加入上述溶液并搅拌均匀,然后再加入质量分数为40%~60%的植酸溶液并搅拌,最终得到混合物;所述聚苯乙烯微球分散液含有的聚苯乙烯微球质量、五倍子酸水溶液含有的五倍子酸质量、三价铁离子盐水溶液所含有的三价铁离子质量、壳聚糖水溶液含有的壳聚糖质量、氧化石墨烯水溶液含有的氧化石墨烯质量与植酸溶液含有的植酸的质量比例分别在0.5~1:1~2:0.1~0.3:1~2:0.08~0.3:0.2~0.4;
b.将步骤a所得到的混合物进行离心分离,将所得沉淀物冷冻干燥,得到干燥产物;
c.将步骤b所得的干燥产物在惰性气氛中,700℃~900℃下煅烧1.5~4小时,然后将煅烧产物在1~3mol/L的盐酸、硫酸或硝酸中浸渍刻蚀,然后边过滤边加水洗涤,直至滤液pH在6~8,然后将所得的固体烘干,即得到用于水中离子脱除的掺杂三维多孔碳。
2.根据权利要求1所述用于水中离子脱除的掺杂三维多孔碳,其特征在于所述的含有三价铁离子的溶液是三氯化铁、硫酸铁、硝酸铁、乙酸铁中的一种的水溶液。
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