CN113546625B - 一种静电纺缺陷态TiO2/Fe3O4复合纳米纤维材料及其制备方法 - Google Patents
一种静电纺缺陷态TiO2/Fe3O4复合纳米纤维材料及其制备方法 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 40
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- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 13
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 48
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- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 3
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种缺陷态TiO2/Fe3O4复合纳米纤维材料及其制备方法,属于材料技术领域。本发明中材料的制备方法包括以下步骤,首先将钛源、铁源和高分子聚合物分散在溶剂中制成稳定均匀的溶液;随后通过静电纺丝技术将上述溶液制成纳米纤维膜;将纳米纤维膜进行煅烧,再将煅烧后的材料与硼氢化钠研磨,在氮气氛围中进行还原,得到缺陷态TiO2/Fe3O4复合纳米纤维材料。本方法操作简单易控制,环境友好,且可以连续化生产,获得的缺陷态TiO2/Fe3O4复合纳米纤维材料具有良好的结晶性和光响应性,对水环境中的有机污染物具有优异的降解性能。
Description
技术领域
本发明涉及一种缺陷态TiO2/Fe3O4复合纳米纤维材料及其制备方法,属于材料技术领域。
背景技术
在高级氧化工艺中,大量的前期研究工作多集中于通过芬顿技术降解污染物。但芬顿法需要在酸性条件下进行,且反应后产生的含铁污泥也需要进一步处理,限制了芬顿法的发展。光催化技术作为另一类的高级氧化工艺,具有反应条件温和,技术设备简单且无二次污染的优点。将芬顿反应引入光催化体系中形成光芬顿体系可有效解决芬顿过程中高价金属离子/低价金属离子的问题,同时,也可以解决光催化过程中光生载流子复合率高引起的光催化活性低的问题。为了充分利用芬顿技术和光催化技术在污染物降解中的各自优势,构建新型的具有宽太阳光谱响应的光芬顿催化剂具有重要意义。在各类光催化剂中,TiO2的化学性质稳定,无毒且成本低廉,因此已成为最广泛使用的光催化剂之一。但TiO2带隙较宽,光吸收范围窄,光能利用率低,光催化活性不高,而在高温或高压下对TiO2进行氢化,可得到缺陷态TiO2,通过引入晶格缺陷来改善TiO2的晶体结构,可以优化其电子能级结构,缩短带隙宽度,改善光学性能,并将其光学响应范围从紫外区扩展到可见区。
而针对纳米粉体的光催化剂极易团聚影响光吸收效率,且难以分离回收,存在二次污染的问题,可利用高压静电纺丝技术将其制备成纳米纤维,能有效解决粉体光催化剂的流失问题,达到光催化剂的快速回收再利用,还能更为有效地利用太阳光更好发挥催化剂特性,提高光催化活性。
发明内容
本发明的主要目的是提供一种条件温和、环境友好的制备缺陷态TiO2/Fe3O4复合纳米纤维材料的方法。
本发明中的缺陷态TiO2/Fe3O4复合纳米纤维材料的具体制备方法如下:
1)将钛源、铁源和高分子聚合物分散在溶剂中,制成稳定均一的溶液;
2)通过静电纺丝技术将步骤1)得到的溶液制成纳米纤维膜。纺丝溶液在高压电场力的牵引下流动拉伸成为亚微米级甚至纳米级别尺寸的超细纤维,然后经溶体挥发或冷却,高分子聚合物固化,钛源会与空气中的水分进行快速的水解缩合反应,生成无定形的氧化钛;
3)将步骤2)中的纳米纤维膜先在空气中进行煅烧,再与硼氢化钠粉末进行均匀混合后,在惰性气体氛围中进行还原,得到缺陷态TiO2/Fe3O4复合纳米纤维材料。
步骤1)中钛与铁的原子比为(5-100):1;钛源和铁源质量之和与高分子聚合物的质量的比为(1-10):1;搅拌时间为60-720min。所述钛源为钛酸四正丁酯或钛酸四乙酯;所述铁源为无水氯化铁、九水硝酸铁、硫酸铁中的一种;所述的高分子聚合物为聚乙烯吡咯烷酮或聚丙烯腈与聚甲基丙烯酸甲酯中两种混合。所述溶剂为二甲基甲酰胺和二甲基乙酰胺中的一种或两种混合。
步骤2)所述的静电纺丝技术的过程参数为:纺丝电压为15-40kV;滚筒转速为200-1000r/min;溶液的给料流速为0.1-5mL/h;纺丝针头与滚筒的距离为10-30cm。
步骤3)所述的煅烧是指在350-1000℃条件下保持0.5-3h;所述的在惰性气体氛围中的还原是指在氮气或氩气的保护下,温度从室温升高至200-500℃,升温速率为1-10°C/min,并在最高温度条件下保持0.5-2h。
本发明还提出以上所述的制备方法制备的一种缺陷态TiO2/Fe3O4复合纳米纤维材料,所述的复合纳米纤维材料的纤维直径为200-700nm;光响应范围为紫外以及可见光区域。所述的复合纳米纤维材料具有良好的结晶性和可见光响应性。所述的复合纳米纤维材料可应用于废水中有机污染物的降解以及光解水制氢。
本发明的原理与方法
钛源溶胶通常可纺性较差,铁源的添加使得纺丝难度大幅增加,而添加高分子聚合物可作为助纺剂增加其可纺性。在静电纺丝过程中,纺丝溶液在高压电场力的牵引下流动拉伸成为亚微米级甚至纳米级别尺寸的超细纤维,然后经溶体挥发或冷却,高分子聚合物固化,钛源会与空气中的水分进行快速的水解缩合反应,生成无定形的氧化钛,而铁离子则会均匀分布在单根纳米纤维上,得到复合纳米纤维。煅烧过程中,经预氧化处理后的纤维将会发生分解,残留的N、H、O元素进一步脱除。还原过程中,在充满氮气的氛围中,部分四价钛离子被硼氢化钠还原为三价钛,由于三价钛的自掺杂,改善了TiO2的晶体结构,优化电子能级结构,缩短带隙宽度,使得光学响应范围从紫外区扩展到可见区。而三价铁离子则被还原为四氧化三铁,具有很高的氧化活性,与氧化钛复合,可大幅度提高材料的光催化活性。
本发明的主要优点
相比于现有的光催化纳米纤维材料及其制备方法,本发明具有以下优点:
1.本发明所述的缺陷态TiO2/Fe3O4复合纳米纤维材料在制备过程中采用一步还原生成缺陷态氧化钛和二价铁的方法,制备条件简单、温和安全,且实现了材料微观的良好复合,不会存在颗粒的脱落问题。
2.本发明所述的缺陷态TiO2/Fe3O4复合纳米纤维材料采用掺杂及复合的方法协同增强材料的光学特性:通过还原的方法获得Ti3+自掺杂,引入晶格缺陷改善TiO2的晶体结构,优化电子能级结构,缩短带隙宽度,使得光学响应范围从紫外区扩展到可见区。同时还原得到的四氧化三铁与缺陷态氧化钛形成类光芬顿体系,可大幅度提高材料的光催化活性,而且,相较于芬顿体系通常需要较低pH的局限性(pH<3),所建立的类光芬顿体系具有更宽的pH适应范围,且在中性条件下效果更好,处理废水时无需调节水质酸碱性,可节约成本。
附图说明
图1为本发明实施例1制备的缺陷态TiO2/Fe3O4复合纳米纤维材料的照片。
图2为本发明实施例1制备的缺陷态TiO2/Fe3O4复合纳米纤维材料的微观扫描电镜图。
图3为本发明实施例1制备的缺陷态TiO2/Fe3O4复合纳米纤维材料的X射线衍射图谱。
图4为本发明实施例1制备的缺陷态TiO2/Fe3O4复合纳米纤维材料的紫外-可见漫反射光谱。
图5为以实施例1制备的缺陷态TiO2/Fe3O4复合纳米纤维材料为催化剂,水中环丙沙星的降解曲线。
具体实施方式
下面通过实施例结合附图对本发明进行详细的描述。
实施例1
将1.6g聚乙烯吡咯烷酮和3.2g聚甲基丙烯酸甲酯固体粉末加入20mL二甲基甲酰胺中,在室温下经磁力搅拌形成均一溶液,随后加入2ml乙酸和4ml钛酸四正丁酯和0.095g无水氯化铁,继续搅拌2h,获得均匀的纺丝液,其中Ti和Fe原子比为20:1。将配制好的纺丝液转移至20ml的注射器中用于高压静电纺丝。静电纺丝控制电压为18kV,滚筒转速为400r/min,纺丝头针尖至滚筒接收器之间的距离为15cm,纺丝液给液流速为1mL h-1,使用铝箔接收,制备纳米纤维膜;将获得的纳米纤维膜置于管式炉中进行煅烧处理,升温速率为10℃min-1,温度设为700℃,煅烧时间为2h;将煅烧后的材料与NaBH4研磨,并在氮气流量为100mLmin-1的氛围中进行还原,其中TiO2与NaBH4的质量比为1:2,升温速率为10℃ min-1,还原温度设为300℃,1h后获得成品。
实施例2
将1.0g聚乙烯吡咯烷酮和2.0g聚甲基丙烯酸甲酯固体粉末加入20mL二甲基甲酰胺中,在室温下经磁力搅拌形成均一溶液,随后加入2ml乙酸和4ml钛酸四正丁酯和0.095g无水氯化铁,继续搅拌2h,获得均匀的纺丝液,其中Ti和Fe原子比为20:1。将配制好的纺丝液转移至20ml的注射器中用于高压静电纺丝。静电纺丝控制电压为15kV,滚筒转速为400r/min,纺丝头针尖至滚筒接收器之间的距离为15cm,纺丝液给液流速为1mL h-1,使用铝箔接收,制备纳米纤维膜;将获得的纳米纤维膜置于管式炉中进行煅烧处理,升温速率为10℃min-1,温度设为350℃,煅烧时间为3h;将煅烧后的材料与NaBH4研磨,并在氮气流量为100mLmin-1的氛围中进行还原,其中TiO2与NaBH4的质量比为1:2,升温速率为10℃ min-1,还原温度设为200℃,2h后获得成品。
实施例3
将1.6g聚乙烯吡咯烷酮和3.2g聚甲基丙烯酸甲酯固体粉末加入20mL二甲基乙酰胺中,在室温下经磁力搅拌形成均一溶液,随后加入2ml乙酸和4ml钛酸四乙酯和0.04g无水氯化铁,继续搅拌0.5h,获得均匀的纺丝液,其中Ti和Fe原子比为50:1。将配制好的纺丝液转移至20ml的注射器中用于高压静电纺丝。静电纺丝控制电压为18kV,滚筒转速为400r/min,纺丝头针尖至滚筒接收器之间的距离为20cm,纺丝液给液流速为1mL h-1,使用铝箔接收,制备纳米纤维膜;将获得的纳米纤维膜置于管式炉中进行煅烧处理,升温速率为10℃min-1,温度设为600℃,煅烧时间为2.5h;将煅烧后的材料与NaBH4研磨,并在氮气流量为100mL min-1的氛围中进行还原,其中TiO2与NaBH4的质量比为1:2,升温速率为8℃ min-1,还原温度设为400℃,1.5h后获得成品。
实施例4
将1.5g聚乙烯吡咯烷酮和3.0g聚甲基丙烯酸甲酯固体粉末加入10mL二甲基甲酰胺和10mL二甲基乙酰胺的混合液中,在室温下经磁力搅拌形成均一溶液,随后加入2ml乙酸和4ml钛酸四正丁酯和0.067g无水氯化铁,继续搅拌2h,获得均匀的纺丝液,其中Ti和Fe原子比为30:1。将配制好的纺丝液转移至20ml的注射器中用于高压静电纺丝。静电纺丝控制电压为20kV,滚筒转速为400r/min,纺丝头针尖至滚筒接收器之间的距离为20cm,纺丝液给液流速为2mL h-1,使用铝箔接收,制备纳米纤维膜;将获得的纳米纤维膜置于管式炉中进行煅烧处理,升温速率为10℃ min-1,温度设为800℃,煅烧时间为2h;将煅烧后的材料与NaBH4研磨,并在氮气流量为100mL min-1的氛围中进行还原,其中TiO2与NaBH4的质量比为1:2,升温速率为10℃ min-1,还原温度设为400℃,2h后获得成品。
实施例5
将2.0g聚丙烯腈和4.0g聚甲基丙烯酸甲酯固体粉末加入20mL二甲基甲酰胺中,在室温下经磁力搅拌形成均一溶液,随后加入2ml乙酸和4ml钛酸四正丁酯和0.19g九水硝酸铁,继续搅拌2h,获得均匀的纺丝液,其中Ti和Fe原子比为10:1。将配制好的纺丝液转移至20ml的注射器中用于高压静电纺丝。静电纺丝控制电压为25kV,滚筒转速为400r/min,纺丝头针尖至滚筒接收器之间的距离为25cm,纺丝液给液流速为3mL h-1,使用铝箔接收,制备纳米纤维膜;将获得的纳米纤维膜置于管式炉中进行煅烧处理,升温速率为10℃ min-1,温度设为900℃,煅烧时间为1.5h;将煅烧后的材料与NaBH4研磨,并在氮气流量为100mL min-1的氛围中进行还原,其中TiO2与NaBH4的质量比为1:2,升温速率为10℃ min-1,还原温度设为500℃,0.5h后获得成品。
实施例6
将2.4g聚乙烯吡咯烷酮和4.8g聚甲基丙烯酸甲酯固体粉末加入20mL二甲基甲酰胺中,在室温下经磁力搅拌形成均一溶液,随后加入2ml乙酸和4ml钛酸四乙酯和0.38g硫酸铁,继续搅拌3h,获得均匀的纺丝液,其中Ti和Fe原子比为5:1。将配制好的纺丝液转移至20ml的注射器中用于高压静电纺丝。静电纺丝控制电压为28kV,滚筒转速为400r/min,纺丝头针尖至滚筒接收器之间的距离为30cm,纺丝液给液流速为5mL h-1,使用铝箔接收,制备纳米纤维膜;将获得的纳米纤维膜置于管式炉中进行煅烧处理,升温速率为10℃ min-1,温度设为1000℃,煅烧时间为1h;将煅烧后的材料与NaBH4研磨,并在氮气流量为100mL min-1的氛围中进行还原,其中TiO2与NaBH4的质量比为1:2,升温速率为10℃ min-1,还原温度设为500℃,1h后获得成品。
实施例7
将1.6g聚丙烯腈和3.2g聚甲基丙烯酸甲酯固体粉末加入20mL二甲基乙酰胺中,在室温下经磁力搅拌形成均一溶液,随后加入2ml乙酸和4ml钛酸四正丁酯和0.095g无水氯化铁,继续搅拌2h,获得均匀的纺丝液,其中Ti和Fe原子比为20:1。将配制好的纺丝液转移至20ml的注射器中用于高压静电纺丝。静电纺丝控制电压为20kV,滚筒转速为500r/min,纺丝头针尖至滚筒接收器之间的距离为18cm,纺丝液给液流速为1.5mL h-1,使用铝箔接收,制备纳米纤维膜;将获得的纳米纤维膜置于管式炉中进行煅烧处理,升温速率为10℃ min-1,温度设为700℃,煅烧时间为3h;将煅烧后的材料与NaBH4研磨,并在氮气流量为100mL min-1的氛围中进行还原,其中TiO2与NaBH4的质量比为1:2,升温速率为5℃min-1,还原温度设为300℃,2h后获得成品。
Claims (6)
1.一种缺陷态TiO2/Fe3O4复合纳米纤维材料在水中降解环丙沙星的应用,其特征在于,所述的复合纳米纤维材料的制备步骤为:
1)将钛源、铁源和高分子聚合物分散在溶剂中制成稳定均一的溶液,所述钛源的种类为钛酸四正丁酯或钛酸四乙酯,所述铁源的种类为无水氯化铁、九水硝酸铁、硫酸铁中的一种;
2)通过静电纺丝技术将步骤1)得到的溶液制成纳米纤维膜;
3)将步骤2)中的纳米纤维膜先在空气中进行煅烧,再与硼氢化钠粉末进行均匀混合后,在惰性气体氛围中进行还原,得到缺陷态TiO2/Fe3O4复合纳米纤维材料。
2.根据权利要求1所述的应用,其特征在于所述的步骤1)中钛与铁的原子比为(5-100):1;钛源和铁源质量之和与高分子聚合物的质量的比为(1-10):1。
3.根据权利要求1所述的应用,其特征在于,所述的高分子聚合物为聚乙烯吡咯烷酮与聚甲基丙烯酸甲酯的混合物或者聚丙烯腈与聚甲基丙烯酸甲酯的混合物;所述溶剂为二甲基甲酰胺和二甲基乙酰胺中的一种或两种混合。
4.根据权利要求1所述的应用,其特征在于,步骤3)所述的煅烧是指在350-1000℃条件下保持0.5-3h;所述的在惰性气体氛围中的还原是指在氮气或氩气的保护下,温度从室温升高至200-400℃,升温速率为1-10℃/min,并在最高温度条件下保持0.5-2h。
5.根据权利要求1-4中任一项所述的应用,其特征在于,该复合纳米纤维材料的纤维直径为200-700nm。
6.根据权利要求1-4中任一项所述的应用,其特征在于,该复合纳米纤维材料具有良好的结晶性和可见光响应性。
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