CN106693947A - 一种钙掺杂的二氧化钛纳米纤维光催化剂的制备方法 - Google Patents
一种钙掺杂的二氧化钛纳米纤维光催化剂的制备方法 Download PDFInfo
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Abstract
本发明公开一种钙掺杂的二氧化钛纳米纤维光催化剂的制备方法，其包括以下步骤：（1）配置溶液A：将一定量的乙酸、聚乙烯比咯烷酮加到乙醇溶液，搅拌后形成透明溶液A；（2）取一定量的钛酸异丙酯和乙酸钙加到（1）配置的溶液A中。搅拌均匀后得到透明的溶胶溶液B；（3）将上述制备的溶胶溶液B进行静电纺丝；（4）将（3）制备的样品室温干燥24~96小时，然后置于高温炉中在450~700°C煅烧，即可制得Ca2+掺杂的TiO2纳米纤维。采用该方法制备的Ca2+掺杂的TiO2纳米纤维对有机染料具有优异的光催化降解性能。
Description
技术领域
本发明涉及一种钙掺杂的二氧化钛纳米纤维光催化剂的制备方法，属于材料制备技术领域。
背景技术
自1972年Fujishima和Honda报道了在光电池中光辐射二氧化钛(TiO2)可持续地发生水的氧化还原反应并产生氢气以来，有关TiO2等半导体光催化剂的研究已成为催化领域的研究热点。纳米TiO2因其价格低廉、无毒无污染、催化活性高、性能稳定及可回收利用等优点，使其在光催化领域得到广泛研究。但是TiO2的禁带宽度为3.0 ～3.2 eV，只能在紫外光区才有吸收，而紫外光在太阳光中只占3%～5%，这严重限制了其在光催化领域的应用。因此，为提高二氧化钛的光催化效果，人们通过采用贵金属沉积，半导体复合, 金属或非金属掺杂等方法来对二氧化钛改性以促进其吸收光向长波方向移动，拓展其光谱响应范围(>387 nm)，提高其可见光活性并抑制电子-空穴对的复合。20世纪90年代以来的相关研究结果表明,掺杂Ag+ 、Fe3+ 、Mo5+ 、Ru3+ 、Os3+ 、Re5+ 、V4+ 和Rh3+ 可显著提高TiO2催化剂的光催化氧化效果。
本文以乙酸钙作为钙源，钛酸异丙酯为钛源，采用静电纺丝和溶胶-凝胶法制备了不同Ca2+掺杂浓度的TiO2纳米纤维光催化剂，研究结果表明Ca2+掺杂对TiO2光催化活性有很大的提高。
发明内容
本发明所要解决的技术问题是基于不同Ca2+掺杂浓度的TiO2纳米纤维的优良的光催化性能，提供一种制备基于钙掺杂的二氧化钛纳米纤维光催化剂的制备方法。
本发明解决上述技术问题所采用的技术方案为：该钙掺杂的二氧化钛纳米线光催化剂的制备方法包括以下步骤：
（1）配置溶液A：将一定量的乙酸、聚乙烯比咯烷酮加到乙醇溶液，搅拌后形成透明溶液A；（2）取一定量的钛酸异丙酯和乙酸钙加到（1）配置的溶液A中，搅拌均匀后得到透明的溶胶溶液B；（3）将上述制备的溶胶溶液B进行静电纺丝；（4）将（3）制备的样品室温干燥24~96小时，然后置于高温炉中在450~700°C煅烧，即可制得Ca2+掺杂的TiO2纳米纤维。
与现有技术相比，本发明的优点在于：
与已报道的没有掺杂的TiO2纳米纤维光催化剂相比，本发明实现了Ca2+掺杂的TiO2纳米纤维的制备，极大地提高了TiO2纳米纤维的光催化性能。
附图说明
图1为本发明实施例1所制得的Ca2+掺杂的TiO2纳米纤维在紫外光不同照射时间下光催化降解罗丹明B水溶液的紫外光吸收光谱图；
图2为本发明实施例1~实施例3所制得的Ca2+掺杂的TiO2纳米纤维及同样方法实施例4制备的不掺杂TiO2纳米纤维光降解罗丹明B水溶液的影响曲线图，曲线1~4依次为实施例1~实施例4。
具体实施方式
以下结合附图实施例对本发明作进一步的详细描述。
实施例1
（1）将1mL乙酸、1.1g聚乙烯比咯烷酮加到9mL乙醇溶液，搅拌后形成透明溶液A；
（2）取0.9mL钛酸异丙酯和0.01g乙酸钙加到（1）配置的溶液A中；搅拌均匀后得到透明的溶胶溶液B； (3) 将上述制备的溶胶溶液B进行静电纺丝。所制得的电纺丝样品室温干燥48小时，然后置于高温炉中，于600°C保温24小时，自然冷却到室温后，即得具有优异光催化性能的Ca2+掺杂的TiO2纳米纤维光催化剂。图1给出了实施例1所制备的Ca2+掺杂的TiO2纳米纤维在365nm的紫外光照射100分钟条件下，几乎可以将浓度为1 × 10-5 mol/L罗丹明B水溶液完全降解，说明所得的催化剂具有优异的光催化性能。
实施例2
（1）将2mL乙酸、1 g聚乙烯比咯烷酮加到8mL乙醇溶液，搅拌后形成透明溶液A；
（2）取1mL钛酸异丙酯和0.015g乙酸钙加到（1）配置的溶液A中；搅拌均匀后得到透明的溶胶溶液B；（3）将上述制备的溶胶溶液B进行静电纺丝。所制得的电纺丝样品室温干燥60小时，然后置于高温炉中，于550°C保温30小时，自然冷却到室温后，即得具有优异光催化性能的Ca2+掺杂的TiO2纳米纤维光催化剂，然后进行光催化实验。
实施例3
（1）将1.5mL乙酸、0.8g聚乙烯比咯烷酮加到8.5mL乙醇溶液，搅拌后形成透明溶液A；
（2）取2mL钛酸异丙酯和0.02g乙酸钙加到（1）配置的溶液A中；搅拌均匀后得到透明的溶胶溶液B；（3）将上述制备的溶胶溶液B进行静电纺丝。所制得的电纺丝样品室温干燥30小时，然后置于高温炉中，于650°C保温20小时，自然冷却到室温后，即得具有优异光催化性能的Ca2+掺杂的TiO2纳米纤维光催化剂，然后进行光催化实验。
实施例4
（1）将2mL乙酸、1 g聚乙烯比咯烷酮加到8mL乙醇溶液，搅拌后形成透明溶液A；
（2）取1mL钛酸异丙酯加到（1）配置的溶液A中；搅拌均匀后得到透明的溶胶溶液B； （3）将上述制备的溶胶溶液B进行静电纺丝。所制得的电纺丝样品室温干燥60小时，然后置于高温炉中，于550°C保温30小时，自然冷却到室温后，即得作为对比的不掺杂的TiO2纳米纤维光催化剂。
显然，本发明的上述实施例仅为清楚地说明本发明而做的说明举例，而并非是对本发明的实施方式的限定，因为这里无法对所有的实施方式予以穷举。因此凡是属于本发明的技术方案所引伸出的本领域的技术人员可以引伸出的变化或变动仍处于本发明的保护范围之列。
Claims (4)
1.一种钙掺杂的二氧化钛纳米纤维的制备方法，其包括以下具体步骤：
（1）配置溶液：将一定量的乙酸、聚乙烯比咯烷酮加到乙醇溶液，搅拌后形成透明溶液A；
（2）取一定量的钛酸异丙酯和乙酸钙加到（1）配置的溶液A中，搅拌均匀后得到透明的溶胶溶液B；
（3）将上述制备的溶胶溶液B进行静电纺丝；
（4）将（3）制备的样品室温干燥24~96小时，然后置于高温炉中在450~700°C空气气氛下煅烧，即可制得Ca2+掺杂的TiO2纳米纤维。
2.根据权利要求1所述的钙掺杂的二氧化钛纳米纤维的制备方法，其特征在于：所述步骤（1）中聚乙烯比咯烷酮的浓度为80~150g/L，乙酸浓度为0.08~0.3 L /L。
3.根据权利要求1所述的钙掺杂的二氧化钛纳米纤维的制备方法，其特征在于：所述步骤（2）中0.05~0.2 L钛酸异丙酯加入到1L溶液A中，乙酸钙以Ca：Ti= 0.5~15%的摩尔比加入到前述的钛酸异丙酯溶液A中。
4.根据权利要求1所述的钙掺杂的二氧化钛纳米纤维的制备方法，其特征在于，步骤（4）高温保持时间为10~40小时。
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