CN106540675B - 基于Cu+/Cu的氧化还原制备多孔氧化锡-CNTs光催化材料 - Google Patents
基于Cu+/Cu的氧化还原制备多孔氧化锡-CNTs光催化材料 Download PDFInfo
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Abstract
基于Cu+/Cu的氧化还原制备多孔氧化锡‑CNTs光催化材料，本发明涉及一种基于酸性介质中Cu+/Cu的氧化还原来制备用于光降解有机污染物的多孔氧化锡‑CNTs复合材料的方法。本发明是要解决目前薄膜光催化材料催化活性低的问题。基于Cu+/Cu的氧化还原制备多孔氧化锡‑CNTs光催化材料：(1)在导电玻璃表面电沉积仿金青铜‑CNTs；(2)仿金青铜‑CNTs的一价铜沥出；(3)多孔锡‑CNTs的氧化，制备出高效的多孔氧化锡‑CNTs光催化降解复合材料。基于Cu+/Cu的氧化还原制备出的多孔氧化锡‑CNTs光催化材料提高了催化材料的比表面积和吸附性能，并可防止光电子与空穴的复合，可以大幅度提高材料的催化性能。
Description
技术领域
本发明属于光催化材料制备领域，涉及一种基于酸性溶液中Cu+/Cu的氧化还原来制备多孔氧化锡-CNTs光催化材料的方法。
背景技术
经济发展给人类社会提供了进步的驱动力，同时也带来了诸多难以消除的影响，比如环境污染问题随着经济发展的加剧，而且环保问题在发展中国家尤为突出，各种污染物排放至水体及大气中，造成了人民生活环境的破坏。因此，必须对各种污染物的排放采取严格的控制，并对污染物的治理采取具有针对性的手段，开发能把污染物去除的技术，才能够改善生存环境。
对于水体污染的治理，采取光催化材料对污染物进行处理，可以将太阳能作为污染治理的能源，产生的光生电子和光生空穴具有还原和氧化的能力，从而使水体中的污染物被氧化或还原为无毒的物质。光催化降解有机污染物不仅节约能源而且适用性广，可以突破传统环境治理方法无法解决的瓶颈，因此受到了广泛的关注，也很有希望成为解决水体污染的绿色环境治理方式。所以，开发可以产生强氧化还原性光生空穴及光生电子的高效半导体光催化材料成为治理水体污染的重要任务。除了催化剂本身的半导体性质之外，诸多因素都可以对于半导体催化材料的催化活性产生重大影响，比如：半导体催化剂的晶粒大小、晶型、吸附性以及导电性等性质。一般来讲，催化剂的晶粒越小其催化表面就越大，吸附性能越好就能在单位时间内吸附更多的有机污染物，导电性能越好就能防止光生电子与光生空穴的复合，催化剂的催化效果就越好。然而，采用粉体催化剂虽然比表面积更大，但是催化剂不稳定易团聚，且不易回收造成二次污染，采用薄膜半导体催化剂则可以克服这些问题。
目前，人们已经研究了二氧化钛、氧化锌、硫化镉、氧化锡以及二硫化钼等半导体材料及其复合材料作为光催化材料用于分解有机污染物的可行性，而且在薄膜半导体催化剂的制备领域取得了一定的进展。在众多半导体光催化材料中，氧化锡的禁带宽度较宽，其产生的光生空穴的氧化性较强，可以氧化更稳定的有机污染物，产生更好的光催化降解效果。但是，氧化锡薄膜催化剂本身的比表面积较小、导电性较差，且对有机污染物的吸附性能不理想，这些因素都限制了氧化锡薄膜催化剂的催化活性以及在光催化降解有机污染物领域的应用。因此，制备具有巨大催化面积、良好吸附性能以及优良导电性的氧化锡复合薄膜，提高其催化降解有机污染物的能力，对于光催化材料在环境治理领域的实际应用具有重大意义。
发明内容
本发明是要解决目前薄膜光催化材料催化活性低的问题，而提供一种基于酸性介质中Cu+/Cu的氧化还原来制备用于光降解有机污染物的多孔氧化锡-CNTs复合材料的方法。
本发明的基于Cu+/Cu的氧化还原制备多孔氧化锡-CNTs光催化材料按照以下步骤进行：
(1) 在导电玻璃表面电沉积仿金青铜-CNTs：a. 量取8~80 mL盐酸溶于700 mL去离子水中，缓慢加入5~15 g的对苯二酚，然后加入5~12 g酒石酸氢钾，搅拌至全部溶解后加入1~6 g氯化亚锡并陈化24h，配得溶液A；b. 向溶液A中加入35~120 g硫脲，加热搅拌至完全溶解后加入5~35g氧化亚铜，在50~80 ℃条件下搅拌2 h后趁热进行常压过滤，配得溶液B；c. 将0.5~1.0 g CNTs加入到100 ml 65%硝酸中，采用超声波细胞粉碎机处理6~60 h，加入氨水至溶液pH值为5.5~8.5后采用去离子水对CNTs进行离心洗涤5~8次，将CNTs分散于200 mL去离子水中，配得溶液C；d. 混合溶液B与溶液C，定容至1 L，配得仿金青铜-CNTs复合电沉积溶液；e. 将经过丙酮除油的导电玻璃浸入步骤d配制的仿金青铜-CNTs复合电沉积溶液，在电流密度为1.0~5.0 A/dm2并且施加搅拌的条件下电沉积10~120 min，在导电玻璃表面制得仿金青铜-CNTs复合层；
(2) 仿金青铜-CNTs的一价铜沥出：f. 将2~35 mL的盐酸和50~100 g硫脲在55~85℃的温度下溶于600mL去离子水中，然后定容至1 L，配得铜沥出液；g. 将步骤e制备的沉积有仿金青铜-CNTs复合层的导电玻璃浸入到步骤f配制的铜沥出液中，在35~80 ℃条件下浸泡0.5~12 h，完成仿金青铜-CNTs的一价铜沥出，制得导电玻璃/多孔锡-CNTs；
(3) 多孔锡-CNTs的氧化：h. 将步骤g制备的导电玻璃/多孔锡-CNTs在80~150℃的条件下热处理8~60 h，完成多孔锡-CNTs的氧化，在导电玻璃表面获得多孔氧化锡-CNTs光催化材料。
本发明的基于Cu+/Cu的氧化还原制备多孔氧化锡-CNTs光催化材料通过在含有亚铜离子和亚锡离子的溶液中电沉积仿金青铜-CNTs，然后利用铜在含有硫脲的酸性溶液中极易溶解为亚铜离子的特性沥出仿金青铜中的铜元素，得到多孔锡-CNTs复合物，进而氧化生成多孔氧化锡-CNTs复合材料。由于铜的沥出，制备的光催化材料为具有很大比表面积的多孔材料；由于制备的光催化材料多孔且含有具有吸附性能的CNTs，因此光催化材料吸附有机污染物的能力优良，有助于提高其催化降解有机污染物的能力；由于制备的光催化材料含有导电性良好的CNTs，有助于防止光生电子和光生空穴的复合，提高催化材料的催化能力。因此，将本发明制备的多孔氧化锡-CNTs光催化材料用于光降解有机污染物时，可以表现出优良的催化活性，对于水体污染的治理具有重大意义。
附图说明
图1为试验一步骤(1)制备的仿金青铜-CNTs复合材料的SEM图像；
图2为试验一制备的氧化锡-CNTs复合材料的SEM图像；
图3为试验一制备的氧化锡-CNTs复合材料在350 W汞灯照射下对50 mL浓度为30mg/L的甲基橙溶液的光催化降解曲线。
具体实施方式
具体实施方式一：本实施方式的基于Cu+/Cu的氧化还原制备多孔氧化锡-CNTs光催化材料按以下步骤进行：
1、基于Cu+/Cu的氧化还原制备多孔氧化锡-CNTs光催化材料，其特征在于基于Cu+/Cu的氧化还原制备多孔氧化锡-CNTs光催化材料按以下步骤进行：
(1) 在导电玻璃表面电沉积仿金青铜-CNTs：a. 量取8~80 mL盐酸溶于700 mL去离子水中，缓慢加入5~15 g的对苯二酚，然后加入5~12 g酒石酸氢钾，搅拌至全部溶解后加入1~6 g氯化亚锡并陈化24h，配得溶液A；b. 向溶液A中加入35~120 g硫脲，加热搅拌至完全溶解后加入5~35g氧化亚铜，在50~80 ℃条件下搅拌2 h后趁热进行常压过滤，配得溶液B；c. 将0.5~1.0 g CNTs加入到100 ml 65%硝酸中，采用超声波细胞粉碎机处理6~60 h，加入氨水至溶液pH值为5.5~8.5后采用去离子水对CNTs进行离心洗涤5~8次，将CNTs分散于200 mL去离子水中，配得溶液C；d. 混合溶液B与溶液C，定容至1 L，配得仿金青铜-CNTs复合电沉积溶液；e. 将经过丙酮除油的导电玻璃浸入步骤d配制的仿金青铜-CNTs复合电沉积溶液，在电流密度为1.0~5.0 A/dm2并且施加搅拌的条件下电沉积10~120 min，在导电玻璃表面制得仿金青铜-CNTs复合层；
(2) 仿金青铜-CNTs的一价铜沥出：f. 将2~35 mL的盐酸和50~100 g硫脲在55~85℃的温度下溶于600mL去离子水中，然后定容至1 L，配得铜沥出液；g. 将步骤e制备的沉积有仿金青铜-CNTs复合层的导电玻璃浸入到步骤f配制的铜沥出液中，在35~80 ℃条件下浸泡0.5~12 h，完成仿金青铜-CNTs的一价铜沥出，制得导电玻璃/多孔锡-CNTs；
(3) 多孔锡-CNTs的氧化：h. 将步骤g制备的导电玻璃/多孔锡-CNTs在80~150℃的条件下热处理8~60 h，完成多孔锡-CNTs的氧化，在导电玻璃表面获得多孔氧化锡-CNTs光催化材料。
本实施方式的基于Cu+/Cu的氧化还原制备多孔氧化锡-CNTs光催化材料通过在含有亚铜离子和亚锡离子的溶液中电沉积仿金青铜-CNTs，然后利用铜在含有硫脲的酸性溶液中极易溶解为亚铜离子的特性沥出仿金青铜中的铜元素，得到多孔锡-CNTs复合物，进而氧化生成多孔氧化锡-CNTs复合材料。由于铜的沥出，制备的光催化材料为具有很大比表面积的多孔材料；由于制备的光催化材料多孔且含有具有吸附性能的CNTs，因此光催化材料吸附有机污染物的能力优良，有助于提高其催化降解有机污染物的能力；由于制备的光催化材料含有导电性良好的CNTs，有助于防止光生电子和光生空穴的复合，提高催化材料的催化能力。因此，将本实施方式制备的多孔氧化锡-CNTs光催化材料用于光降解有机污染物时，可以表现出优良的催化活性。
具体实施方式二：本实施方式与具体实施方式一不同的是步骤(1)的c中所述的采用超声波细胞粉碎机处理的时间为12~50 h。其它与具体实施方式一相同。
具体实施方式三：本实施方式与具体实施方式一或二不同的是步骤(1)的e中所述的电沉积时间为15~90 min。其它与具体实施方式一或二相同。
具体实施方式四：本实施方式与具体实施方式一至三之一不同的是步骤(2)的g中所述的将步骤e制备的沉积有仿金青铜-CNTs复合层的导电玻璃浸入到步骤f配制的铜沥出液中，在35~80 ℃条件下浸泡的时间为1~10 h。其它与具体实施方式一至三之一相同。
具体实施方式五：本实施方式与具体实施方式一至四之一不同的是步骤(3)的h中所述的将步骤g制备的导电玻璃/多孔锡-CNTs在80~150℃的条件下热处理的时间为10~50h。其它与具体实施方式一至四之一相同。
用以下试验验证本发明的有益效果：
试验一：本试验的基于Cu+/Cu的氧化还原制备多孔氧化锡-CNTs光催化材料按以下步骤进行：
(1) 在导电玻璃表面电沉积仿金青铜-CNTs：a. 量取30 mL盐酸溶于700 mL去离子水中，缓慢加入6 g的对苯二酚，然后加入10 g酒石酸氢钾，搅拌至全部溶解后加入3 g氯化亚锡并陈化24h，配得溶液A；b. 向溶液A中加入50 g硫脲，加热搅拌至完全溶解后加入16g氧化亚铜，在70 ℃条件下搅拌2 h后趁热进行常压过滤，配得溶液B；c. 将0.8 g CNTs加入到100 ml 65%硝酸中，采用超声波细胞粉碎机处理48 h，加入氨水至溶液pH值为7.5后采用去离子水对CNTs进行离心洗涤8次，将CNTs分散于200 mL去离子水中，配得溶液C；d. 混合溶液B与溶液C，定容至1 L，配得仿金青铜-CNTs复合电沉积溶液；e. 将经过丙酮除油的导电玻璃浸入步骤d配制的仿金青铜-CNTs复合电沉积溶液，在电流密度为1.5 A/dm2并且施加搅拌的条件下电沉积30 min，在导电玻璃表面制备仿金青铜-CNTs复合层；
(2) 仿金青铜-CNTs的一价铜沥出：f. 将8 mL的盐酸和80 g硫脲在65 ℃的温度下溶于600mL去离子水中，然后定容至1 L，配得铜沥出液；g. 将步骤e制备的沉积有仿金青铜-CNTs复合层的导电玻璃浸入到步骤f配制的铜沥出液中，在60 ℃条件下浸泡8 h，完成仿金青铜-CNTs的一价铜沥出，制得导电玻璃/多孔锡-CNTs；
(3) 多孔锡-CNTs的氧化：h. 将步骤g制备的导电玻璃/多孔锡-CNTs在120 ℃的条件下热处理20 h，完成多孔锡-CNTs的氧化，在导电玻璃表面获得多孔氧化锡-CNTs光催化材料。
本试验步骤(1)制备的仿金青铜-CNTs复合材料的SEM图像如图1所示。从图1可知仿金青铜与CNTs发生共沉积，得到复合镀层的生长模式为仿金青铜在CNTs的外延生长，产生具有巨大比表面积的三维材料。
本试验制备的氧化锡-CNTs复合材料的SEM图像如图2所示。从图2可知，在浸出铜之后多孔锡骨架附着于CNTs外延，比表面积进一步增加，后续热处理氧化之后生成具有很高比表面积的多孔氧化锡-CNTs复合材料，复合材料既具有巨大的比表面积，同时还兼具CNTs良好的导电性以及吸附性能。
本试验制备的氧化锡-CNTs复合材料在350 W汞灯照射下对50 mL浓度为30 mg/L的甲基橙溶液的光催化降解曲线如图3所示，由图3可知氧化锡-CNTs复合材料在60 min内即可基本将甲基橙降解完全，显示出良好的催化活性。
Claims (5)
1.基于Cu+/Cu的氧化还原制备多孔氧化锡-CNTs光催化材料，其特征在于基于Cu+/Cu的氧化还原制备多孔氧化锡-CNTs光催化材料按以下步骤进行：
(1) 在导电玻璃表面电沉积仿金青铜-CNTs：a. 量取8~80 mL盐酸溶于700 mL去离子水中，缓慢加入5~15 g的对苯二酚，然后加入5~12 g酒石酸氢钾，搅拌至全部溶解后加入1~6 g氯化亚锡并陈化24h，配得溶液A；b. 向溶液A中加入35~120 g硫脲，加热搅拌至完全溶解后加入5~35g氧化亚铜，在50~80 ℃条件下搅拌2 h后趁热进行常压过滤，配得溶液B；c.将0.5~1.0 g CNTs加入到100 ml 65%硝酸中，采用超声波细胞粉碎机处理6~60 h，加入氨水至溶液pH值为5.5~8.5后采用去离子水对CNTs进行离心洗涤5~8次，将CNTs分散于200 mL去离子水中，配得溶液C；d. 混合溶液B与溶液C，定容至1 L，配得仿金青铜-CNTs复合电沉积溶液；e. 将经过丙酮除油的导电玻璃浸入步骤d配制的仿金青铜-CNTs复合电沉积溶液，在电流密度为1.0~5.0 A/dm2并且施加搅拌的条件下电沉积10~120 min，在导电玻璃表面制得仿金青铜-CNTs复合层；
(2) 仿金青铜-CNTs的一价铜沥出：f. 将2~35 mL的盐酸和50~100 g硫脲在55~85 ℃的温度下溶于600mL去离子水中，然后定容至1 L，配得铜沥出液；g. 将步骤e制备的沉积有仿金青铜-CNTs复合层的导电玻璃浸入到步骤f配制的铜沥出液中，在35~80 ℃条件下浸泡0.5~12 h，完成仿金青铜-CNTs的一价铜沥出，制得导电玻璃/多孔锡-CNTs；
(3) 多孔锡-CNTs的氧化：h. 将步骤g制备的导电玻璃/多孔锡-CNTs在80~150℃的条件下热处理8~60 h，完成多孔锡-CNTs的氧化，在导电玻璃表面获得多孔氧化锡-CNTs光催化材料。
2.根据权利要求1所述的基于Cu+/Cu的氧化还原制备多孔氧化锡-CNTs光催化材料，其特征在于步骤(1)的c中所述的采用超声波细胞粉碎机处理的时间为12~50 h。
3.根据权利要求1所述的基于Cu+/Cu的氧化还原制备多孔氧化锡-CNTs光催化材料，其特征在于步骤(1)的e中所述的电沉积时间为15~90 min。
4.根据权利要求1所述的基于Cu+/Cu的氧化还原制备多孔氧化锡-CNTs光催化材料，其特征在于步骤(2)的g中所述的将步骤e制备的沉积有仿金青铜-CNTs复合层的导电玻璃浸入到步骤f配制的铜沥出液中，在35~80 ℃条件下浸泡的时间为1~10 h。
5.根据权利要求1所述的基于Cu+/Cu的氧化还原制备多孔氧化锡-CNTs光催化材料，其特征在于步骤(3)的h中所述的将步骤g制备的导电玻璃/多孔锡-CNTs在80~150℃的条件下热处理的时间为10~50 h。
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