CN112029076B - 一种用于电催化制备过氧化氢的催化剂及其制备方法 - Google Patents
一种用于电催化制备过氧化氢的催化剂及其制备方法 Download PDFInfo
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Abstract
本发明公开一种用于电催化制备过氧化氢的催化剂，提供了一种新的电催化制备过氧化氢的催化剂，将蒽醌‑2‑羧酸接枝到咔唑上并进行电聚合，制备得到的催化剂稳定性良好，便于储存和运输。本发明的催化剂为聚蒽醌‑2‑甲酰咔唑，制备方法包含以下步骤：在氩气持续通气情况下将蒽醌‑2‑羧酸、氯化亚砜溶于四氢呋喃中，在0℃搅拌24小时得到淡黄色的溶液，之后迅速加入咔唑与三乙醇胺的丙酮溶液，然后持续通气，在‑10oC持续反应24小时，所得产物经柱层析法分离得到黄色固体，最后将该固体溶于乙腈中，以高氯酸锂作为导电盐进行循环伏安法电聚合，制备出墨绿色固体，即所述催化剂。
Description
技术领域
本发明属于有机非金属材料领域，尤其涉及一种用于电催化制备过氧化氢的催化剂及其制备方法。
背景技术
过氧化氢的工业制备方式为蒽醌法，能源消耗巨大且副产物众多。同时由于过氧化氢高度活泼的化学性质，其储存运输等方面存在极大的挑战。利用电催化氧还原反应的方式制备过氧化氢已经成为目前研究的热点。常见的电催化氧还原反应制备过氧化氢的催化剂包括：金、钯等贵金属及合金、氧化锡等半导体、碳纳米管及氧化石墨烯等碳材料、贵金属单原子催化剂等。然而上述催化剂或价格昂贵或制备工艺繁琐，不利于大规模工业化生产。咔唑的化学性质稳定，其聚合物具有较好的导电性，在能源存储、光电催化领域得到了广泛应用，其氨基为蒽醌-2-羧酸的良好结合位点。蒽醌则是工业制备过氧化氢的常用催化剂。将二者结合所得产物是电催化氧还原制备过氧化氢的理想催化剂，具有广阔的应用前景。
发明内容
本发明提供了一种用于电催化制备过氧化氢的催化剂及其制备方法，提供了一种新的电催化制备过氧化氢的催化剂，将蒽醌-2-羧酸接枝到咔唑上并进行电聚合，制备得到的催化剂稳定性良好，便于储存和运输。
为实现以上目的，本发明采用以下技术方案：
一种用于电催化制备过氧化氢的催化剂，所述催化剂为聚蒽醌-2-甲酰咔唑，结构为：
一种用于电催化制备过氧化氢的催化剂的制备方法，包括以下步骤：
（1）将蒽醌-2-羧酸溶于四氢呋喃中，搅拌形成透明的溶液；然后逐滴加入含有氯化亚砜的四氢呋喃溶液，每1g蒽醌-2-羧酸对应的氯化亚砜的加入量范围为1~1.5ml，反应环境持续通入惰性气体，在0℃下均匀搅拌24小时直至形成淡黄色溶液；
（2）在步骤（1）得到的溶液中迅速加入含有咔唑、三乙醇胺的丙酮溶液，每1g蒽醌-2-羧酸对应的咔唑加入量为0.5-0.6 g，三乙胺为1-1.2 ml，在-10℃下均匀搅拌24小时；
（3）将步骤（2）得到的溶液经过柱层析法提取，旋蒸后得到黄色固体；
（4）将步骤（3）得到的黄色固体溶于乙腈，以高氯酸锂作为导电盐，以三电极体系进行循环伏安聚合，得到墨绿色固体，即所述催化剂。
以上所述步骤中，步骤（1）中每1-1.2 g蒽醌-2-羧酸溶于30ml无水四氢呋喃，每1-1.5 ml氯化亚砜溶于19mL无水四氢呋喃中，所述惰性气体为氩气或氮气；
步骤（2）中每0.5-0.6 g 咔唑溶于20 mL 丙酮中，每1-1.2 mL三乙胺溶于9 mL 丙酮中；
步骤（3）中柱层析法淋洗液为石油醚和丙酮混合液，石油醚和丙酮的体积比为1：5；
步骤（4）中按步骤（3）所得固体110-300mg 溶于30 mL 乙腈中，该固体的摩尔浓度为10 mM，高氯酸锂30-50 mg 溶于30 mL 乙腈中，高氯酸锂的摩尔浓度为10 mM，三电极体系为：工作电极为FTO导电玻璃，对电极为石墨电极，参比电极为饱和甘汞电极，电位区间为0-1.4 V ,扫描速度为50 mV/s, 经过10-50次循环后在工作电极上收集样品。
有益效果：本发明提供了一种用于电催化制备过氧化氢的催化剂及其制备方法，将蒽醌-2-羧酸接枝到咔唑上并进行电聚合，在工业常用催化剂的基础上与导电聚合物结合，提供了一种新型的用于电催化制备过氧化氢的催化剂聚蒽醌-2-甲酰咔唑，本发明制备工艺简单、原料相比贵金属催化剂价格便宜，而且该催化剂稳定性良好，便于储存和运输，而且用于电催化氧还原反应可高效制备过氧化氢，氧还原二电子过程过氧化氢选择性相较单体提高至接近70%，具有很好的稳定性。本发明制得的产品在碱性环境下过氧化氢选择性接近70%，在废水处理、医用消毒甚至能源存储方面具有很强的现实意义。
附图说明
图1是本发明实施例1所制备的导电聚合物催化剂聚蒽醌-2-甲酰咔唑的红外特征光谱图；
图2是本发明实施例1所制备的导电聚合物催化剂聚蒽醌-2-甲酰咔唑的扫描电子显微镜照片；
图3是本发明实施例2所制备的导电聚合物催化剂单体蒽醌-2-甲酰咔唑的核磁共振图谱；
图4是本发明实施例3所制备的导电聚合物催化剂聚蒽醌-2-甲酰咔唑电催化过氧化氢产生的选择性与转移电子数图谱。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明：
实施例1
一种用于电催化制备过氧化氢的催化剂，所述催化剂为聚蒽醌-2-甲酰咔唑，结构为：
一种用于电催化制备过氧化氢的催化剂的制备方法，包括以下步骤：
（1）将0.5 g蒽醌-2-羧酸（购自Sigma-Aldrich公司）溶于10 ml四氢呋喃，将1 ml氯化亚砜溶于20ml无水丙酮，两种溶液在持续通氩气中快速混合搅拌4h形成淡黄色透明的溶液A；
（2）将1 g的咔唑溶液和1 ml三乙胺加入到20 ml无水丙酮中，超声、搅拌得到透明的溶液B；
（3）然后逐滴将溶液B加于溶液A中，搅拌24h使其混合均匀，从而得到橘黄色的溶液；
（4）将橘黄色的溶液进行柱层析分离，淋洗液采用石油醚和丙酮的混合溶液，石油醚和丙酮的体积比为5：1，收集得到淡黄色溶液迅速旋蒸得到黄色固体；
（4）将50 mg黄色固体和0.5 g高氯酸锂溶于30 ml乙腈中，得到黄色溶液C；
（5）以导电玻璃FTO为工作电极、铂片为对电极、饱和甘汞电极为参比电极，在上述步骤（4）的溶液C中进行循环伏安法电聚合，扫描速度为50 mV/s，扫面区间为0-1.4 V ，进行10次循环，在FTO表面收集墨绿色固体；
（6）所得墨绿色固体在60 ℃烘箱中干燥6h，粉碎后收集备用。
上述产物的红外特征谱图如图1所示，在1369 cm-1处有明显的酰胺键生成，证明合成成功。
实施例2
一种用于电催化制备过氧化氢的催化剂，所述催化剂为聚蒽醌-2-甲酰咔唑，结构为：
一种用于电催化制备过氧化氢的催化剂的制备方法，包括以下步骤：
（1）将200 mg蒽醌-2-羧酸（购自Sigma-Aldrich公司）和1 ml 氯化亚砜溶于10ml四氢呋喃中，加入无水丙酮定容至30 ml，搅拌4h形成透明的溶液A；
（2）将0.5 g咔唑加入到20 ml无水丙酮中，再缓慢加入1 ml三乙胺，磁力搅拌得到透明的溶液B；
（3）然后逐滴将溶液B加于溶液A中，搅拌24h使其混合均匀，从而得到橘黄色的溶液；
（4）将橘黄色的溶液进行柱层析分离，淋洗液为石油醚和乙酸乙酯的混合溶液，体积比为5：1，得到黄色溶液迅速旋蒸，得到橘黄色固体；
（4）将10 mg橘黄色固体和0.25 g高氯酸锂溶于20 ml乙腈中，得到黄色溶液C；
（5）以导电玻璃FTO为工作电极、铂片为对电极、饱和甘汞电极为参比电极，在上述步骤（4）的溶液C中进行循环伏安法电聚合，扫描速度为50 mV/s，扫面区间为0-1.4 V ，进行50次循环，在FTO表面收集墨绿色固体；
（6）所得墨绿色固体在60 ℃烘箱中干燥6h，粉碎后收集备用。
上述产物的扫面电子显微镜图像见图2，由图2可知，合成的产物具有一定的片状形貌。
上述产物单体的核磁共振图谱如图3所示，6种特征氢按正向化学位移比例依次为2:9:10:8:6:4，均处于芳香烃区，证明合成成功，同时，根据比例计算得知，咔唑微过量。
实施例3
一种用于电催化制备过氧化氢的催化剂，所述催化剂为聚蒽醌-2-甲酰咔唑，结构为：
一种用于电催化制备过氧化氢的催化剂的制备方法，包括以下步骤：
（1）将1 g蒽醌-2-羧酸（购自Sigma-Aldrich公司）和1 ml 氯化亚砜溶于20ml四氢呋喃中，加入无水丙酮定容至50 ml，搅拌4h形成透明的溶液A；
（2）将1ml 三乙胺加入到30 ml无水丙酮中，再缓慢加入1 g咔唑，超声5 min得到透明的溶液B；
（3）然后逐滴将溶液B加于溶液A中，搅拌24h使其反应，从而得到橘黄色的溶液；
（4）将橘黄色的溶液进行柱层析分离，淋洗液为石油醚和乙酸乙酯的混合溶液，体积比为5：1，得到黄色溶液迅速旋蒸，得到橘黄色固体；
（4）将100 mg橘黄色固体和0.5 g高氯酸锂溶于30 ml乙腈中，得到黄色溶液C；
（5）以导电玻璃FTO为工作电极、铂片为对电极、饱和甘汞电极为参比电极，在上述步骤（4）的溶液C中进行循环伏安法电聚合，扫描速度为50 mV/s，扫面区间为0-1.4 V，进行30次循环，在FTO表面收集墨绿色固体；
（6）所得墨绿色固体在60 ℃烘箱中干燥6h，粉碎后收集备用。
如图4所示，上述产物的氧还原二电子过程过氧化氢选择性相较单体提高至接近70%，在不同电位下具有很好的稳定性。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下还可以做出若干改进，这些改进也应视为本发明的保护范围。
Claims (8)
1.一种用于电催化制备过氧化氢的催化剂，其特征在于，所述催化剂为聚蒽醌-2-甲酰咔唑，结构为：
所述催化剂合成包括以下步骤：
（1）将蒽醌-2-羧酸溶于四氢呋喃中，搅拌形成透明的溶液；然后逐滴加入含有氯化亚砜的四氢呋喃溶液，每1g蒽醌-2-羧酸对应的氯化亚砜的加入量范围为1~1.5ml，反应环境持续通入惰性气体，在0℃下均匀搅拌24小时直至形成淡黄色溶液；
（2）在步骤（1）得到的溶液中迅速加入含有咔唑、三乙醇胺的丙酮溶液，每1g蒽醌-2-羧酸对应的咔唑加入量为0.5-0.6 g，三乙胺为1-1.2 ml，在-10℃下均匀搅拌24小时；
（3）将步骤（2）得到的溶液经过柱层析法提取，旋蒸后得到黄色固体；
（4）将步骤（3）得到的黄色固体溶于乙腈，以高氯酸锂作为导电盐，以三电极体系进行循环伏安聚合，得到墨绿色固体，即所述催化剂。
2.一种用于电催化制备过氧化氢的催化剂的制备方法，其特征在于，包括以下步骤：
（1）将蒽醌-2-羧酸溶于四氢呋喃中，搅拌形成透明的溶液；然后逐滴加入含有氯化亚砜的四氢呋喃溶液，每1g蒽醌-2-羧酸对应的氯化亚砜的加入量范围为1~1.5ml，反应环境持续通入惰性气体，在0℃下均匀搅拌24小时直至形成淡黄色溶液；
（2）在步骤（1）得到的溶液中迅速加入含有咔唑、三乙醇胺的丙酮溶液，每1g蒽醌-2-羧酸对应的咔唑加入量为0.5-0.6 g，三乙胺为1-1.2 ml，在-10℃下均匀搅拌24小时；
（3）将步骤（2）得到的溶液经过柱层析法提取，旋蒸后得到黄色固体；
（4）将步骤（3）得到的黄色固体溶于乙腈，以高氯酸锂作为导电盐，以三电极体系进行循环伏安聚合，得到墨绿色固体，即所述催化剂。
3. 根据权利要求2所述的用于电催化制备过氧化氢的催化剂的制备方法，其特征在于，步骤（1）中每1-1.2 g蒽醌-2-羧酸溶于30ml无水四氢呋喃，每1-1.5 ml氯化亚砜溶于19mL无水四氢呋喃中。
4.根据权利要求2所述的用于电催化制备过氧化氢的催化剂的制备方法，其特征在于，步骤（1）中所述惰性气体为氩气或氮气。
5. 根据权利要求2所述的用于电催化制备过氧化氢的催化剂的制备方法，其特征在于，步骤（2）中每0.5-0.6 g 咔唑溶于20 mL 丙酮中，每1-1.2 mL三乙胺溶于9 mL 丙酮中。
6.根据权利要求2所述的用于电催化制备过氧化氢的催化剂的制备方法，其特征在于，步骤（3）中柱层析法淋洗液为石油醚和丙酮混合液，石油醚和丙酮的体积比为1：5。
7. 根据权利要求2所述的用于电催化制备过氧化氢的催化剂的制备方法，其特征在于，步骤（4）中按步骤（3）所得固体110-200 mg 溶于30 mL 乙腈中，高氯酸锂30-50 mg 溶于30 mL 乙腈中。
8. 根据权利要求2或7所述的用于电催化制备过氧化氢的催化剂的制备方法，其特征在于，步骤（4）中所述三电极体系为：工作电极为FTO导电玻璃，对电极为石墨电极，参比电极为饱和甘汞电极，电位区间为0-1.4 V ，扫描速度为50 mV/s，经过10-50次循环后在工作电极上收集样品。
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