CN111468128A - 一种复合纳米片催化剂的制备方法 - Google Patents
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Abstract
一种复合纳米片催化剂的制备方法，属于纳米材料制备及催化技术领域，可解决现有保持无机纳米片结构稳定性的方法制备过程繁琐，不利于催化应用的问题，制备方法如下：将含铜类水滑石与石墨粉与无水乙醇混合；将混合的两类层状材料在超临界乙醇中剥离成纳米片并同时完成再组装，即得本发明所述一种复合纳米片催化剂。该催化剂在甲醛乙炔化反应制备1,4‑丁炔二醇的反应中，可以实现甲醛转化率>50%，对1,4‑丁炔二醇的选择性>85%。该复合纳米片在超临界乙醇中实现了剥离/复合一步完成，制备过程不需要稳定剂，操作环节少，避免了常规复合纳米片的复杂制备过程。
Description
技术领域
本发明属于纳米材料制备及催化技术领域，具体涉及一种复合纳米片催化剂的制备方法。
背景技术
纳米片是厚度为几个纳米，水平尺寸超过100纳米以上的二维材料。因为纳米片的特殊二维结构，使其在催化领域备受关注。类水滑石是一类具有阳离子层板结构的层状无机化合物，可通过液相剥离法制备类水滑石纳米片。然而，由于类水滑石纳米片的静电特性导致其易于在溶液中发生再堆积，恢复为多层结构，进而失去纳米片性能优势。保持无机纳米片结构成为当前二维材料制备及应用中的难点。
目前国内外主要通过加入有机聚合物保持纳米片稳定性，但该方法引入了有机聚合物，对随后的催化应用不利。此外，一些研究将纳米片附着于石英片等平面材料上，但该方法制备过程较为繁琐，且对纳米片和附着材料都有较高的要求。
发明内容
本发明针对现有保持无机纳米片结构稳定性的方法制备过程繁琐，不利于催化应用的问题，提供一种复合纳米片催化剂的制备方法。
本发明采用如下技术方案：
一种复合纳米片催化剂的制备方法，包括如下步骤：
第一步，将石墨粉与含铜类水滑石置于无水乙醇混合，得到混合物；
第二步，将第一步得到的混合物加入到超临界反应釜中，调节温度240-320℃之间，保持混合物处于乙醇的超临界状态下60-240min；
第三步，反应结束后，恢复到常温常压后，离心分离混合液，收集固体，干燥后，即得复合纳米片催化剂。
第一步中所述石墨粉的粒径小于100微米。
第一步中所述含铜类水滑石的组成通式为CuxM3-xAl-LDHs，其中M包括二价镁和锌金属阳离子中的任意一种，Al为三价铝阳离子，x为0.1-2。
第一步中所述石墨粉在无水乙醇的混合物中的浓度为0.1g/L-1g/L，含铜类水滑石在无水乙醇的混合物中的浓度为0.05g/L-0.5g/L。
第一步中所述石墨粉和含铜类水滑石的质量比为1:5-2:1。
本发明利用类水滑石与石墨在超临界乙醇中可同步剥离的特点，在超临界乙醇中实现了剥离/组装一步完成。一方面，利用石墨剥离得到的石墨烯为载体，将类水滑石纳米片稳定负载，形成了多层复合纳米材料，解决了类水滑石纳米片再堆积的问题；另一方面，利用石墨烯良好的导电特性，促进了类水滑石纳米片上活性位点之间的电子传递，提高了复合材料的催化活性，进而在在甲醛乙炔化反应制备1,4-丁炔二醇的反应中显示了良好的催化活性。
本发明的有益效果如下：
1. 本发明利用石墨剥离得到的石墨烯为载体，与含铜类水滑石纳米片形成了多层复合纳米材料，避免了类水滑石纳米片的再堆积，保持了其纳米片结构。
2. 本发明在超临界乙醇中实现了类水滑石纳米片与石墨烯的剥离/组装一步完成，简化了复合纳米片的制备流程。
3. 本发明利用石墨烯良好的导电特性，提高了类水滑石纳米片的催化活性。
具体实施方式
实施例1
将0.1g石墨粉，0.5g组成通式为Cu0.1Mg2.9Al-LDHs的含铜类水滑石加入到1000mL无水乙醇中，充分混合；将该混合物加入到到超临界反应釜中，升温到240℃，保持240分钟；恢复到常温、常压后，离心分离收集固体，干燥后得到复合纳米片催化剂。
将0.1g纳米片催化剂与10 mL甲醛(35%)水溶液装入圆底烧瓶中，通氮气吹扫0.5h，加热至沸腾，搅拌条件下通入乙炔气，反应12h。反应后的物料采用气相色谱仪进行组份分析，未反应的甲醛采用碘量法测定。该纳米片催化剂对甲醛转化率50.8%，对1,4-丁炔二醇的选择性87.9%。
实施例2
将1g石墨粉，0.5g组成通式为Cu1.0Mg2.0Al-LDHs的含铜类水滑石加入到1000mL无水乙醇中，充分混合；将该混合物加入到到超临界反应釜中，升温到320℃，保持120分钟；恢复到常温、常压后，离心分离收集固体，干燥后得到复合纳米片催化剂。
将0.1g纳米片催化剂与10 mL甲醛(35%)水溶液装入圆底烧瓶中，通氮气吹扫0.5h，加热至沸腾，搅拌条件下通入乙炔气，反应12h。反应后的物料采用气相色谱仪进行组份分析，未反应的甲醛采用碘量法测定。该纳米片催化剂对甲醛转化率64.3%，对1,4-丁炔二醇的选择性85.5%。
实施例3
将0.1g石墨粉，0.05g组成通式为Cu2.0Mg1.0Al-LDHs的含铜类水滑石加入到1000mL无水乙醇中，充分混合；将该混合物加入到到超临界反应釜中，升温到300℃，保持60分钟；恢复到常温、常压后，离心分离收集固体，干燥后得到复合纳米片催化剂。
将0.1g纳米片催化剂与10 mL甲醛(35%)水溶液装入圆底烧瓶中，通氮气吹扫0.5h，加热至沸腾，搅拌条件下通入乙炔气，反应24h。反应后的物料采用气相色谱仪进行组份分析，未反应的甲醛采用碘量法测定。该纳米片催化剂对甲醛转化率59.5%，对1,4-丁炔二醇的选择性89.1%。
实施例4
将0.1g石墨粉，0.3g组成通式为Cu1.0Mg2.0Al-LDHs的含铜类水滑石加入到1000mL无水乙醇中，充分混合；将该混合物加入到到超临界反应釜中，升温到240℃，保持180分钟；恢复到常温、常压后，离心分离收集固体，干燥后得到复合纳米片催化剂。
将0.1g纳米片催化剂与10 mL甲醛(35%)水溶液装入圆底烧瓶中，通氮气吹扫0.5h，加热至沸腾，搅拌条件下通入乙炔气，反应24h。反应后的物料采用气相色谱仪进行组份分析，未反应的甲醛采用碘量法测定。该纳米片催化剂对甲醛转化率72.4%，对1,4-丁炔二醇的选择性86.6%。
实施例5
将0.3g石墨粉，0.3g组成通式为Cu1.5Mg1.5Al-LDHs的含铜类水滑石加入到1000mL无水乙醇中，充分混合；将该混合物加入到到超临界反应釜中，升温到300℃，保持240分钟；恢复到常温、常压后，离心分离收集固体，干燥后得到复合纳米片催化剂。
将0.1g纳米片催化剂与10 mL甲醛(35%)水溶液装入圆底烧瓶中，通氮气吹扫0.5h，加热至沸腾，搅拌条件下通入乙炔气，反应12h。反应后的物料采用气相色谱仪进行组份分析，未反应的甲醛采用碘量法测定。该纳米片催化剂对甲醛转化率70.6%，对1,4-丁炔二醇的选择性89.2%。
Claims (5)
1.一种复合纳米片催化剂的制备方法，其特征在于：包括如下步骤：
第一步，将石墨粉与含铜类水滑石置于无水乙醇混合，得到混合物；
第二步，将第一步得到的混合物加入到超临界反应釜中，调节温度240-320℃之间，保持混合物处于乙醇的超临界状态下60-240min；
第三步，反应结束后，恢复到常温常压后，离心分离混合液，收集固体，干燥后，即得复合纳米片催化剂。
2.根据权利要求1所述的一种复合纳米片催化剂的制备方法，其特征在于：第一步中所述石墨粉的粒径小于100微米。
3.根据权利要求1所述的一种复合纳米片催化剂的制备方法，其特征在于：第一步中所述含铜类水滑石的组成通式为CuxM3-xAl-LDHs，其中M包括二价镁和锌金属阳离子中的任意一种，Al为三价铝阳离子，x为0.1-2。
4.根据权利要求1所述的一种复合纳米片催化剂的制备方法，其特征在于：第一步中所述石墨粉在无水乙醇的混合物中的浓度为0.1g/L-1g/L，含铜类水滑石在无水乙醇的混合物中的浓度为0.05g/L-0.5g/L。
5.根据权利要求1所述的一种复合纳米片催化剂的制备方法，其特征在于：第一步中所述石墨粉和含铜类水滑石的质量比为1:5-2:1。
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| CN112108148A (zh) * | 2020-09-24 | 2020-12-22 | 华东理工大学 | 一种甲醇蒸汽重整制氢的负载型铜基催化剂及其制备方法和应用 |
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