CN115448365B - 一种单层1T′相TMDs空心结构电催化剂制备方法 - Google Patents
一种单层1T′相TMDs空心结构电催化剂制备方法 Download PDFInfo
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Abstract
本发明涉及一种单层1T′相TMDs空心结构电催化剂制备方法,包括以下步骤:将长碳链表面活性剂和十八烯的混合物加热到100~120℃抽真空,然后在惰性气体保护下升温至280~320℃后向混合物中注射加入模板和前驱体进行反应,反应结束后自然冷却至室温,然后加入正己烷和乙醇超声洗涤后离心并分散在乙醇中,去除模板得到单层1T′相TMDs空心结构电催化剂,其中所述前驱体为硫粉或二苯联硒和五氯化钼或六氯化钨按摩尔比2:1分散在油胺中的混合物。本发明制得的单层1T′‑TMDs空心结构具有相纯度高、尺寸均一、在极性溶剂分散良好的优点,并且具有较高的导电性和丰富的催化活性位点。
Description
技术领域
本发明属于,涉及一种属于材料化学技术领域,具体涉及一种单层1T′相TMDs空心结构电催化剂制备方法。
背景技术
电催化产氢,是迎接“氢能经济”时代、实现我国“碳达峰、碳中和”目标最具前景的制氢技术方向之一。虽然贵金属铂基材料作为电催化剂在析氢反应中表现出优异的催化性能,但因其储量稀少、价格昂贵等缺点极大限制了该技术的工业化发展。因此,探寻一种地球储量丰富、成本低的材料来代替铂/碳催化剂是众多研究者的目标。其中,拥有层状结构的过渡金属二硫属化合物(TMDs)因其储量丰富、制备成本低、理论电催化活性高等优势被认为是代替商业铂/碳催化剂最有潜力的材料之一。TMDs材料根据过渡金属原子与硫族原子的结合与排布方式不同又分为半导体2H相、金属1T相和半金属1T′相。其中,半金属1T′相TMDs具有相态结构相对稳定、导电性高、催化活性位点丰富等优点被广泛应用于电催化领域。此外,构建单层空心结构可充分暴露TMDs催化活性位点,减少催化剂的用量,有利于节约成本。同时,得益于空心结构产生的表面应力可极大提高单层1T′-TMDs的相态稳定性,进而提高1T′-TMDs电催化剂的催化耐久性。
目前,单层1T′-TMDs的制备方式主要有机械剥离法和化学沉积法,这些方法普遍存在效率低、产物纯度低(70%~80%)、制备过程复杂等方面的不足。重要的是,单层1T′-TMDs纳米空心结构的可控制备方法鲜有报道。此外,晶相调控、空心结构设计及单层构建策略可助力TMDs实现其在电催化能源转换领域的大规模应用。因此,探索一种成本低且操作简单的制备方法可控合成单层1T′-TMDs纳米空心结构对其在电催化领域的推广具有重要研究意义和产业价值。
发明内容
鉴于现有技术的上述情况,本发明提出一种简易的单层1T′相TMDs空心结构电催化剂制备方法,该方法制得的单层1T′-TMDs空心结构具有半金属1T′相结构,并且合成的样品有相纯度高、尺寸均一、形貌均匀,易分散于极性溶剂中等优点。
本发明的上述目的是通过以下技术方案实现的:
将长碳链表面活性剂和十八烯的混合物(长碳链表面活性剂和十八烯的体积优选为2:3)加热到100~120℃抽真空(目的是去除氧气、水、低沸点溶剂等杂质),然后在惰性气体(通常为氮气或氩气)保护下升温至280~320℃后向混合物中注射加入模板和前驱体进行反应(反应时间一般为10~30分钟),反应结束后自然冷却至室温,超声洗涤(通常采用正己烷和乙醇的任意比例的混合物)后将反应产物离心并分散在乙醇中,去除模板得到单层1T′相TMDs空心结构电催化剂,其中所述前驱体为硫粉(或二苯联硒)和五氯化钼(或六氯化钨)按摩尔比2:1分散在油胺中的混合物。
所述长碳链表面活性剂为油胺、油酸、十二烷基胺、十六烷基胺或十八烷基胺中的一种或两种的任意比例的混合物。
所述模板为不同形貌的纳米金属或金属硫化物,所述不同形貌包括纳米颗粒、纳米片、纳米线或纳米棒等,或它们的任意组合,优选地,所述纳米金属或金属硫化物选自铋纳米材料、硫化铋纳米材料或硫化铜纳米材料等。
其中所述模板是通过加入盐酸、硫酸、硝酸或三辛基膦中的任意一种在室温~100℃下去除的。
本发明制得的单层1T′-TMDs空心结构具有相纯度高、尺寸均一、在极性溶剂分散良好的优点,并且具有较高的导电性和丰富的催化活性位点。
附图说明
图1为本发明实施例1制得的单层1T′相MoS2纳米空心结构的X射线光电子能谱图。
图2为本发明实施例1制得的单层1T′相MoS2纳米空心结构的透射电子显微镜照片。
图3为本发明制得的单层1T′相MoS2纳米空心结构的电催化稳定性能。
具体实施方式
为了更清楚地理解本发明的目的、技术方案及优点,以下结合附图及实施例,对本发明进行进一步详细说明。
实施例1:
将2mL油胺和3mL十八烯混合加热到120℃抽真空,然后在氮气保护下升温至300℃先注射0.01mmol五氯化钼、0.1mmol铋纳米颗粒和1mL油胺的混合溶液,然后注射0.02mmol硫粉和200μL油胺的混合溶液、反应10分钟。自然冷却至室温后,加入5mL正己烷和20mL乙醇,超声洗涤后加入3mL乙醇将反应产物离心并分散在其中,然后加入3mL盐酸在80℃下反应1小时,得到尺寸大小为20nm的黑色粉末,即为单层1T′相硫化钼(MoS2)纳米空心结构电催化剂,其中对盐酸的浓度没有特别要求,只要能够去除铋纳米颗粒即可,这同样适用下后续的各个实施例。
参见图1,制备的产物经X射线光电子能谱鉴定为半金属1T′相MoS2。
参见图2,用透射电镜观察到该产品为分散单层MoS2纳米空心结构,尺寸大小为20nm。
实施例2:
将3mL油胺和2mL十八烯混合加热到100℃抽真空,然后在氮气保护下升温至280℃先注射0.01mmol六氯化钨、0.1mmol铋纳米颗粒和1mL油胺的混合溶液,然后注射0.02mmol硫粉和500μL油胺的混合溶液、反应20分钟,自然冷却至室温后,加入4mL正己烷和20mL乙醇,超声洗涤后加入5mL乙醇将反应产物离心并分散在其中,然后加入6mL盐酸在60℃下反应1.5小时,得到尺寸大小为20nm的黑色粉末,即为单层1T′相硫化钨(WS2)纳米空心结构电催化剂。
实施例3:
将5mL油胺和4mL十八烯混合加热到110℃抽真空,然后在氩气保护下升温至320℃先注射0.02mmol五氯化钼、0.2mmol铋纳米颗粒和1mL油胺的混合溶液,然后注射0.04mmol二苯联硒和600μL油胺的混合溶液、反应30分钟,自然冷却至室温后,加入6mL正己烷和25mL乙醇,超声洗涤后加入4mL乙醇将反应产物离心并分散在其中,然后加入5mL盐酸在90℃下反应40分钟,得到尺寸大小为20nm的黑色粉末,即为单层1T′相硒化钼(MoSe2)纳米空心结构电催化剂。
实施例4:
将3mL油胺和3mL十八烯混合加热到120℃抽真空,然后在氮气保护下升温至300℃先注射0.01mmol六氯化钨、0.2mmol铋纳米颗粒和1mL油胺混合溶液,然后注射0.02mmol二苯联硒和200μL油胺的混合溶液、反应10分钟,自然冷却至室温后,加入5mL正己烷和20mL乙醇,超声洗涤后加入6mL乙醇将反应产物离心并分散在其中,然后加入8mL盐酸在80℃下反应1小时,得到尺寸大小为20nm的黑色粉末,即为单层1T′相硒化钨(WSe2)纳米空心结构电催化剂。
实施例5:
将2mL油胺和3mL十八烯混合加热到110℃抽真空,然后在氩气保护下升温至290℃先注射0.01mmol五氯化钼、0.1mmol硫化铜纳米线和1mL油胺的混合溶液,然后注射0.02mmol硫粉和200μL油胺的混合溶液、反应10分钟,自然冷却至室温后,依次加入5mL正己烷和20mL乙醇,超声洗涤后加入5mL乙醇将反应产物离心并分散在其中,然后加入3mL三辛基膦在80℃下反应1小时,得到粒径大小为20nm的黑色粉末,即为单层1T′相MoS2纳米管电催化剂。
尽管在上述实施例1-5中,作为硫粉(或二苯联硒)和五氯化钼(或六氯化钨)按2:1的摩尔比分散在油胺中的混合物的前驱体是如上所述先后注射加入的,不过本领域的技术人员公知,上述前驱体也可以同时注射加入,即,按2:1的摩尔比分散在油胺中的硫粉(或二苯联硒)和五氯化钼(或六氯化钨)以及纳米材料可以同时注射加入,与实施例1-5中所述的先后加入方式并不实质区别。另外,所述油胺的用量并无特别限定,可以比实施例中的用量更多或更少。
另外,发明人发现在油胺和十八烯的混合比为体积比2:3的情况下,最终的结果最佳。另外,对模板和前驱体的加入量没有特别限定,只要前驱体通过反应能在模板上得到单层的1T′-TMDs即可,具体用量可以根据需要调整。
本发明利用湿化学合成方法,通过将模板和相关前驱体注射到高温表面活性剂中,实现对1T′相TMDs晶体成核和生长过程的控制,继而在去模板后获得1T′相态纯度高、尺寸均一、形貌可控的单层1T′相TMDs纳米空心结构。除此之外,所得的单层纳米空心结构还可以稳定分散在水、乙醇等极性溶剂中,为其在生物和电催化方面的应用提供了可能性。
图3采用电化学工作站通过连续电解产氢12小时,测试了单层1T′-MoS2纳米空心结构的电催化稳定性。在经过连续12小时的产氢反应后,单层1T′相MoS2纳米空心结构在10mA/cm2处的电流密度并没有明显的下降趋势,说明本发明制备的电催化剂具有优异的催化耐久性。
本发明通过混合长碳链表面活性剂和十八烯,高温下注射模板和相关前驱体,在模板上得到单层的1T′-TMDs,去除模板后得到单层1T′-TMDs纳米空心结构。此外,本发明制得的单层1T′-TMDs纳米空心结构具有相纯度高、尺寸均一、在极性溶剂分散良好的优点。
本发明的反应条件温和,操作简单,成本低,适于大规模工业化生产。本发明还可拓展到其他半金属相纳米结构的制备。另外,本发明中去除模板后会产生相关的金属盐,可以重复利用,符合可持续发展战略。
本发明制备的单层1T′-TMDs纳米空心结构具有较高导电性,且单层的空心结构可充分暴露TMDs材料的催化活性位点。作为电催化剂在电催化方面表现出优异的析氢性能,例如:低的起始过电位,小的Tafel斜率以及长效稳定性。
Claims (4)
1.一种单层1T′相TMDs空心结构电催化剂制备方法,其特征在于包括以下步骤:
将体积比为2:3的长碳链表面活性剂和十八烯的混合物加热到100~120℃抽真空,然后在惰性气体保护下升温至280~320℃后向混合物中注射加入模板和前驱体进行反应,反应时间为10~30分钟,反应结束后自然冷却至室温,超声洗涤后将反应产物离心并分散在乙醇中,去除模板得到单层1T′相TMDs空心结构电催化剂,其中所述前驱体为硫粉或二苯联硒和五氯化钼或六氯化钨按摩尔比2:1分散在油胺中的混合物,其中所述模板为不同形貌的纳米金属或金属硫化物,其中所述不同形貌包括纳米颗粒、纳米片、纳米线或纳米棒,或它们的任意组合,其中所述纳米金属或金属硫化物选自铋纳米材料、硫化铋纳米材料或硫化铜纳米材料,其中
所述长碳链表面活性剂为油胺、油酸、十二烷基胺、十六烷基胺或十八烷基胺中的一种或两种的任意比例的混合物。
2.按照权利要求1所述的制备方法,其中所述模板是通过加入盐酸、硫酸、硝酸或三辛基膦中的任意一种在室温~100℃下去除的。
3.按照权利要求1所述的制备方法,其中所述超声洗涤采用的溶剂是己烷和乙醇的任意比例的混合物。
4.按照权利要求1所述的制备方法,其中所述惰性气体为氮气或氩气。
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