CN106910908A - 氧还原催化剂及其制备方法、氧还原电极和电池 - Google Patents
氧还原催化剂及其制备方法、氧还原电极和电池 Download PDFInfo
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Abstract
本申请公开了一种氧还原催化剂及其制备方法、氧还原电极和电池，本发明阴离子功能化的聚离子液体作为前驱体从而制备具有卷曲结构的氮氟磷三掺的炭纳米片材料作为氧还原催化剂。使用本发明的方法，能得到一种卷曲碳纳米片催化剂，使其比表面得以显著提高，并能使其活性位点数明显增多，使碳的sp2电子得到活化，从而使其催化性能得以明显提高。
Description
技术领域
本申请涉及一种氧还原催化剂及其制备方法、氧还原电极和电池。
背景技术
环境污染，能源短缺等问题在当今社会受到越来越受到人们的关注，因此为了解决这一问题我们就必须找出一种新型绿色的能源。而具有较高能量密度和较低污染物排放等优点的金属-空气电池以及燃料电池被认为是一种极具潜力的替代电源。对于这两种电池而言，其中氧还原反应是一种重要的电极反应(Chang,C.；Wen,T.An investigation ofthermally prepared electrodes for oxygen reduction in alkalinesolution.Mater.Chem.Phys.1997,47,203.)，在电池反应中有着十分重要的影响。但由于这个反应活化能较大，从而导致反应难度偏大，因此为了促进电极反应使其得以发生，在多数情况下就需要使用大量贵金属催化剂，尤其是Pt催化剂，以保证电池的正常工作。但是贵金属催化剂不仅价格高且地壳中储量稀少，从而导致电源成本很高，使得广泛应用这类电源的进程受到了极大的限制。此前已有很多研究人员进行了许多工作来减少贵金属用量已解决这个问题。但长远看来，寻找非贵金属催化剂以代替贵金属催化剂才能最终解决这一问题。(Chen,Z.W.；Higgins,D.；Yu,A.P.；Zhang,L.；Zhang,J.J.A review on non-precious metal electrocatalysts for PEM fuel cells.Energy Environ.Sci.2011,4,3167)。
对非贵金属催化剂的研究始于上世纪60年代(Jasinski.A new fuel cellcathode catalyst.Nature 1964,201,1212)，到目前为止已得到了多种可行的非贵金属催化剂，基于金属氧化物的掺氮碳材料来作为非贵金属催化剂则是其中最有希望的一种，但这类催化剂在性能上仍需进一步提高。此外还有一类无金属掺氮碳材料催化剂也受到诸多关注，多种因素影响其性能，催化剂前驱体、催化剂的微观结构等是其中较为重要的影响因素。
近些年，掺氮碳纳米管，掺氮石墨烯等一些具有微观结构的掺氮碳材料作为氧还原的非金属催化剂受到越来越多的关注(Gong,K.,Du,F.,Xia,Z.,Durstock,M.&Dai,L.Nitrogen-doped carbon nanotube arrays with high electrocatalytic activityfor oxygen reduction.Science 323,760–764(2009).Liu,R.,Wu,D.,Feng,X.&Müllen,K.Nitrogen-doped ordered mesoporous graphitic arrays with highelectrocatalytic activity for oxygen reduction.Angew.Chem.Int.Ed.49,2565–2569(2010).Wang,S.et al.BCN graphene as efficient metal-free electrocatalyst forthe oxygen reduction reaction.Angew.Chem.Int.Ed.51,209–4212(2012).但是这些碳材料也有不易制备，价格不便宜等一些缺点。因此，廉价易得性能可观的碳材料的开发以用作氧还原的催化剂就显得十分重要。
当前离子液体作为新型催化剂前驱体而受到了广泛关注，离子液体中重要的一类就是聚离子液体，其兼具离子液体和聚合物的共同优势，最近也有将其用作催化剂前躯体的研究(Gao,Jian Ma,Na，Zhai,Junfeng，Li,Tianyan，Qin,Wei，Zhang,Tingting Yin,Zhen，Polymerizable Ionic Liquid as Nitrogen-Doping Precursor for Co-N-CCatalyst with Enhanced Oxygen Reduction Activity，Ind.Eng.Chem.Res,2015,54,7984)。但现有研究中离子液体多数用于含金属的催化剂。
发明内容
本发明的目的在于提供一种成本较低且环境友好并能作为非金属催化剂前驱体的碳材料。
为实现上述目的，本发明提供如下技术方案：
本申请实施例公开一种氧还原催化剂，其为具有卷曲结构的氮氟磷三掺的炭纳米片。
优选的，在上述的氧还原催化剂中，起始电位为0.9VRHE。
本申请实施例还公开了一种氧还原电极，其具有：
气体扩散层、和
配置在所述气体扩散层上的催化剂层，所述催化剂层是所述的氧还原催化剂。
优选的，在上述的氧还原电极中，所述气体扩散层为碳基板。
本申请还公开了一种电池，包括：
所述的氧还原电极，以及
分别位于所述氧还原电极的外侧的隔板。
优选的，在所述的电池中，该电池为燃料电池或金属-空气电池。
本实施例还公开了一种氮氟磷三掺的炭纳米片的制备方法，在惰性气体保护下，于850～1000℃高温煅烧功能化可聚合咪唑类六氟磷酸盐离子液体单体，获得目标产物。
优选的，在上述的氮氟磷三掺的炭纳米片的制备方法中，功能化可聚合咪唑类六氟磷酸盐离子液体单体的制备方法包括：将咪唑类阳离子、硝酸和六氟磷酸钠按照摩尔比(1～1.5):(1～1.5):(1～1.5)混合反应，咪唑类阳离子选自甲基咪唑、乙烯基咪唑、丙烯基咪唑中的一种或多种。
与现有技术相比，本发明的优点在于：利用本发明方法制得的样品具有卷曲的微观形貌，不但能使比表面得到提高，而且可以有效地增加其活性位点数目，使碳的sp2电子得到活化，从而具有良好的催化活性。且通过实验还发现所得的催化剂也具有产氧的催化性能，可用作一种催化氧还原和产氧两种反应的双功能催化剂。
附图说明
为了更清楚地说明本申请实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请中记载的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1所示为本发明具体实施例1中线性扫描测试结果示意图；
图2所示为本发明具体实施例2中线性扫描测试结果示意图；
图3所示为本发明具体实施例3中线性扫描测试结果示意图；
图4所示为本发明具体实施例4中线性扫描测试结果示意图。
具体实施方式
本发明以阴离子功能化的聚离子液体作为前驱体从而制备具有卷曲结构的氮氟磷三掺的炭纳米片材料作为氧还原催化剂，类似前驱体传统上多是普通的离子液体，且一般不能发生聚合，在阴离子方面也没有进行功能化。这类传统催化剂虽有一定催化性能，但其性能仍需提高。使用本发明的方法，能得到一种卷曲碳纳米片催化剂，使其比表面得以显著提高，并能使其活性位点数明显增多，使碳的sp2电子得到活化，从而使其催化性能得以明显提高。
本发明通过下列实施例作进一步说明：根据下述实施例，可以更好地理解本发明。然而，本领域的技术人员容易理解，实施例所描述的具体的物料比、工艺条件及其结果仅用于说明本发明，而不应当也不会限制权利要求书中所详细描述的本发明。
实施例1：
(1)在单口烧瓶中加入0.1mol甲基咪唑，随后滴加0.1mol硝酸，再加入0.1mol六氟磷酸钠，常温搅拌1小时后，升温至50℃并搅拌2～4小时，得到粘稠液体。
(2)将得到的液体取出，放入瓷舟中，在管式炉中煅烧，用N2作为保护气，先升温至100℃，再以5℃/分钟的速度升温至850℃，在850℃保温1小时后自然降温，得黑色蓬松固体。
(4)将上述固体研磨后，取得到的固体2.5mg与50μLNafion溶液和450μL乙醇溶液混合，再超声震荡30分钟将其分散均匀，制得催化剂浆液。取10μL浆液滴加到玻碳电极上，干燥1小时后进行电化学测试，主要有循环伏安、线性扫描等。电化学测试结果如图1所示。
实施例2：
(1)在单口烧瓶中加入0.1mol乙烯基咪唑，随后滴加0.1mol硝酸，再加入0.1mol六氟磷酸钠，常温搅拌2小时后，升温至50℃并搅拌2～4小时，得到粘稠液体。
(2)将得到的液体取出，放入瓷舟中，在管式炉中煅烧，用N2作为保护气，先升温至100℃，再以5℃/分钟的速度升温至950℃，在950℃保温1小时后自然降温，得黑色蓬松固体。
(4)将上述固体研磨后，取得到的固体2.5mg与50μLNafion溶液和450μL乙醇溶液混合，再超声震荡30分钟将其分散均匀，制得催化剂浆液。
取10μL浆液滴加到玻碳电极上，干燥1小时后进行电化学测试，主要有循环伏安、线性扫描等。
参图2，可见其起始电位可以达到0.9VRHE，已经很接近常用的炭载铂(Pt/C)催化剂的起始电位(～1V)。
实施例3：
(1)在单口烧瓶中加入0.15mol丙烯基咪唑，随后滴加0.15mol硝酸，再加入0.1mol六氟磷酸钠，常温搅拌1小时后，升温至50℃并搅拌2～4小时，得到粘稠液体。
(2)将得到的液体取出，放入瓷舟中，在管式炉中煅烧，用N2作为保护气，先升温至100℃，再以5℃/分钟的速度升温至900℃，在900℃保温2小时后自然降温，得黑色蓬松固体。
(4)将上述固体研磨后，取得到的固体2.5mg与50μLNafion溶液和450μL乙醇溶液混合，再超声震荡30分钟将其分散均匀，制得催化剂浆液。取10μL浆液滴加到玻碳电极上，干燥1小时后进行电化学测试，主要有循环伏安、和如图所示的线性扫描如图3。
实施例4：
(1)在单口烧瓶中加入0.1mol丙烯基咪唑，随后滴加0.1mol硝酸，再加入0.15mol六氟磷酸钠，常温搅拌2小时后，升温至50℃并搅拌2～4小时，得到粘稠液体。
(2)将得到的液体取出，放入瓷舟中，在管式炉中煅烧，用N2作为保护气，先升温至100℃，再以5℃/分钟的速度升温至1000℃，在1000℃保温2小时后自然降温，得黑色蓬松固体。
(4)将上述固体研磨后，取得到的固体2.5mg与50μLNafion溶液和450μL乙醇溶液混合，再超声震荡30分钟将其分散均匀，制得催化剂浆液。取10μL浆液滴加到玻碳电极上，干燥1小时后进行电化学测试，主要有循环伏安、线性扫描等。线性扫描结果如图4所示。
在此，还需要说明的是，为了避免因不必要的细节而模糊了本发明，在附图中仅仅示出了与根据本发明的方案密切相关的结构和/或处理步骤，而省略了与本发明关系不大的其他细节。
综上所述，本发明以乙烯基咪唑为阳离子，以六氟磷酸根阴离子的功能化的聚离子液体，这种聚离子液体在煅烧过程中由于剧烈放出气体，从而可以获得氮氟磷三掺的卷曲纳米碳片，从电化学测试中看出得到的产物在氧还原催化方面具有较好的性能
最后，还需要说明的是，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。
Claims (7)
1.一种氧还原催化剂，其为具有卷曲结构的氮氟磷三掺的炭纳米片。
2.根据权利要求1所述的氧还原催化剂，其特征在于：起始电位为0.9VRHE。
3.一种氧还原电极，其具有：
气体扩散层、和
配置在所述气体扩散层上的催化剂层，所述催化剂层是权利要求1或2所述的氧还原催化剂。
4.根据权利要求3所述的氧还原电极，其特征在于：所述气体扩散层为碳基板。
5.一种电池，其特征在于：该电池为燃料电池或金属-空气电池，包括权利要求3或4所述的氧还原电极。
6.一种氮氟磷三掺的炭纳米片的制备方法，其特征在于：在惰性气体保护下，于850～1000℃高温煅烧功能化可聚合咪唑类六氟磷酸盐离子液体单体，获得目标产物。
7.根据权利要求6所述的氮氟磷三掺的炭纳米片的制备方法，其特征在于：功能化可聚合咪唑类六氟磷酸盐离子液体单体的制备方法包括：将咪唑类阳离子、硝酸和六氟磷酸钠按照摩尔比(1～1.5):(1～1.5):(1～1.5)混合反应，咪唑类阳离子选自甲基咪唑、乙烯基咪唑、丙烯基咪唑中的一种或多种。
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| CN106374117A (zh) * | 2016-11-25 | 2017-02-01 | 天津工业大学 | 一种n,p共掺非金属氧还原催化剂的制备 |
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| CN106374117A (zh) * | 2016-11-25 | 2017-02-01 | 天津工业大学 | 一种n,p共掺非金属氧还原催化剂的制备 |
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